CN112242515B - Preparation method and application of modified lithium-rich manganese-based layered oxide positive electrode material - Google Patents
Preparation method and application of modified lithium-rich manganese-based layered oxide positive electrode material Download PDFInfo
- Publication number
- CN112242515B CN112242515B CN202011042139.4A CN202011042139A CN112242515B CN 112242515 B CN112242515 B CN 112242515B CN 202011042139 A CN202011042139 A CN 202011042139A CN 112242515 B CN112242515 B CN 112242515B
- Authority
- CN
- China
- Prior art keywords
- lithium
- source
- manganese
- layered oxide
- based layered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 72
- 239000011572 manganese Substances 0.000 title claims abstract description 72
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 150000002641 lithium Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000007774 positive electrode material Substances 0.000 title abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 60
- 239000002243 precursor Substances 0.000 claims abstract description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000012266 salt solution Substances 0.000 claims abstract description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000010406 cathode material Substances 0.000 claims description 27
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical group [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 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 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 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 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
Images
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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method and application of a modified lithium-rich manganese-based layered oxide positive electrode material. The method comprises the following steps: s1, fully dissolving a manganese source, a nickel source and a cobalt source in deionized water to obtain a mixed metal salt solution; s2, adding an inorganic strong base and an ammonia water solution to adjust the pH value of the mixed metal salt solution obtained in the step S1 to 7.5-8.5, continuously stirring, fully reacting, filtering, washing and drying in vacuum to obtain a lithium-rich manganese-based layered oxide precursor containing manganese, nickel and cobalt; s3, fully dissolving the precursor obtained in the step S2 and a strong oxidant in deionized water, continuously stirring, washing, centrifuging and drying in vacuum; s4, fully grinding and mixing the precursor obtained in the step S3 and a lithium source, calcining the obtained mixture at 480-520 ℃ for 5.5-6.5 h, calcining at 800-900 ℃ for 11.5-12.5 h, and fully grinding to obtain the lithium ion battery. The anode material has excellent charge-discharge efficiency, discharge specific capacity, rate capability and cycle performance in the discharge head circle, has low voltage attenuation, and can be widely applied to the preparation of lithium ion batteries.
Description
Technical Field
The invention belongs to the technical field of battery anode materials. More particularly, relates to a preparation method and application of a modified lithium-rich manganese-based layered oxide cathode material.
Background
With the continuous consumption of non-renewable fossil energy, the continuous occurrence of problems of environmental pollution, greenhouse effect and the like, the method creates a serious challenge for the sustainable development of the modern society. The development of clean renewable energy is a necessary way for the development of the future society. Solar energy, potential energy, tidal energy, wind energy, geothermal energy and other novel clean energy resources continuously receive wide attention of people. The development of new energy inevitably drives continuous progress in the field of energy storage. However, new energy is difficult to store, and the storage cost is high, so that a clean renewable energy storage device becomes a key factor for restricting the application of the energy. Lithium ion batteries stand out due to the advantages of excellent energy conversion efficiency, longer cycle life, low cost, and the like. However, the critical component determining the performance of the energy storage device is the positive electrode material of the lithium ion battery.
Currently, a series of lithium ion positive electrode materials have been developed, such as: transition metal oxide of layered structure, transition metal oxide of spinel structure and polyanion compound of olivine structure. Wherein, the lithium-rich manganese-based layered oxide cathode material xLi2MnO3·(1-x)LiMO2(0<x<1, M ═ Mn, Ni, Co) has a high specific capacity: (>250mAh·g-1) High voltage (c)>4.5V) and low cost, etc., which are widely researched by experts at home and abroad and are considered as one of the most potential lithium ion positive battery materials of the next generation (Zhang Yidi, preparation of the positive material of the layered lithium-rich manganese-based lithium ion battery and electrochemical properties thereof, Zhejiang university, 2016). However, the materials have lower first-turn coulombic efficiency, poorer cycle stability and rate capability, and the problems seriously hinder the industrialization and the practical application of the lithium-rich manganese-based layered oxide cathode material and urgently need to be solved.
Therefore, the development of the modified lithium-rich manganese-based layered oxide cathode material with higher energy conversion, better cycling stability and rate capability and smaller voltage attenuation has important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of low coulombic efficiency, poor cycle stability, rapid voltage attenuation and low rate capability of the first circle of the existing lithium-rich manganese-based layered oxide positive electrode material, and provides a preparation method and application of a modified lithium-rich manganese-based layered oxide positive electrode material.
The invention aims to provide a preparation method of a modified lithium-rich manganese-based layered oxide cathode material.
The invention also aims to provide application of the modified lithium-rich manganese-based layered oxide cathode material prepared by the method in preparation of a lithium ion battery.
The above purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of a modified lithium-rich manganese-based layered oxide anode material, which comprises the following steps:
s1, fully dissolving a manganese source, a nickel source and a cobalt source in deionized water to obtain a mixed metal salt solution;
s2, adding an inorganic strong base and an ammonia water solution to adjust the pH value of the mixed metal salt solution obtained in the step S1 to 7.5-8.5, continuously stirring, fully reacting, filtering, washing and drying in vacuum to obtain a lithium-rich manganese-based layered oxide precursor containing manganese, nickel and cobalt;
s3, fully dissolving the precursor obtained in the step S2 and a strong oxidant in deionized water, continuously stirring, washing, centrifuging and drying in vacuum;
and S4, fully grinding and mixing the precursor obtained in the step S3 and a lithium source, calcining the obtained mixture at 480-520 ℃ for 5.5-6.5 h, calcining at 800-900 ℃ for 11.5-12.5 h, and fully grinding to obtain the modified lithium-rich manganese-based layered oxide cathode material.
The inventor creatively utilizes a strong oxidant (potassium ferrate) to rapidly hydrolyze into colloid in deionized water, and Fe (OH) is generated in the continuous stirring process because the size of colloid particles is in a nanometer level3The particles can be fully attached to the surfaces of the precursor particles to form uniform coating layers. And then washing with deionized water for 2-3 times and absolute ethyl alcohol for 2-3 times, and fully washing away the K ions. And finally, in the lithium intercalation stage, under the condition of long-time high-temperature calcination, part of Fe atoms can be diffused into the interior of the crystal lattice of the material and between primary particle intervals, and the dual regulation and control are carried out on the material interface and the interior crystal lattice.
Preferably, the concentration of the metal in the mixed metal salt solution in the step S1 is 1.8-2.2 mol/L.
More preferably, the concentration of the metal in the mixed metal salt solution of step S1 is 2 mol/L.
Preferably, the pH of the mixed metal salt solution of step S2 is 8.
Preferably, the temperature of the vacuum drying in steps S2 and S3 is 115 ℃ to 125 ℃.
More preferably, the temperature of the vacuum drying in steps S2 and S3 is 120 ℃.
Preferably, the detergents used in the washing in step S2 are deionized water and absolute ethyl alcohol.
Preferably, the calcining conditions in step S4 are: calcining at 500 ℃ for 6h and then calcining at 850 ℃ for 12 h.
Preferably, the molar ratio of the manganese source, the nickel source and the cobalt source in the step S1 is 53-55: 12-14.
More preferably, the molar ratio of the manganese source, the nickel source and the cobalt source in the step S1 is 54: 13. The positive electrode material obtained by the manganese source, the nickel source and the cobalt source with the specific ratio has more excellent first-turn coulombic efficiency, circulation stability and rate capability, and meanwhile, voltage attenuation is effectively inhibited.
Manganese sources, nickel sources, and cobalt sources conventional in the art may be used in the present invention. Preferably, the manganese source in step S1 is any one or more of manganese acetate, manganese nitrate or manganese sulfate; the nickel source is any one or more of nickel acetate, nickel nitrate or nickel sulfate; the cobalt source is any one or more of cobalt acetate, cobalt nitrate or cobalt sulfate.
More preferably, the manganese source of step S1 is manganese acetate; the nickel source is nickel acetate; the nickel source is nickel acetate.
Preferably, the molar ratio of the metal and the ammonia water in the mixed metal salt solution in the step S2 is 10: 1-3.
More preferably, the molar ratio of the metal and the ammonia water in the mixed metal salt solution in the step S2 is 5: 1.
Preferably, the concentration of the ammonia water solution in the step S2 is 1.0-1.4 mol/L.
More preferably, the concentration of the aqueous ammonia solution in the step S2 is 1.2 mol/L.
Preferably, the mass ratio of the metal and the strong oxidant in the precursor in the step S3 is 20-100: 1.
More preferably, the mass ratio of the metal and the strong oxidant in the precursor in step S3 is 60: 1.
Preferably, the strong oxidant in step S3 is potassium ferrate.
Preferably, the molar ratio of the metal in the precursor in step S4 to the lithium source is 1: 1.4-1.42.
More preferably, the molar ratio of the metal in the precursor of step S4 to the lithium source is 1: 1.41.
Preferably, in step S4, the lithium source is any one or more of lithium carbonate, lithium bicarbonate, lithium hydroxide or lithium nitrate.
More preferably, in step S4, the lithium source is lithium carbonate.
Preferably, the concentration of the inorganic strong base in the step S2 is 1.8-2.2 mol/L.
More preferably, the concentration of the inorganic strong base in the step S2 is 2 mol/L.
Preferably, the inorganic strong base in step S2 is Na2CO3。
The application of the modified lithium-rich manganese-based layered oxide cathode material prepared by the method in the preparation of lithium ion batteries also falls within the protection scope of the invention.
The invention has the following beneficial effects:
the invention provides a preparation method and application of a modified lithium-rich manganese-based layered oxide positive electrode material. The preparation method has simple process and easy operation, and the first-circle charge-discharge specific capacity of 0.1C of the modified lithium-rich manganese-based layered oxide anode material prepared by the method is 291 mAh.g-1The coulombic efficiency of the first circle is 82.84%, and the charging and discharging specific capacity under the 5C multiplying power is 125.93mAh g-1The capacity retention rate of 100 cycles of 1C circulation is 88.2%, the coulombic efficiency, the multiplying power performance and the circulation performance of the first cycle are obviously improved, and the voltage attenuation is effectively inhibited; therefore, the modified lithium-rich manganese-based layered oxide cathode material prepared by the method has wide application prospect in the preparation of lithium ion batteries.
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of a modified lithium-rich manganese-based layered oxide cathode material prepared by the method.
Fig. 2 is an SEM image of an unmodified lithium-rich manganese-based layered oxide positive electrode material.
FIG. 3 is an SEM image of the modified lithium-rich manganese-based layered oxide cathode material prepared by the method.
FIG. 4 is a 0.1C charge-discharge curve diagram of the modified lithium-rich manganese-based layered oxide positive electrode material prepared by the invention at a test temperature of 25 ℃ and a test voltage of 2.0-4.8V.
FIG. 5 is a 0.1C cycle performance diagram of the modified lithium-rich manganese-based layered oxide positive electrode material prepared by the invention at a test temperature of 25 ℃ and a test voltage of 2.0-4.8V.
FIG. 6 is a graph showing the rate performance of 0.1C, 0.5C, 1C, 3C and 5C when the testing temperature is 25 ℃ and the testing voltage is 2.0-4.8V.
FIG. 7 is an electrical property diagram of the modified lithium-rich manganese-based layered oxide positive electrode material prepared by the invention with different charge-discharge cycles at a test temperature of 25 ℃ and a test voltage of 2.0-4.8V.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1 preparation of modified lithium-rich manganese-based layered oxide cathode Material
A preparation method of a modified lithium-rich manganese-based layered oxide cathode material comprises the following steps:
s1, fully dissolving manganese acetate, nickel acetate and cobalt acetate (the molar ratio is 54: 13) in deionized water to obtain a mixed metal salt solution (the concentration of metal in the mixed metal salt solution is 2mol/L), and adding the mixed metal salt solution into a 5L reaction kettle at a constant speed by using a peristaltic pump;
s2, adding Na into the reaction kettle at a constant speed2CO3(the concentration is 2mol/L) and an ammonia water solution (the concentration is 1.2mol/L) to adjust the pH value of the mixed metal salt solution obtained in the step S1 to be 8, continuously stirring, fully reacting at 50 ℃ for 10h, filtering, washing, and vacuum drying at 120 ℃ for 12h to obtain a lithium-rich manganese-based layered oxide precursor containing manganese, nickel and cobalt;
wherein the molar ratio of the metal and the ammonia water in the mixed metal salt solution is 5: 1;
s3, fully dissolving the precursor obtained in the step S2 and potassium ferrate (the mass ratio of metal in the precursor to the strong oxidant is 60:1) in deionized water, continuously stirring, washing with the deionized water for 2 times, then washing with absolute ethyl alcohol for 2 times, centrifuging, and drying in vacuum at 120 ℃ for 12 hours;
and S4, placing the precursor obtained in the step S3 and lithium carbonate (the molar ratio of metal in the precursor to a lithium source is 1:1.41) in a mortar for fully grinding and mixing, calcining the obtained mixture at 500 ℃ for 6h, then calcining at 850 ℃ for 12h, naturally cooling to room temperature, and placing in the mortar for fully grinding to obtain the modified lithium-rich manganese-based layered oxide cathode material.
Example 2 preparation of modified lithium-rich manganese-based layered oxide cathode Material
A preparation method of a modified lithium-rich manganese-based layered oxide cathode material comprises the following steps:
s1, fully dissolving manganese nitrate, nickel nitrate and cobalt nitrate (the molar ratio is 53: 12) in deionized water to obtain a mixed metal salt solution (the concentration of metal in the mixed metal salt solution is 1.8mol/L), and adding the mixed metal salt solution into a 5L reaction kettle at a constant speed by using a peristaltic pump;
s2, adding Na into the reaction kettle at a constant speed2CO3(the concentration is 2.2mol/L) and an ammonia water solution (the concentration is 1.0mol/L) to adjust the pH value of the mixed metal salt solution obtained in the step S1 to be 8.5, continuously stirring, fully reacting at 50 ℃ for 10h, filtering, washing, and vacuum drying at 115 ℃ for 12h to obtain a manganese-nickel-cobalt-containing lithium-rich manganese-based layered oxide precursor;
wherein the molar ratio of the metal in the mixed metal salt solution to the ammonia water is 10: 3;
s3, fully dissolving the precursor obtained in the step S2 and potassium ferrate (the mass ratio of metal in the precursor to the strong oxidant is 20:1) in deionized water, continuously stirring, washing with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, centrifuging, and drying in vacuum at 125 ℃ for 12 hours;
s4, placing the precursor obtained in the step S3 and lithium bicarbonate (the molar ratio of metal in the precursor to a lithium source is 1:1.42) in a mortar for fully grinding and mixing, calcining the obtained mixture at 480 ℃ for 6.5h, then calcining at 800 ℃ for 12.5h, naturally cooling to room temperature, and placing in the mortar for fully grinding to obtain the modified lithium-rich manganese-based layered oxide cathode material.
Example 3 preparation of modified lithium-rich manganese-based layered oxide cathode Material
A preparation method of a modified lithium-rich manganese-based layered oxide cathode material comprises the following steps:
s1, fully dissolving manganese sulfate, nickel sulfate and cobalt sulfate (the molar ratio is 55: 14) in deionized water to obtain a mixed metal salt solution (the concentration of metal in the mixed metal salt solution is 2.2mol/L), and adding the mixed metal salt solution into a 5L reaction kettle at a constant speed by using a peristaltic pump;
s2, adding Na into the reaction kettle at a constant speed2CO3(the concentration is 1.8mol/L) and an ammonia water solution (the concentration of the ammonia water solution is 1.4mol/L), adjusting the pH value of the mixed metal salt solution obtained in the step S1 to be 7.5, continuously stirring, fully reacting at 50 ℃ for 10h, filtering, washing, and vacuum drying at 125 ℃ for 12h to obtain a manganese-nickel-cobalt-containing lithium-rich manganese-based layered oxide precursor;
wherein the molar ratio of the metal and the ammonia water in the mixed metal salt solution is 10: 1;
s3, fully dissolving the precursor obtained in the step S2 and potassium ferrate (the mass ratio of metal in the precursor to the strong oxidant is 100:1) in deionized water, continuously stirring, washing with the deionized water for 2 times, then washing with absolute ethyl alcohol for 3 times, centrifuging, and drying in vacuum at 115 ℃ for 12 hours;
s4, placing the precursor obtained in the step S3 and lithium hydroxide (the molar ratio of metal in the precursor to a lithium source is 1:1.42) in a mortar for fully grinding and mixing, calcining the obtained mixture at 520 ℃ for 5.5h, calcining at 900 ℃ for 11.5h, naturally cooling to room temperature, and placing in the mortar for fully grinding to obtain the modified lithium-rich manganese-based layered oxide cathode material.
Example 4 preparation of modified lithium-rich manganese-based layered oxide cathode Material
A preparation method of a modified lithium-rich manganese-based layered oxide cathode material comprises the following steps:
s1, fully dissolving manganese acetate, nickel nitrate and cobalt sulfate (the molar ratio is 53: 14) in deionized water to obtain a mixed metal salt solution (the concentration of metal in the mixed metal salt solution is 2.1mol/L), and adding the mixed metal salt solution into a 5L reaction kettle at a constant speed by using a peristaltic pump;
s2, adding Na into the reaction kettle at a constant speed2CO3(the concentration is 1.9mol/L) and an ammonia water solution (the concentration of the ammonia water solution is 1.1mol/L), adjusting the pH value of the mixed metal salt solution obtained in the step S1 to be 7.8, continuously stirring, fully reacting at 50 ℃ for 10h, filtering, washing, and vacuum drying at 123 ℃ for 12h to obtain a lithium-rich manganese-based layered oxide precursor containing manganese, nickel and cobalt;
wherein the molar ratio of the metal and the ammonia water in the mixed metal salt solution is 4: 1;
s3, fully dissolving the precursor obtained in the step S2 and potassium ferrate (the mass ratio of metal in the precursor to the strong oxidant is 50:1) in deionized water, continuously stirring, washing with deionized water for 3 times, then washing with absolute ethyl alcohol for 2 times, centrifuging, and vacuum-drying at 123 ℃ for 12 hours;
s4, placing the precursor obtained in the step S3 and lithium nitrate (the molar ratio of metal in the precursor to a lithium source is 1:1.41) in a mortar for fully grinding and mixing, calcining the obtained mixture at 510 ℃ for 5.8h, then calcining at 870 ℃ for 12.3h, naturally cooling to room temperature, and placing in the mortar for fully grinding to obtain the modified lithium-rich manganese-based layered oxide cathode material.
Application example 1 Performance test of modified lithium-rich manganese-based layered oxide cathode material
1. Experimental methods
Taking example 1 as an example, the modified lithium-rich manganese-based layered oxide positive electrode material prepared in example 1, acetylene black and PVDF were mixed and coated on an aluminum foil, vacuum-dried, sliced to be a positive electrode, a metal lithium sheet as a negative electrode, a microporous polypropylene film as a separator, 1mol/L LiPF6 (solvent is VEC: mixed solution of VDEC 1: 1) as an electrolyte, a lithium ion half cell (CR2025 button cell) was assembled by the order of a positive electrode case, a positive electrode, a separator, a negative electrode, and a negative electrode case, and the electrochemical performance of the modified lithium-rich manganese-based layered oxide positive electrode material prepared in examples 1 to 4 was tested.
The modified lithium-rich manganese-based layered oxide positive electrode material prepared in example 1 is subjected to X-ray diffraction analysis and scanning electron microscope analysis, and electrical property test is carried out at a test temperature of 25 ℃ and a test voltage of 2.0-4.8V.
2. Results of the experiment
The XRD pattern of the modified lithium-rich manganese-based layered oxide anode material prepared by the invention is shown in figure 1, and it can be seen that K is2FeO4The main structure of the lithium-rich manganese-based layered oxide is not damaged.
The SEM image of the unmodified lithium-rich manganese-based layered oxide positive electrode material is shown in fig. 2, and the SEM image of the modified lithium-rich manganese-based layered oxide positive electrode material prepared by the present invention is shown in fig. 3, which shows that the surface of the modified lithium-rich layered oxide positive electrode material is denser than that of the unmodified lithium-rich manganese-based layered oxide positive electrode material.
The charge-discharge curve chart of 0.1C of the modified lithium-rich manganese-based layered oxide anode material prepared by the invention at the test temperature of 25 ℃ and the test voltage of 2.0-4.8V is shown in figure 4, and it can be seen that the charge-discharge specific capacity of the first circle of 0.1C is 291mAh g-1。
The charge-discharge curve of the modified lithium-rich manganese-based layered oxide anode material prepared by the invention at the test temperature of 25 ℃ and the test voltage of 2.0-4.8V at 0.1C is shown in FIG. 4, and it can be seen that the coulombic efficiency of the first cycle is 82.84%, and the capacity retention rate of 100 cycles of 1C cycle is 88.2%.
The multiplying power performance diagram of 0.1C, 0.5C, 1C, 3C and 5C of the modified lithium-rich manganese-based layered oxide anode material prepared by the invention at the test temperature of 25 ℃ and the test voltage of 2.0-4.8V is shown in figure 6, and it can be seen that the charging and discharging specific capacity at the multiplying power of 5C is 125.93mAh g-1。
The electrical property diagram of the modified lithium-rich manganese-based layered oxide anode material prepared by the invention with different charging and discharging turns at the test temperature of 25 ℃ and the test voltage of 2.0-4.8V is shown in figure 7, and it can be seen that the voltage attenuation is effectively inhibited.
The above results show that: the modified lithium-rich manganese-based layered oxide positive electrode material prepared by the invention has excellent charge-discharge efficiency, discharge specific capacity, rate capability and cycle performance in the discharge first loop, and the voltage attenuation is effectively inhibited.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of a modified lithium-rich manganese-based layered oxide cathode material is characterized by comprising the following steps:
s1, fully dissolving a manganese source, a nickel source and a cobalt source in deionized water to obtain a mixed metal salt solution;
s2, adding an inorganic strong base and an ammonia water solution to adjust the pH value of the mixed metal salt solution obtained in the step S1 to 7.5-8.5, continuously stirring, fully reacting, filtering, washing and drying in vacuum to obtain a lithium-rich manganese-based layered oxide precursor containing manganese, nickel and cobalt;
s3, fully dissolving the precursor obtained in the step S2 and a strong oxidant in deionized water, continuously stirring, washing, centrifuging and drying in vacuum;
s4, fully grinding and mixing the precursor obtained in the step S3 and a lithium source, calcining the obtained mixture at 480-520 ℃ for 5.5-6.5 h, calcining at 800-900 ℃ for 11.5-12.5 h, and fully grinding to obtain a modified lithium-rich manganese-based layered oxide cathode material;
in the step S1, the manganese source is any one or more of manganese acetate, manganese nitrate or manganese sulfate; the nickel source is any one or more of nickel acetate, nickel nitrate or nickel sulfate; the cobalt source is any one or more of cobalt acetate, cobalt nitrate or cobalt sulfate;
in step S3, the strong oxidant is potassium ferrate.
2. The method according to claim 1, wherein the molar ratio of the manganese source, the nickel source and the cobalt source in step S1 is 53-55: 12-14.
3. The method of claim 1, wherein the molar ratio of the metal and the ammonia water in the mixed metal salt solution in step S2 is 10: 1-3.
4. The method of claim 1, wherein the concentration of the aqueous ammonia solution in step S2 is 1.0-1.4 mol/L.
5. The method according to claim 1, wherein the mass ratio of the metal and the strong oxidant in the precursor in step S3 is 20-100: 1.
6. The method according to claim 1, wherein the molar ratio of the metal to the lithium source in the precursor in step S4 is 1: 1.4-1.42.
7. The method of claim 1, wherein in step S4, the lithium source is any one or more of lithium carbonate, lithium bicarbonate, lithium hydroxide or lithium nitrate.
8. The application of the modified lithium-rich manganese-based layered oxide cathode material prepared by the method of any one of claims 1 to 7 in the preparation of lithium ion batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011042139.4A CN112242515B (en) | 2020-09-28 | 2020-09-28 | Preparation method and application of modified lithium-rich manganese-based layered oxide positive electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011042139.4A CN112242515B (en) | 2020-09-28 | 2020-09-28 | Preparation method and application of modified lithium-rich manganese-based layered oxide positive electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112242515A CN112242515A (en) | 2021-01-19 |
| CN112242515B true CN112242515B (en) | 2022-02-08 |
Family
ID=74171871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011042139.4A Active CN112242515B (en) | 2020-09-28 | 2020-09-28 | Preparation method and application of modified lithium-rich manganese-based layered oxide positive electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112242515B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112786877A (en) * | 2021-03-08 | 2021-05-11 | 昆明理工大学 | Preparation method of lithium-rich manganese-based positive electrode material |
| CN117080427B (en) * | 2023-06-16 | 2024-07-26 | 安徽理士新能源发展有限公司 | Transition metal layered oxide sodium battery positive electrode material, preparation method and application |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW521451B (en) * | 2000-03-13 | 2003-02-21 | Canon Kk | Process for producing an electrode material for a rechargeable lithium battery, an electrode structural body for a rechargeable lithium battery, process for producing said electrode structural body, a rechargeable lithium battery in which said electrode |
| IL141260A0 (en) * | 2001-02-04 | 2002-03-10 | Chemergy Energy Technologies O | New cathode formulations for super-iron batteries |
| CN101217196A (en) * | 2008-01-21 | 2008-07-09 | 大庆石油学院 | Cathode materials for potassium ferrate batteries |
| CN101428862B (en) * | 2008-12-23 | 2010-09-01 | 孝感学院 | A kind of preparation method of potassium ferrate doped with potassium permanganate |
| CN105742595A (en) * | 2016-03-04 | 2016-07-06 | 广东精进能源有限公司 | Nickel-containing lithium-rich and manganese-based positive electrode material and preparation method thereof, positive electrode and battery |
| CN109256557A (en) * | 2018-10-23 | 2019-01-22 | 乳源东阳光磁性材料有限公司 | Nickelic layered oxide lithium electricity positive electrode of a kind of perofskite type oxide cladding and preparation method thereof |
| CN109713296A (en) * | 2018-12-17 | 2019-05-03 | 成都新柯力化工科技有限公司 | A kind of processing method for the nickelic tertiary cathode material electric conductivity improving lithium battery |
| CN111403721B (en) * | 2020-04-16 | 2021-06-29 | 旭派电源有限公司 | A kind of preparation method of lithium ion battery lithium titanate negative electrode material |
-
2020
- 2020-09-28 CN CN202011042139.4A patent/CN112242515B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112242515A (en) | 2021-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107215900B (en) | A method for constructing a spinel structure on the surface of a lithium-rich manganese-based cathode material | |
| CN109167056B (en) | A tungsten ion-doped high nickel layered oxide lithium battery cathode material and preparation method thereof | |
| CN108539141B (en) | Preparation method of ternary layered positive electrode material for sodium-ion battery | |
| CN111509224B (en) | A linkage modified lithium-rich manganese-based cathode material and preparation method thereof | |
| CN110862108A (en) | A method for improving the electrochemical performance of high nickel ternary cathode materials by fluorine doping modification | |
| CN108598394B (en) | Carbon-coated titanium manganese phosphate sodium microspheres and preparation method and application thereof | |
| CN108520944A (en) | A kind of nitrogen-doped carbon cladding mangano-manganic oxide composite material and preparation method and application | |
| CN108123128A (en) | Adulterate Al in a kind of surface layer3+NCM tertiary cathode materials preparation method | |
| CN108172808B (en) | A modification method of lithium-rich manganese-based positive electrode material coated with cerium-tin composite oxide | |
| CN102208611A (en) | Induced crystallization synthesis method for anode powder material of lithium ion secondary battery | |
| CN114671471A (en) | A spinel/layered heterostructure modified cobalt-free lithium-rich manganese-based cathode material and preparation method thereof | |
| CN114229921B (en) | Al2O3-ZrO2 coated lithium-rich manganese-based cathode material and preparation method thereof | |
| CN103531778A (en) | Solid solution sodium-ion battery positive material and preparation method therefor | |
| CN108091854A (en) | A kind of high-voltage spinel type anode material for lithium-ion batteries of Anion-cation multiple dope and preparation method thereof | |
| CN103078099A (en) | Anode material for lithium ion cell and preparation method thereof | |
| CN107069032A (en) | A kind of preparation method of lithium ion battery hollow ball shape lithium-rich manganese-based anode material | |
| CN118919714B (en) | A P2-type nickel-manganese base oxide cathode material for sodium-ion batteries and its preparation method | |
| CN113422048A (en) | Preparation method and application of novel water-based zinc ion battery positive electrode material | |
| WO2019080310A1 (en) | Molybdenum-doped lithium-rich manganese-based cathode material and preparation method therefor | |
| CN112242515B (en) | Preparation method and application of modified lithium-rich manganese-based layered oxide positive electrode material | |
| CN111048775A (en) | An in-situ sodium-doped modification method for improving lithium storage performance of ternary cathode materials | |
| CN118248865A (en) | Sodium ion battery high entropy layered positive electrode material, preparation method and battery | |
| CN114122389B (en) | Zinc-manganese selenide solid solution positive electrode material for water-based zinc ion battery and preparation method thereof | |
| CN106784657A (en) | A kind of method that sodium and iron codope prepare High-performance lithium manganate anode material | |
| CN112242510A (en) | Preparation method and application of epitaxial growth layer and sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220422 Address after: 512721 Building 1, Songtian plant area, Gonghe village committee, Rucheng Town, Ruyuan Yao Autonomous County, Shaoguan City, Guangdong Province Patentee after: Ruyuan dongyangguang new energy material Co.,Ltd. Patentee after: Shaoguan East Sunshine Technology R & D Co., Ltd Address before: 512721 Ruyuan County Development Zone, Guangdong, Shaoguan Patentee before: RUYUAN DONG YANG GUANG MATERIALS Co.,Ltd. Patentee before: Shaoguan East Sunshine Technology R & D Co., Ltd |
|
| TR01 | Transfer of patent right |