CN112447946B - Li (lithium ion battery) 2 TiO 3 、Li 2 ZrO 3 Preparation method of composite coated ternary positive electrode material - Google Patents
Li (lithium ion battery) 2 TiO 3 、Li 2 ZrO 3 Preparation method of composite coated ternary positive electrode material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000003756 stirring Methods 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 19
- 150000003754 zirconium Chemical class 0.000 claims abstract description 19
- 239000002585 base Substances 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 235000019441 ethanol Nutrition 0.000 claims abstract description 5
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000010406 cathode material Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000002431 foraging effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000002572 peristaltic effect Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 238000004448 titration Methods 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 10
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 4
- 229910052751 metal Inorganic materials 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 2
- 238000001556 precipitation Methods 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 239000010416 ion conductor Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 3
- 241000080590 Niso Species 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a lithium ion battery anode material, in particular to Li 2 TiO 3 、Li 2 ZrO 3 Composite coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 A preparation method of ternary positive electrode material. The method comprises the following steps: (1) Preparing ternary nickel, manganese and cobalt metal salt aqueous solution, mixed alkali aqueous solution and reaction base solution; (2) Respectively adding a metal salt aqueous solution and a mixed alkaline aqueous solution into the base solution at a certain flow rate to carry out precipitation reaction; (3) After the precipitation reaction is finished, filtering, washing and drying are carried out to obtain a precursor; (4) dispersing the precursor in ethanol to form a suspension; respectively dissolving a titanium compound and zirconium salt in absolute ethyl alcohol, slowly adding the absolute ethyl alcohol into the suspension, stirring for 5-6 hours, evaporating the solvent to dryness to obtain solid particles, and presintering the solid particles at a low temperature for 4-7 hours to obtain a presintered product; (5) Then mixing and grinding the presintered product with lithium salt, and performing high-temperature solid-phase reaction in oxygen or air atmosphere to obtain the Li 2 TiO 3 、Li 2 ZrO 3 Composite coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 Ternary positive electrode material.
Description
Technical Field
The preparation method belongs to the technical field of new energy materials, relates to a preparation method of a lithium ion battery anode material, and in particular relates to Li 2 TiO 3 、Li 2 ZrO 3 Composite coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 The preparation method of the ternary positive electrode material comprises the following steps.
Background
At present, the comprehensive performance of lithium ion batteries is gradually improved, and the lithium ion batteries are becoming a main power source of portable electronic products, electric tools, hybrid power and pure electric vehicles. Compared with the traditional lead-acid battery, nickel-cadmium battery and nickel-hydrogen battery, the lithium ion battery has obvious advantage of high energy density as an energy storage material. However, for high capacityDevelopment and research of electrode materials is continued. LiCoO of lithium ion battery 2 The positive electrode material is widely applied to the field of 3C equipment, but the energy density required in an electric automobile is 2-5 times that of the existing lithium ion battery. LiCoO 2 The lithium ion battery has the defects of toxicity, low specific capacity (150 mAh/g), high cost and the like, and can not meet the requirements of high-energy-density power lithium ion batteries gradually. With the expansion of the application market of electric automobiles, high-energy density batteries have become a hot spot for application research. High nickel layered cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 The lithium ion power battery has the characteristics of high capacity (about 180 mAh/g), low price and high energy density, and is considered as one of the most competitive materials of the next generation of lithium ion power batteries.
LiNi 0.8 Co 0.1 Mn 0.1 O 2 The Co content in the anode material is low, the cost performance is good, the specific capacity is high, and the requirement of high energy density of the current power battery can be met. Although the specific capacity of the high nickel cathode material increases significantly with the increase of the nickel content, there are also problems such as poor storage property, rapid capacity fade, poor high temperature performance, and the like. These negative factors are mainly derived from the inherent structural collapse or phase transformation of the material, lithium nickel misce-discharge, electrode surface side reactions and external process conditions. Although surface coating has achieved significant success in improving the cathode material, most coating materials are insulators such as MgO, al 2 O 3 ZnO, etc., which will negatively impact the actual specific capacity or rate capability.
The lithium ion fast ion conductor has a certain progress in the aspect of coating the anode material, such as LiAlO 2 、Li 2 ZrO 3 、Li 2 TiO 3 And the like, but basically, the coating is a single fast ion conductor, and the research on the composite fast ion conductor coating and the high-voltage performance is not yet reported. The invention provides Li 2 TiO 3 、Li 2 ZrO 3 The preparation method of the composite coated ternary positive electrode material has good lithium storage performance under high voltage. Surface coating treatment is carried out on the positive electrode material by utilizing a composite fast ion conductor, wherein the composite fast ion conductor is arranged on the positive electrode materialThe material has stable and synergistic effect in the aspects of structure, surface morphology and electrochemical performance, and further improves the electrochemical performance of the main material.
Disclosure of Invention
In order to prepare the high-nickel ternary positive electrode material with high specific capacity and excellent cycle performance under high voltage, the invention provides a Li 2 TiO 3 、Li 2 ZrO 3 Composite coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 A preparation method of ternary positive electrode material.
The technical scheme of the invention is as follows: li (lithium ion battery) 2 TiO 3 、Li 2 ZrO 3 The preparation method of the composite coated ternary cathode material comprises the following steps:
(1) Taking nickel salt, cobalt salt and manganese salt as raw materials, weighing according to a molar ratio of 8:1:1, dissolving in deionized water, and uniformly stirring to prepare a mixed salt solution with a concentration of 1-3 mol/L;
(2) Weighing 2-6 mol of soluble alkali and 0.5-1.5 mol of complexing agent, dissolving in deionized water at the same time, and uniformly stirring to prepare 2-6 mol/L of mixed alkali solution;
(3) Adding deionized water accounting for 20-26% of the total volume of a reaction container into a continuous stirring reaction kettle as reaction base solution, adding a complexing agent into the base solution to adjust the pH value of the base solution to 11.0-11.3, filling nitrogen, and keeping the temperature in the reaction kettle at 55-65 ℃;
(4) The prepared mixed salt solution and mixed alkali solution are vermicular fed into a reaction kettle through a peristaltic pump at a titration rate of 1.0-3.0 ml/min, the stirring rate is controlled to be 200-600 r/min, the reaction time is controlled to be 8-14 h, and the reaction precipitate is obtained by continuously maintaining the set fixed temperature and stirring rate for aging for 10-12 h after the reaction is finished;
(5) Washing and filtering the reaction precipitate for many times until the reaction precipitate is neutral, and putting the reaction precipitate into a constant-temperature blast drying oven at 100-120 ℃ for drying for 20-24 hours to obtain a ternary cathode material precursor;
(6) Dissolving and dispersing the dried precursor in absolute ethyl alcohol, wherein the mass ratio of the precursor to the ethyl alcohol is 1:9-29, and stirring for 1-3 hours in a water bath kettle at normal temperature to form a suspension; as same asWhen the titanium compound and the zirconium salt are dissolved in absolute ethyl alcohol to prepare titanium-zirconium mixed solution, wherein the adding amount of the titanium compound and the zirconium salt is the same (namely, the adding amount of the titanium compound and the zirconium salt is respectively converted into TiO 2 And ZrO(s) 2 The mass ratio of the titanium compound to the zirconium salt is 1:1), and the mass ratio of the total mass of the titanium compound and the zirconium salt to the absolute ethyl alcohol is 1:4-19; adding the mixed solution of titanium and zirconium into the suspension to convert into TiO 2 And ZrO(s) 2 The mass ratio of the total mass of the precursor to the dried precursor is controlled to be 1:11.5-99; and (3) regulating the temperature of the suspension to 50-70 ℃, continuously stirring at the temperature for 5-6 hours, evaporating the solvent to dryness to obtain solid particles, drying the solid particles, and presintering the solid particles in oxygen or air atmosphere at 400-600 ℃ for 4-7 hours to obtain a presintered product.
(7) Ball-milling and uniformly mixing the presintered product and lithium salt according to the molar ratio of 1:1.05-1.1, then placing into an oxygen or air atmosphere furnace, heating to 750-850 ℃ for high-temperature solid-phase reaction for 14-20 h, and finally cooling to room temperature to obtain the Li 2 TiO 3 、Li 2 ZrO 3 And (3) compounding the coated ternary positive electrode material.
In the step (1), the nickel salt is one of nickel sulfate and nickel nitrate, the manganese salt is one of manganese sulfate and manganese nitrate, and the cobalt salt is one of cobalt sulfate and cobalt nitrate.
The soluble alkali in the step (2) is one of sodium hydroxide and sodium carbonate.
The complexing agent in the step (2) is one of ammonia water and ammonium bicarbonate.
The titanium compound in the step (6) is tetrabutyl titanate; the zirconium salt is one of zirconium nitrate and zirconium acetate.
The lithium salt in the step (7) is one of lithium hydroxide, lithium carbonate and lithium acetate.
Drawings
FIG. 1 is Li in embodiment 1 of the present invention 2 TiO 3 、Li 2 ZrO 3 Scanning electron microscope pictures of the composite coated ternary anode material.
FIG. 2 is Li in embodiment 1 of the present invention 2 TiO 3 、Li 2 ZrO 3 XRD pattern of the composite coated ternary cathode material.
FIG. 3 is Li in embodiment 1 of the present invention 2 TiO 3 、Li 2 ZrO 3 The composite coated ternary positive electrode material circulates for 100 times at the 1C multiplying power under the high voltage of 2.75-4.4V at the temperature of 25 ℃, the horizontal axis represents the discharge times, and the vertical axis represents the specific capacity.
Detailed Description
The examples of the present invention are as follows, but are not limited thereto.
Example 1
(1) By NiSO 4 ·6H 2 O、MnSO 4 ·H 2 O、CoSO 4 ·7H 2 O is used as a raw material, is weighed according to a molar ratio of 8:1:1 and is dissolved in ionized water, and 1L of mixed salt solution with the concentration of 2mol/L is prepared after uniform stirring;
(2) Weighing 4mol of sodium hydroxide, dissolving in deionized water, adding 1mol of concentrated ammonia water into the sodium hydroxide, stirring uniformly, and preparing into 1L of 4mol/L mixed alkali solution;
(3) Adding 1200ml of deionized water as a reaction base solution into a continuous stirring reaction kettle, adding ammonia water into the base solution to adjust the pH value of the base solution to be 11.2, filling nitrogen, and keeping the reaction temperature at 60 ℃;
(4) The prepared mixed salt solution and mixed alkali solution are vermicular fed into a reaction kettle through a peristaltic pump at a titration rate of 1.6ml/min, the stirring rate is controlled at 400r/min, the reaction time is controlled at 12h, and the preset fixed temperature and stirring rate are kept for aging for 12h after the reaction is finished;
(5) Washing and filtering the reaction product for many times until the reaction product is neutral, and putting the reaction product into a constant-temperature blast drying oven at 120 ℃ for drying for 24 hours to obtain a ternary positive electrode material precursor;
(6) 18.5g (0.2 mol) of the dried precursor was weighed and dissolved in 300g of absolute ethyl alcohol, and stirred in a water bath at normal temperature for 2 hours, and 2.3g of C was simultaneously added 16 H 36 O 4 Ti and 1.86g Zr (NO) 3 ) 4 ·5H 2 O (converted TiO) 2 And ZrO(s) 2 The mass ratio of the total mass of the titanium compound and the zirconium salt to the dry precursor is controlled to be 1:12.5) is dissolved in 37.4g of absolute ethyl alcohol (the mass ratio of the total mass of the titanium compound and the zirconium salt to the absolute ethyl alcohol is 1:9), and then the mixture is slowly added into the suspensionAnd (3) regulating the temperature of the water bath kettle to 65 ℃, continuously stirring for 5 hours at the temperature, drying the obtained mixed solution, and then, placing the dried mixed solution into a tubular furnace for presintering for 5 hours at the low temperature of 550 ℃ in an oxygen atmosphere to obtain a presintered product.
(7) Fully ball-milling and mixing the presintered product and 0.216mol of LiOH (the molar ratio of the presintered product to the lithium salt is 1:1.08), then placing the mixture into an oxygen atmosphere furnace, heating to 800 ℃ for high-temperature solid-phase reaction for 16 hours, and finally cooling to room temperature to obtain the Li 2 TiO 3 、Li 2 ZrO 3 And (3) compounding and coating a ternary positive electrode material. At 25 ℃, the initial discharge capacity of the ternary cathode material 1C is up to 180mAh/g within the voltage range of 2.75V-4.4V, and the specific capacity is kept to be more than 161mAh/g after 100 times.
Example 2
(1) With Ni (NO) 3 ) 2 ·6H 2 O、Mn(NO 3 ) 2 (50% solution), co (NO) 3 ) 2 ·6H 2 O is used as a raw material, weighed according to a molar ratio of 8:1:1 and dissolved in ionized water, and 0.5L of 3mol/L mixed salt solution is prepared after uniform stirring;
(2) 3mol of sodium carbonate is weighed and dissolved in deionized water, 0.5mol of ammonium bicarbonate is added into the sodium carbonate and stirred uniformly to prepare 0.75L of 2mol/L mixed alkali solution;
(3) Adding 1000ml of deionized water as a reaction base solution into a continuous stirring reaction kettle, adding ammonium bicarbonate into the base solution to adjust the pH of the base solution to be 11.3, filling nitrogen, and keeping the reaction temperature to be 65 ℃;
(4) The prepared mixed salt solution and mixed alkali solution are respectively vermicular fed into a reaction kettle through peristaltic pumps at titration rates of 3ml/min and 1ml/min, the stirring rate is controlled at 600r/min, the reaction time is controlled at 8h, and certain reaction temperature and stirring rate are kept for aging for 10h after the reaction is finished;
(5) Washing and filtering the reaction product for many times until the reaction product is neutral, and putting the reaction product into a 100 ℃ constant-temperature blast drying oven to be dried for 24 hours to obtain a ternary positive electrode material precursor;
(6) 18.5g (0.2 mol) of the dried precursor was weighed and dissolved in 351.5g of absolute ethanol (mass ratio of precursor to ethanol 1:19)Stirring in a water bath at normal temperature for 3h while adding 3.04g of C 16 H 36 O 4 Ti and 2.48g Zr (NO) 3 ) 4 ·5H 2 O (converted TiO) 2 And ZrO(s) 2 The mass ratio of the total mass of the titanium compound and the zirconium salt to the dry precursor is controlled to be 1:11.5) is dissolved in 22.1g of absolute ethyl alcohol (the mass ratio of the total mass of the titanium compound and the zirconium salt to the absolute ethyl alcohol is 1:4), then the solution is slowly added into the suspension, the temperature of the water bath kettle is adjusted to 50 ℃, stirring is continued for 6 hours at the temperature, and the obtained mixed solution is dried and then is presintered for 4 hours in an oxygen atmosphere at 700 ℃ to obtain a presintered product.
(7) The presintered product was reacted with 0.11mol of Li 2 CO 3 (the molar ratio of the presintered product to the lithium salt is 1:1.1) fully ball-milling and mixing, then placing into an oxygen atmosphere furnace, heating to 750 ℃ for high-temperature solid-phase reaction for 20 hours, and finally cooling to room temperature to obtain the Li of the invention 2 TiO 3 、Li 2 ZrO 3 And (3) compounding and coating a ternary positive electrode material.
Example 3
(1) By NiSO 4 ·6H 2 O、MnSO 4 ·H 2 O、CoSO 4 ·7H 2 O is used as a raw material, is weighed according to a molar ratio of 8:1:1 and is dissolved in ionized water, and 1.5L of mixed salt solution with the concentration of 1mol/L is prepared after uniform stirring;
(2) Weighing 3mol of sodium hydroxide, dissolving in deionized water, adding 1.5mol of ammonia water into the sodium hydroxide, and uniformly stirring to prepare 0.5L of 6mol/L mixed alkali solution;
(3) 1300ml of deionized water is added into a continuous stirring reaction kettle to serve as reaction base solution, ammonia water is added into the base solution to adjust the pH value of the base solution to be 11.0, nitrogen is filled, and the reaction temperature is kept at 55 ℃;
(4) The prepared mixed salt solution and mixed alkali solution are vermicular fed into a reaction kettle through a peristaltic pump at titration rates of 1ml/min and 3ml/min, the stirring rate is controlled at 200r/min, the reaction time is controlled at 14h, and the set reaction temperature and stirring rate are kept for aging for 10h after the reaction is finished;
(5) Washing and filtering the reaction product for many times until the reaction product is neutral, and putting the reaction product into a 110 ℃ constant temperature blast drying oven to dry for 20 hours to obtain a ternary positive electrode material precursor;
(6) 18.5g (0.2 mol) of the dried precursor is weighed and dissolved in 181.5g of absolute ethyl alcohol (the mass ratio of the precursor to the ethyl alcohol is 1:9), and the mixture is stirred for 3 hours at normal temperature in a water bath, and simultaneously 0.38g of C is added 16 H 36 O 4 Ti and 0.24g Zr (CH) 3 COO) 4 (after conversion of TiO) 2 And ZrO(s) 2 The mass ratio of the total mass of the titanium compound and the zirconium salt to the mass ratio of the absolute ethyl alcohol of the dry precursor is controlled to be 1:99) to be dissolved in 13.1g of absolute ethyl alcohol (the mass ratio of the total mass of the titanium compound and the zirconium salt to the absolute ethyl alcohol is 1:19), then the solution is slowly added into the suspension, the temperature of the water bath kettle is adjusted to 50 ℃, stirring is continued for 6 hours at the temperature, and the obtained mixed solution is dried and then presintered for 4 hours at the low temperature of 700 ℃ in an oxygen atmosphere, so as to obtain a presintered product.
(7) The presintered product is reacted with 0.21mol of CH 3 Fully ball-milling and mixing COOLi (pre-sintered product and lithium salt according to the mol ratio of 1:1.05), then placing into air, heating to 850 ℃ and carrying out high-temperature solid-phase reaction for 14h, and finally cooling to room temperature to obtain the Li disclosed by the invention 2 TiO 3 、Li 2 ZrO 3 And (3) compounding and coating a ternary positive electrode material.
Claims (6)
1. Li (lithium ion battery) 2 TiO 3 、Li 2 ZrO 3 The preparation method of the composite coated ternary cathode material is characterized by comprising the following steps of:
(1) Taking nickel salt, cobalt salt and manganese salt as raw materials, weighing according to a molar ratio of 8:1:1, dissolving in deionized water, and uniformly stirring to prepare a mixed salt solution with a concentration of 1-3 mol/L;
(2) Weighing 2-6 mol of soluble alkali and 0.5-1.5 mol of complexing agent, dissolving in deionized water at the same time, and uniformly stirring to prepare 2-6 mol/L of mixed alkali solution;
(3) Adding deionized water accounting for 20-26% of the total volume of a reaction container into a continuous stirring reaction kettle as reaction base solution, adding a complexing agent into the base solution to adjust the pH value of the base solution to 11.0-11.3, filling nitrogen, and keeping the temperature in the reaction kettle at 55-65 ℃;
(4) The prepared mixed salt solution and mixed alkali solution are vermicular fed into a reaction kettle through a peristaltic pump at a titration rate of 1.0-3.0 ml/min, the stirring rate is controlled to be 200-600 r/min, the reaction time is controlled to be 8-14 h, and the reaction precipitate is obtained by continuously maintaining the set fixed temperature and stirring rate for aging for 10-12 h after the reaction is finished;
(5) Washing and filtering the reaction precipitate for many times until the reaction precipitate is neutral, and putting the reaction precipitate into a constant-temperature blast drying oven at 100-120 ℃ for drying for 20-24 hours to obtain a ternary cathode material precursor;
(6) Dissolving and dispersing the dried precursor in absolute ethyl alcohol, wherein the mass ratio of the precursor to the ethyl alcohol is 1:9-19, and stirring for 1-3 hours in a water bath kettle at normal temperature to form a suspension; simultaneously dissolving a titanium compound and a zirconium salt in absolute ethyl alcohol to prepare a titanium-zirconium mixed solution, wherein the adding amount of the titanium compound and the zirconium salt is the same, and the adding amount of the titanium compound and the zirconium salt is converted into TiO respectively 2 And ZrO(s) 2 The mass ratio of the titanium compound to the zirconium salt is 1:1, and the mass ratio of the total mass of the titanium compound and the zirconium salt to the absolute ethyl alcohol is 1:4-19; adding the mixed solution of titanium and zirconium into the suspension to convert into TiO 2 And ZrO(s) 2 The mass ratio of the total mass of the precursor to the precursor is controlled to be 1:11.5-99; regulating the temperature of the suspension to 50-70 ℃, continuously stirring for 5-6 hours at the temperature, evaporating the solvent to dryness to obtain solid particles, drying the solid particles, and then placing the solid particles into oxygen or air to presintere for 4-7 hours at 400-600 ℃ to obtain a presintered product;
(7) Ball-milling and uniformly mixing the presintered product and lithium salt according to the molar ratio of 1:1.05-1.1, then placing into an oxygen or air atmosphere furnace, heating to 750-850 ℃ for high-temperature solid-phase reaction for 14-20 h, and finally cooling to room temperature to obtain the Li 2 TiO 3 、Li 2 ZrO 3 And (3) compounding the coated ternary positive electrode material.
2. A Li as claimed in claim 1 2 TiO 3 、Li 2 ZrO 3 The preparation method of the composite coated ternary cathode material is characterized by comprising the following steps of: in the step (1), the nickel salt is one of nickel sulfate and nickel nitrate, the manganese salt is one of manganese sulfate and manganese nitrate, and the cobalt salt is one of cobalt sulfate and cobalt nitrate.
3. A Li as claimed in claim 1 2 TiO 3 、Li 2 ZrO 3 The preparation method of the composite coated ternary cathode material is characterized by comprising the following steps of: the soluble alkali in the step (2) is one of sodium hydroxide and sodium carbonate.
4. A Li as claimed in claim 1 2 TiO 3 、Li 2 ZrO 3 The preparation method of the composite coated ternary cathode material is characterized by comprising the following steps of: the complexing agent in the step (2) is one of ammonia water and ammonium bicarbonate.
5. A Li as claimed in claim 1 2 TiO 3 、Li 2 ZrO 3 The preparation method of the composite coated ternary cathode material is characterized by comprising the following steps of: the titanium compound in the step (6) is tetrabutyl titanate; the zirconium salt is one of zirconium nitrate and zirconium acetate.
6. A Li as claimed in claim 1 2 TiO 3 、Li 2 ZrO 3 The preparation method of the composite coated ternary cathode material is characterized by comprising the following steps of: the lithium salt in the step (7) is one of lithium hydroxide, lithium carbonate and lithium acetate.
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