CN117756194A - Modified lithium-rich manganese-based positive electrode material and preparation method and application thereof - Google Patents
Modified lithium-rich manganese-based positive electrode material and preparation method and application thereof Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 50
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 47
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 38
- 150000002641 lithium Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 43
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- 239000013239 manganese-based metal-organic framework Substances 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000004729 solvothermal method Methods 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000010405 anode material Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 239000011565 manganese chloride Substances 0.000 claims description 6
- 235000002867 manganese chloride Nutrition 0.000 claims description 6
- 229940099607 manganese chloride Drugs 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 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 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- 229910052742 iron Inorganic materials 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
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 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
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-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
- 230000035484 reaction time Effects 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 229940099596 manganese sulfate Drugs 0.000 claims 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 8
- 229910018663 Mn O Inorganic materials 0.000 abstract description 4
- 229910003176 Mn-O Inorganic materials 0.000 abstract description 4
- 229910018553 Ni—O Inorganic materials 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 238000000227 grinding Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910008522 Li1.2Mn0.54Co0.13Ni0.13O2 Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009837 dry grinding Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000005536 Jahn Teller effect Effects 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- GEIJUOCMDNDDBH-UHFFFAOYSA-L [OH-].[OH-].[Mn].[Co++] Chemical compound [OH-].[OH-].[Mn].[Co++] GEIJUOCMDNDDBH-UHFFFAOYSA-L 0.000 description 1
- 239000011149 active material 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
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- DYAZFWWXRXSNJY-UHFFFAOYSA-N boranylidynecerium Chemical compound [Ce].[B] DYAZFWWXRXSNJY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- -1 boron ions Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012073 inactive phase Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a modified lithium-rich manganese-based positive electrode material, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Mixing manganese salt, doped metal salt and terephthalic acid solution, and performing solvothermal reaction to obtain a doped Mn-MOF material; (2) Mixing the doped Mn-MOF material with an oxidant and a solvent, regulating pH value, and performing high-pressure hydrothermal reaction to obtain doped MnO 2 A material; (3) The doped MnO 2 Material and nickel source, cobaltMixing the source and the lithium source, and roasting to obtain the modified lithium-rich manganese-based anode material. The doped manganese dioxide is prepared in a mode of preparing the doped Mn-MOF in advance, so that the doped elements can be ensured to be accurately doped into target positions, the bulk doped elements can stabilize adjacent Mn-O, co-O and Ni-O bonds, and the migration energy barriers of Mn, co and Ni are improved, so that the structural stability of the lithium-rich anode material is greatly improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a modified lithium-rich manganese-based positive electrode material, and a preparation method and application thereof.
Background
High energy density is a permanent direction of development of lithium ion batteries. In lithium ion batteries, the positive electrode material is critical to increasing the energy density of the lithium ion battery. In the current power battery, the commercial positive electrode material mainly comprises LiFePO with an olivine structure 4 And a layered structure of LiNi x Co y Mn 1-x-y O 2 The electron transfer of these materials during the electrode reaction is all controlled by metal cation pairs (Fe 2+ /Fe 3+ 、Ni 2+ /Ni 3+ /Ni 4+ 、Co 3+ /Co 4+ ) Charge compensation is carried out by the oxidation-reduction reaction of (a), which essentially limits its specific capacity. The lithium-rich manganese-based positive electrode material LRMO can realize high specific capacity exceeding 280mAh/g in the voltage range of 2-4.8V due to a unique anion redox reaction mechanism, and creates conditions for realizing higher energy density.
However, the lithium-rich manganese-based positive electrode material has low intrinsic conductivity, irreversible escape of lattice oxygen and transition from a layer-like phase to a spinel-like phase in circulation, resulting in poor rate performance, low initial coulombic efficiency, and fast capacity and voltage decay, which limits its practical application.
CN116639733A is prepared by mixing and roasting a manganese cobalt hydroxide precursor, a lithium source, cerium nitrate and sodium borohydride to obtain the boron-cerium double-doped lithium-rich manganese-based positive electrode material, and the co-doping of cerium and boron ions can effectively reduce the increased transfer internal resistance of the positive electrode material in the circulation process, reduce the phase transition speed of the material and maintain higher median voltage.
CN116605921a discloses a preparation method of a tungsten doped lithium-rich manganese-based positive electrode material, after tungsten doping, structural collapse caused by material phase change can be relieved, impedance is reduced, charge transfer capacity is improved, thermal stability of the material is improved, and good cycle performance and rate capability are finally shown.
The doping method has a certain improvement on performance, but can not prevent the discharge voltage from continuously decreasing due to phase change, and the added doping elements are often gathered on the surface of the material, so that the crystal structure of the material can not be regulated.
Disclosure of Invention
The invention aims to provide a modified lithium-rich manganese-based positive electrode material, a preparation method and application thereof, and the doped manganese dioxide is prepared by preparing the doped Mn-MOF in advance, so that the doped elements can be ensured to be accurately doped into a target position, the bulk doped elements can firmly adjacent Mn-O, co-O and Ni-O bonds, and the migration energy barrier of Mn, co and Ni is improved, so that the structural stability of the lithium-rich positive electrode material is greatly improved.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a modified lithium-rich manganese-based cathode material, the method comprising the steps of:
(1) Mixing manganese salt, doped metal salt and terephthalic acid solution, and performing solvothermal reaction to obtain a doped Mn-MOF material;
(2) Mixing the doped Mn-MOF material with an oxidant and a solvent, regulating pH value, and performing high-pressure hydrothermal reaction to obtain doped MnO 2 A material;
(3) The doped MnO 2 Mixing the material with a nickel source, a cobalt source and a lithium source, and roasting to obtain the modified lithium-rich manganese-based anode material.
The invention synthesizes the Mn-based bimetallic MOF doped with cations by a solvothermal method firstly, and then converts the Mn-based bimetallic MOF into MnO doped with the element M by hydrothermal conversion 2 (M= Ru, mg, al, fe), and finally mechanically mixing the lithium source, the nickel source, the cobalt source and the lithium source, and calcining at high temperature to obtain the lithium-rich manganese-based anode material with Ru, mg, al, fe and other elements doped in situ. The invention prepares doped MnO after doping metal elements in Mn-MOF 2 On one hand, the material can relieve the generation of phase change, thereby improving the structural stability of the crystal; meanwhile, the irreversible precipitation behavior of oxygen is inhibited, the first coulombic efficiency of the lithium-rich manganese-based positive electrode material (LRMO) is improved, and the electrochemical performance of the LRMO positive electrode material is improved.
Preferably, the manganese salt of step (1) comprises any one or a combination of at least two of manganese sulphate, nitrate or chloride.
Preferably, the doped metal salt comprises any one or a combination of at least two of a chloride, nitrate or sulfate salt containing Ru, mg, al or Fe.
Preferably, the mass ratio of the manganese salt to the doped metal salt is (3-8) 1, for example: 3:1, 4:1, 5:1, 6:1, or 8:1, etc.
Preferably, the solvent of the terephthalic acid solution comprises any one or a combination of at least two of N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or methanol.
Preferably, the concentration of the terephthalic acid solution is 10-50 g/L, for example: 10g/L, 20g/L, 30g/L, 40g/L, 50g/L, etc.
Preferably, the alkali liquor is added and stirred before the solvothermal reaction in step (1).
Preferably, the concentration of the lye is 0.2 to 0.8mol/L, for example: 0.2mol/L, 0.3mol/L, 0.5mol/L, 0.6mol/L or 0.8mol/L, etc.
Preferably, the solvothermal reaction temperature is 90-120 ℃, for example: 90 ℃, 95 ℃,100 ℃, 110 ℃ or 120 ℃ and the like.
Preferably, the solvothermal reaction time is 8 to 12 hours, for example: 8h, 9h, 10h, 11h or 12h, etc.
Preferably, the solvothermal reaction is followed by a washing and drying treatment.
Preferably, the washed detergent comprises deionized water and/or ethanol.
Preferably, the oxidizing agent of step (2) comprises potassium permanganate.
Preferably, the mass ratio of the doped Mn-MOF material to the oxidant is (1.5-2.5): 1, for example: 1.5:1, 1.8:1, 2:1, 2.2:1, or 2.5:1, etc.
Preferably, the solvent comprises deionized water.
Preferably, the pH in step (2) is from 0.5 to 1.5, for example: 0.5, 0.8, 1, 1.2, 1.5, etc.
Preferably, the apparatus for high pressure hydrothermal reaction comprises an autoclave.
Preferably, the temperature of the high-pressure hydrothermal reaction is 120 to 180 ℃, for example: 120 ℃, 130 ℃,150 ℃, 160 ℃ or 180 ℃ and the like.
Preferably, the time of the high-pressure hydrothermal reaction is 20 to 30 hours, for example: 20h, 22h, 25h, 28h or 30h, etc.
Preferably, the high pressure hydrothermal reaction is followed by centrifugation, washing and drying.
Preferably, the washed detergent comprises deionized water and/or ethanol.
Preferably, the nickel source of step (3) comprises any one or a combination of at least two of nickel nitrate, nickel chloride or nickel sulphate.
Preferably, the cobalt source comprises any one or a combination of at least two of cobalt nitrate, cobalt chloride or cobalt sulfate.
Preferably, the lithium source comprises lithium hydroxide and/or lithium carbonate.
Preferably, the atmosphere of the calcination treatment in step (3) comprises oxygen and/or air.
Preferably, the firing treatment includes one-step firing and two-step firing.
Preferably, the one-step firing temperature is 300 to 600 ℃, for example: 300 ℃, 350 ℃, 400 ℃, 500 ℃ or 600 ℃ and the like.
Preferably, the one-step firing time is 3 to 10 hours, for example: 3h, 5h, 6h, 8h or 10h, etc.
Preferably, the temperature of the two-step firing is 600 to 1000 ℃, for example: 600 ℃, 700 ℃, 800 ℃, 900 ℃ or 1000 ℃ and the like.
Preferably, the two-step firing time is 10 to 20 hours, for example: 10h, 12h, 15h, 18h or 20h, etc.
In a second aspect, the present invention provides a modified lithium-rich manganese-based cathode material, the modified lithium-rich manganese-based cathode material being produced by the method as described in the first aspect.
In a third aspect, the invention provides a positive electrode sheet comprising the modified lithium-rich manganese-based positive electrode material according to the second aspect.
In a fourth aspect, the present invention provides a lithium ion battery comprising the positive electrode sheet according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The doped manganese dioxide is prepared in a mode of preparing the doped Mn-MOF in advance, so that doped elements can be ensured to be accurately doped into a target position without being gathered on the surface of a material, the bond energy of doped metal and oxygen is higher than that of nickel, cobalt, manganese and oxygen, the doped manganese dioxide has stronger binding force on O, and O loss and vacancy generation can be effectively slowed down.
(2) According to the invention, bulk doping is carried out on the lithium-rich manganese-based positive electrode material, and the bulk doped elements can stabilize adjacent Mn-O, co-O and Ni-O bonds, so that the migration energy barriers of Mn, co and Ni are improved, and the structural stability of the lithium-rich positive electrode material is greatly improved. Meanwhile, the bulk doping of the elements can increase the average valence state of the internal structure of the electron, inhibit the unit cell structure of the material from being converted from a lamellar state to a spinel state, and relieve the Jahn-Teller effect.
(3) The modified lithium-rich manganese-based positive electrode material prepared by the method has better performance, the first-circle capacity can be more than 286.9mAh/g, and the capacity retention rate of 100 circles of circulation can be more than 89.1%.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a modified lithium-rich manganese-based positive electrode material, and the preparation method of the modified lithium-rich manganese-based positive electrode material comprises the following steps:
(1) 3g of terephthalic acid (TPA) was weighed and dissolved in 100mL of N, N-Dimethylformamide (DMF), 2g of manganese chloride and 0.57g of ruthenium trichloride were then weighed and added to the above solution, stirred uniformly at room temperature, then 10mL of NaOH having a concentration of 0.4mol/L was added dropwise, stirred for 30min, transferred to a high-pressure reaction vessel, and solvothermal reaction was carried out at 100℃for 10h. After the reaction is finished and cooled to room temperature, collecting precipitate through centrifugation, washing the precipitate with deionized water and ethanol for 2 times in turn, and drying the precipitate to obtain the Ru-doped Mn-MOF material;
(2) 1g of Ru-doped Mn-MOF material and 0.5g of potassium permanganate are added into 20mL of deionized water, sulfuric acid is added dropwise to adjust the pH to 1, and the mixture is transferred into a high-pressure reaction kettle for hydrothermal reaction at 150 ℃ for 24 hours. After the reaction is cooled to room temperature, collecting precipitate by centrifugation, washing with deionized water and ethanol for 2 times in turn, and drying to obtain Ru doped MnO 2 A material;
(3) According to Li 1.2 Mn 0.54 Co 0.13 Ni 0.13 O 2 The ratio of each element is measured and Ru doped MnO is weighed 2 The material, nickel nitrate, cobalt nitrate and lithium hydroxide (1.05 times the slight excess of lithium hydroxide was 1.2) were mixed in a mortar and an appropriate amount of ethanol was added as a grinding aid. After full grinding, the mortar is placed in an oven, and dry grinding is fully performed after the ethanol is volatilized. And roasting the uniformly ground powder for 5 hours in an air atmosphere at 500 ℃, and roasting for 12 hours in an air atmosphere at 900 ℃ after grinding to obtain the modified lithium-rich manganese-based anode material.
Example 2
The embodiment provides a modified lithium-rich manganese-based positive electrode material, and the preparation method of the modified lithium-rich manganese-based positive electrode material comprises the following steps:
(1) 3g of terephthalic acid (TPA) is weighed and dissolved in 100mL of N, N-Dimethylformamide (DMF), 2g of manganese chloride and 0.26g of magnesium chloride are weighed and added into the solution, the solution is stirred uniformly at room temperature, then 15mL of NaOH with the concentration of 0.2mol/L is added dropwise, the solution is stirred for 30min and then transferred into a high-pressure reaction kettle, and solvothermal reaction is carried out for 12h at 90 ℃. After the reaction is finished and cooled to room temperature, collecting precipitate through centrifugation, washing the precipitate with deionized water and ethanol for 2 times in turn, and drying the precipitate to obtain the Mg-doped Mn-MOF material;
(2) 1.5g of Mg-doped Mn-MOF material and 1g of potassium permanganate are added into 30mL of deionized water, sulfuric acid is added dropwise to adjust the pH to 1.2, the mixture is transferred into a high-pressure reaction kettle, and the mixture is subjected to hydrothermal reaction at 120 ℃ for 30h. After the reaction is cooled to room temperature, collecting precipitate by centrifugation, washing with deionized water and ethanol for 2 times in turn, and drying to obtain Mg doped MnO 2 A material;
(3) According to Li 1.2 Mn 0.54 Co 0.13 Ni 0.13 O 2 The ratio of each element is measured and Mg doped MnO is weighed 2 The material, nickel nitrate, cobalt nitrate and lithium hydroxide (1.05 times the slight excess of lithium hydroxide was 1.2) were mixed in a mortar and an appropriate amount of ethanol was added as a grinding aid. After full grinding, the mortar is placed in an oven, and dry grinding is fully performed after the ethanol is volatilized. And roasting the uniformly ground powder for 10 hours in an air atmosphere at 400 ℃, and roasting for 15 hours in an air atmosphere at 800 ℃ after grinding to obtain the modified lithium-rich manganese-based anode material.
Example 3
The embodiment provides a modified lithium-rich manganese-based positive electrode material, and the preparation method of the modified lithium-rich manganese-based positive electrode material comprises the following steps:
(1) 3g of terephthalic acid (TPA) was weighed and dissolved in 100mL of N, N-Dimethylformamide (DMF), 2.4g of manganese chloride and 0.37g of aluminum chloride were then weighed and added to the above solution, stirred uniformly at room temperature, then 5mL of NaOH having a concentration of 0.8mol/L was added dropwise, stirred for 30min, transferred to a high-pressure autoclave, and solvothermal reaction was carried out at 120℃for 8h. After the reaction is finished and cooled to room temperature, collecting precipitate through centrifugation, washing the precipitate with deionized water and ethanol for 2 times in turn, and drying the precipitate to obtain an Al-doped Mn-MOF material;
(2) 2.5g of Al-doped Mn-MOF material and 1g of potassium permanganate are added into 30mL of deionized water, sulfuric acid is added dropwise to adjust the pH to 1, and the mixture is transferred into a high-pressure reaction kettle for hydrothermal reaction at 180 ℃ for 20h. After the reaction is cooled to room temperature, collecting precipitate by centrifugation, washing with deionized water and ethanol for 2 times in turn, and drying to obtain Al doped MnO 2 A material;
(3) According to Li 1.2 Mn 0.54 Co 0.13 Ni 0.13 O 2 The ratio of each element is weighed and Al doped MnO is weighed 2 The material, nickel nitrate, cobalt nitrate and lithium hydroxide (1.05 times the slight excess of lithium hydroxide was 1.2) were mixed in a mortar and an appropriate amount of ethanol was added as a grinding aid. After full grinding, the mortar is placed in an oven, and dry grinding is fully performed after the ethanol is volatilized. Then roasting the uniformly ground powder at 600 ℃ under air atmosphere for 3 timesAnd h, after grinding, roasting for 15 hours in an air atmosphere at 800 ℃ to obtain the modified lithium-rich manganese-based anode material.
Example 4
This example differs from example 1 only in that the mass ratio of manganese salt (manganese chloride) to doped metal salt (ruthenium trichloride) is 2:1, and the other conditions and parameters are exactly the same as example 1.
Example 5
This example differs from example 1 only in that the mass ratio of manganese salt (manganese chloride) to doped metal salt (ruthenium trichloride) is 10:1, and the other conditions and parameters are exactly the same as in example 1.
Example 6
This example differs from example 1 only in that the mass ratio of doped Mn-MOF material to oxidant (potassium permanganate) is 1:1, the other conditions and parameters being exactly the same as in example 1.
Example 7
This example differs from example 1 only in that the mass ratio of doped Mn-MOF material to oxidant (potassium permanganate) is 3:1, the other conditions and parameters being exactly the same as in example 1.
Comparative example 1
This comparative example differs from example 1 only in that no doping element was added, and other conditions and parameters were exactly the same as example 1.
Performance test:
the active materials, super P and polyvinylidene fluoride (PVDF) were prepared as positive electrodes in the examples and comparative examples, respectively, at 90:5:5 weight ratio of the mixture was dispersed in N-methylpyrrolidone (NMP) to form a uniform slurry. The slurry was then cast on aluminum foil by doctor blade method and vacuum dried at 60 ℃ for 12 hours to obtain LRMO positive plate. CR-2025 button cell is assembled in a glove box, a metal lithium sheet is used as a negative electrode, a diaphragm adopts a PP/PE/PP microporous membrane, and 1M LiPF 6 (DMC: dec=1:1) was used as electrolyte. To ensure that the internal electrolyte fully wets the electrodes, the assembled button cell was left to stand at room temperature for 24 hours and then tested. The assembled button half cell is subjected to constant current charge and discharge test in a blue cell test system, and the voltage interval is 2.0-4.8V #vs.Li + Li) at normal temperature, the battery was activated at 0.1C for two weeks, and then subjected to performance tests at 1C for different cycle times, the test results are shown in table 1:
TABLE 1
| Capacity (mAh/g) | First effect (%) | Cycle 100 cycle capacity retention (%) | |
| Example 1 | 287.8 | 84.9 | 89.7 |
| Example 2 | 286.9 | 84.3 | 89.5 |
| Example 3 | 287.1 | 84.4 | 89.1 |
| Example 4 | 265.5 | 84.7 | 90.1 |
| Example 5 | 245.3 | 76.8 | 75.9 |
| Example 6 | 262.5 | 82.5 | 88.4 |
| Example 7 | 271.4 | 81.9 | 86.3 |
| Comparative example 1 | 235.2 | 73.8 | 56.7 |
As can be seen from Table 1, the modified lithium-rich manganese-based positive electrode material prepared by the method disclosed by the invention has better performance, the initial capacity of the modified lithium-rich manganese-based positive electrode material can be more than 286.9mAh/g, and the capacity retention rate of the modified lithium-rich manganese-based positive electrode material in 100 cycles can be more than 89.1%.
As can be seen from comparison of examples 1 and 4-5, in the preparation process of the modified lithium-rich manganese-based positive electrode material, the mass ratio of manganese salt to doped metal salt influences the performance of the modified lithium-rich manganese-based positive electrode material, the mass ratio of manganese salt to doped metal salt is controlled to be 3-8:1, the prepared lithium-rich manganese-based positive electrode material has better performance, if the doped metal salt is added in an excessively small amount, the improvement effect on the structure and electrochemical performance of the material is limited, and if the doped metal salt is added in an excessively large amount, doped elements do not completely enter the crystal lattice of the material, so that inactive phases are increased, and the capacity of the material is reduced.
As can be seen from comparison of examples 1 and examples 6-7, in the preparation process of the modified lithium-rich manganese-based positive electrode material, the mass ratio of the doped Mn-MOF material to the oxidant influences the performance of the modified lithium-rich manganese-based positive electrode material, the mass ratio of the doped Mn-MOF material to the oxidant is controlled to be 1.5-2.5:1, the prepared lithium-rich manganese-based positive electrode material has good performance, if the addition amount of the oxidant is too small, formed particles are smaller, side reactions are aggravated, circulation is poor, and if the addition amount of the oxidant is too large, formed particles have larger particle size, longer ion electron transmission distance and low capacity.
By comparing the embodiment 1 with the comparative embodiment 1, the bulk doping is carried out on the lithium-rich manganese-based positive electrode material, and the bulk doped elements can stabilize adjacent Mn-O, co-O and Ni-O bonds, so that the migration energy barriers of Mn, co and Ni are improved, and the structural stability of the lithium-rich positive electrode material is greatly improved. Meanwhile, the bulk doping of the elements can increase the average valence state of the internal structure of the electron, inhibit the unit cell structure of the material from being converted from a lamellar state to a spinel state, and relieve the Jahn-Teller effect.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. The preparation method of the modified lithium-rich manganese-based positive electrode material is characterized by comprising the following steps of:
(1) Mixing manganese salt, doped metal salt and terephthalic acid solution, and performing solvothermal reaction to obtain a doped Mn-MOF material;
(2) The doped Mn-MOF materialMixing the material with oxidant and solvent, regulating pH value to make high-pressure hydrothermal reaction so as to obtain doped MnO 2 A material;
(3) The doped MnO 2 Mixing the material with a nickel source, a cobalt source and a lithium source, and roasting to obtain the modified lithium-rich manganese-based anode material.
2. The method of claim 1, wherein the manganese salt of step (1) comprises any one or a combination of at least two of manganese sulfate, manganese nitrate, or manganese chloride;
preferably, the doped metal salt comprises any one or a combination of at least two of chloride, nitrate or sulfate containing Ru, mg, al or Fe;
preferably, the mass ratio of the manganese salt to the doped metal salt is (3-8): 1;
preferably, the solvent of the terephthalic acid solution comprises any one or a combination of at least two of N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or methanol;
preferably, the concentration of the terephthalic acid solution is 10-50 g/L.
3. The process according to claim 1 or 2, wherein alkali is added and stirred before the solvothermal reaction in step (1);
preferably, the concentration of the alkali liquor is 0.2-0.8 mol/L;
preferably, the temperature of the solvothermal reaction is 90-120 ℃;
preferably, the solvothermal reaction time is 8-12 hours;
preferably, the solvothermal reaction is followed by washing and drying treatments;
preferably, the washed detergent comprises deionized water and/or ethanol.
4. A method according to any one of claims 1 to 3, wherein the oxidant of step (2) comprises potassium permanganate;
preferably, the mass ratio of the doped Mn-MOF material to the oxidant is (1.5-2.5): 1;
preferably, the solvent comprises deionized water.
5. The process according to any one of claims 1 to 4, wherein the pH in step (2) is from 0.5 to 1.5;
preferably, the device for high-pressure hydrothermal reaction comprises an autoclave;
preferably, the temperature of the high-pressure hydrothermal reaction is 120-180 ℃;
preferably, the time of the high-pressure hydrothermal reaction is 20-30 hours;
preferably, the high-pressure hydrothermal reaction is followed by centrifugation, washing and drying;
preferably, the washed detergent comprises deionized water and/or ethanol.
6. The method of any one of claims 1-5, wherein the nickel source of step (3) comprises any one or a combination of at least two of nickel nitrate, nickel chloride, or nickel sulfate;
preferably, the cobalt source comprises any one or a combination of at least two of cobalt nitrate, cobalt chloride or cobalt sulfate;
preferably, the lithium source comprises lithium hydroxide and/or lithium carbonate.
7. The method according to any one of claims 1 to 6, wherein the atmosphere of the calcination treatment in step (3) comprises oxygen and/or air;
preferably, the firing treatment includes one-step firing and two-step firing;
preferably, the temperature of the one-step roasting is 300-600 ℃;
preferably, the one-step roasting time is 3-10 hours;
preferably, the temperature of the two-step roasting is 600-1000 ℃;
preferably, the two-step roasting time is 10-20 hours.
8. A modified lithium-rich manganese-based cathode material, characterized in that it is produced by the method according to any one of claims 1 to 7.
9. A positive electrode sheet comprising the modified lithium-rich manganese-based positive electrode material of claim 8.
10. A lithium ion battery comprising the positive electrode sheet of claim 9.
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