CN113830841A - Anode solid solution material and preparation method and application thereof - Google Patents
Anode solid solution material and preparation method and application thereof Download PDFInfo
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- CN113830841A CN113830841A CN202111091803.9A CN202111091803A CN113830841A CN 113830841 A CN113830841 A CN 113830841A CN 202111091803 A CN202111091803 A CN 202111091803A CN 113830841 A CN113830841 A CN 113830841A
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- 239000000463 material Substances 0.000 title claims abstract description 45
- 239000006104 solid solution Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 238000007710 freezing Methods 0.000 claims abstract description 9
- 230000008014 freezing Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 229910013172 LiNixCoy Inorganic materials 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 3
- 229910052691 Erbium Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001816 cooling Methods 0.000 abstract description 5
- 239000012071 phase Substances 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 5
- 238000010583 slow cooling Methods 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000011572 manganese Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910013191 LiMO2 Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910015634 LiNi0.81 Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 229960003390 magnesium sulfate Drugs 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 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 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Images
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- C01G53/006—
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention provides a positive solid solution material and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing the precursor with a lithium source to obtain a mixture; (2) and (2) carrying out multi-stage roasting on the mixture obtained in the step (1), and then carrying out freezing treatment to obtain the anode solid solution material. The invention adopts the improved high-temperature solid-phase sintering method to treat the precursor, the prepared material can show excellent performances including good structural stability, thermal stability, rate capability and the like through multi-section roasting, and after roasting, as partial doped element component structure can be segregated in the slow cooling process, and the material is transformed to polycrystallization, the creative low-temperature rapid cooling process is added to rapidly skip the phase transition temperature zone, so that the consistency of the material is greatly improved, and the commercial application becomes possible.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and relates to an anode solid solution material and a preparation method and application thereof.
Background
The currently commercialized layered positive electrode material (especially high-nickel ternary positive electrode material) in the market has some intrinsic disadvantages, such as poor cycle stability caused by irreversible structural phase change due to cyclic phase change under high voltage; the electron conductivity is low and the multiplying power performance caused by Li/Ni mixed discharge is poor; in the highly delithiated state, Ni4+Has a strong oxidizing property tending to reduce to form Ni3+To release O2Resulting in poor thermal stability. At present, ion doping is the main means for improving the material performance, and some metal ions and non-metal ions are doped in material lattices, so that the electronic conductivity and the ionic conductivity can be improved to a certain degree, and the structural stability of the material can be improved. How to prepare the material doped with various metal ions into the anode material meeting the requirements and simultaneously ensure that the component proportion is not segregated in the preparation process to form a mature product with higher consistency, and no related report is provided at present.
CN104518214A discloses a preparation method of a layered lithium-rich solid solution cathode material, which effectively reduces Li in the material by adopting a preparation method of excessive lithium source sintering, washing and carrying out surface modification on a treated intermediate product+/Ni2+The residual alkali on the surface of the material is reduced and the stability of the material is improved while mixed drainage is carried out.
CN103311513A discloses a high-performance layered solid solution lithium battery positive electrode material and a preparation method thereof, and the chemical formula of the positive electrode material with low strength is Li [ ]1/3Mn2/3]O2·(1-x)LiMO2(M ═ Ni, Co, or Mn) is a layered compound of Li [ Li ]1/3Mn2/3]O2(i.e. Li)2MnO3) And LiMO2And (4) forming. The preparation method comprises the following steps: firstly, dissolving sulfates, nitrates, acetates and the like of manganese, nickel and cobalt in water according to a certain proportion to prepare a mixed cation solution, adding a proper precipitator into the mixed solution at a certain speed with stirring to synthesize a mixed hydroxide or carbonate coprecipitation precursor, mixing the dried precursor and lithium salt at a high speed according to a certain substance amount than a wet method, putting the precursor into an atmosphere furnace, and introducing oxygen to perform fractional sintering to obtain the solid solution material.
The scheme has the problems of poor cycling stability, poor multiplying power or low conductivity and the like, so that the development of the cathode solid solution material with good cycling stability, good multiplying power and high conductivity is necessary.
Disclosure of Invention
The invention aims to provide a positive solid solution material, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a solid solution material for a positive electrode, the method comprising the steps of:
(1) mixing the precursor with a lithium source to obtain a mixture;
(2) performing multi-stage roasting on the mixture obtained in the step (1), and performing freezing treatment to obtain the anode solid solution material;
the chemical formula of the precursor is NixCoyMn0.95-x-yA0.05(OH)2Wherein, x + y<0.95, a + b + c + d + e is 1, and a is at least five of Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu, or Er.
The invention adopts the improved high-temperature solid-phase sintering method to treat the precursor, the prepared material can show excellent performances including good structural stability, thermal stability, rate capability and the like through multi-section roasting, and after roasting, as partial doped element component structure can be segregated in the slow cooling process, and the material is transformed to polycrystallization, the creative low-temperature rapid cooling process is added to rapidly skip the phase transition temperature zone, so that the consistency of the material is greatly improved, and the commercial application becomes possible.
Preferably, the molar ratio of the precursor to the lithium source in the step (1) is 1 (0.9-1.2), such as: 1:0.9, 1:1.0, 1:1.1 or 1:1.2, etc.
Preferably, the lithium source comprises any one of lithium carbonate, lithium acetate or lithium hydroxide or a combination of at least two thereof.
Preferably, the multi-stage roasting of step (2) includes a first-stage roasting and a second-stage roasting.
Preferably, the atmosphere of the multi-stage roasting is oxygen.
Preferably, the temperature of the first-stage roasting is 300-500 ℃, such as: 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C or 500 deg.C.
Preferably, the period of time for the first roasting is 3-6 hours, such as: 3h, 3.5h, 4h, 4.5h, 5h or 6h and the like.
Preferably, the temperature of the second-stage roasting is 700-750 ℃, for example: 700 deg.C, 710 deg.C, 720 deg.C, 730 deg.C, 740 deg.C or 750 deg.C.
Preferably, the secondary roasting time is 20-30 h, for example: 20h, 22h, 25h, 28h or 30h and the like.
Preferably, the atmosphere of the freezing treatment in the step (2) is an oxygen atmosphere.
Preferably, the temperature of the freezing treatment in the step (2) is-10 to-20 ℃, for example: -10 ℃, -12 ℃, -15 ℃, -18 ℃ or-20 ℃ and the like.
Preferably, the end point of the freezing process is the reduction of the material temperature to room temperature.
In a second aspect, the present invention provides a positive electrode solid solution material produced by the method of the first aspect, the positive electrode solid solution material having a chemical formula of LiNixCoyMn0.95-x-yA0.05O2Wherein, x + y<0.95, a + b + c + d + e is 1, and a is at least five of Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu, or Er.
In a third aspect, the invention provides a positive electrode plate, which comprises the positive electrode solid solution material as described in the second aspect.
In a fourth aspect, the invention provides a lithium ion battery, which comprises the positive electrode plate according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the improved high-temperature solid-phase sintering method to treat the precursor, the prepared material can show excellent performances including good structural stability, thermal stability, rate capability and the like through multi-section roasting, and after roasting, as partial doped element component structure can be segregated in the slow cooling process, and the material is transformed to polycrystallization, the creative low-temperature rapid cooling process is added to rapidly skip the phase transition temperature zone, so that the consistency of the material is greatly improved, and the commercial application becomes possible.
Drawings
Fig. 1 is an SEM image of a solid solution material of a positive electrode according to example 1 of the present invention.
FIG. 2 is a graph showing the first specific charge-discharge capacity of a button cell made of the material of example 1 at 3-4.3V and 0.1C.
Fig. 3 is an SEM image of the positive electrode solid solution material according to example 2 of the present invention.
Fig. 4 is a graph of the rate performance at 3-4.3V for a button cell made from the material described in example 2.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The precursors adopted in the embodiments and the comparative examples of the invention are all prepared by the following methods:
(1) dissolving nickel sulfate, cobalt sulfate, manganese sulfate, zinc sulfate, magnesium sulfate and chromium sulfate in deionized water to prepare a solution A, dissolving tin sulfate and aluminum sulfate in 10L of 0.5M IDS solution to prepare a solution B, preparing 10L of a complexing agent (namely ammonia water solution) with the concentration of 0.4M, and adding 0.02M sodium tungstate as a tungsten source to obtain a solution C;
(2) adding 5L of deionized water into a 30L reaction kettle, adding 200mL of 25% concentrated ammonia water serving as a base solution, adjusting the pH to 11, maintaining the temperature at 50 ℃, introducing 4h of nitrogen into the reaction kettle, maintaining the inert gas environment, injecting the prepared solution A, solution B and solution C into the reaction kettle with the nitrogen protection atmosphere at the rotating speed of 600rmp at the speed of 200mL/h, simultaneously adding the solution A, solution B and solution C into the base solution at a constant speed (namely 200mL/h) in a parallel flow manner, adjusting the pH in the reaction process by sodium hydroxide, carefully adjusting the flow rate of an alkali solution, and controlling the pH to be 11 by an online pH controller; ensuring that the final Ni: co: mn: sn: zn: mg: w: cr: molar ratio of Al 0.82: 0.1: 0.03: 0.01: 0.01: 0.01: 0.01: 0.005: 0.005; and after the reaction is carried out for 25 hours, the salt solution and the complexing agent are completely injected into the reaction kettle, the coprecipitation process is finished after the aging is carried out for 10 hours, the solid-liquid mixture is centrifugally filtered and separated, washed to be neutral by deionized water, and dried for 25 hours at the temperature of 100 ℃ to obtain the precursor.
Example 1
The embodiment provides a positive solid solution material, which is characterized in that the preparation method of the positive solid solution material is as follows:
(1) mixing the precursor and lithium hydroxide according to a molar ratio of 1:1.05 to obtain a mixture;
(2) and (2) placing the mixture obtained in the step (1) in a tubular furnace for multistage oxygen-introducing roasting, firstly heating from room temperature to 470 ℃ at a heating rate of 6 ℃, preserving heat for 6h, then heating to 750 ℃ and preserving heat for 20h, cooling to room temperature at a low temperature of-15 ℃, introducing oxygen in the whole process, grinding and sieving to obtain the anode solid solution material.
Obtaining the spherical layered high-entropy chemically stable cathode material LiNi0.81Co0.1Mn0.04(Sn0.01Zn0.01Mg0.01W0.01Cr0.005Al0.005)O2The scanning electron microscope is shown in FIG. 1, the particle size D50 is 8.33 μm, and the tap density is 2.11g/cm3。
The positive electrode material is made into a 2032 button cell, and as shown in fig. 2, the first charge-discharge specific capacity curve of the button cell at 3-4.3V and 0.1C shows that the first discharge specific capacity can reach 197.5mAh/g, and the efficiency can reach 84.7%.
Example 2
The embodiment provides a positive solid solution material, which is characterized in that the preparation method of the positive solid solution material is as follows:
(1) mixing the precursor and lithium hydroxide according to a molar ratio of 1:1.03 to obtain a mixture;
(2) and (2) placing the mixture obtained in the step (1) in a tubular furnace for multistage oxygen-introducing roasting, firstly heating to 500 ℃ from room temperature at a heating rate of 5 ℃ and preserving heat for 6h, then heating to 750 ℃ and preserving heat for 30h, cooling to room temperature at-12 ℃, introducing oxygen in the whole process, grinding and sieving to obtain the anode solid solution material.
Obtaining the spherical layered high-entropy chemically stable cathode material LiNi0.8Co0.1Mn0.05Mo0.015W0.015Zr0.005Al0.00 5Y0.01O2. The scanning electron microscope is shown in FIG. 3, the particle size D50 is 5.49 μm, and the tap density is 1.89g/cm3。
The positive electrode material is made into a 2032 button cell, and a rate performance graph of the button cell under a 3-4.3V test condition is shown in figure 4.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a solid solution material of a positive electrode is characterized by comprising the following steps:
(1) mixing the precursor with a lithium source to obtain a mixture;
(2) performing multi-stage roasting on the mixture obtained in the step (1), and performing freezing treatment to obtain the anode solid solution material;
the chemical formula of the precursor is NixCoyMn0.95-x-yA0.05(OH)2Wherein, x + y<0.95, a + b + c + d + e is 1, A is at least five of Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu or Er。
2. The preparation method according to claim 1, wherein the molar ratio of the precursor to the lithium source in step (1) is 1 (0.9-1.2);
preferably, the lithium source comprises any one of lithium carbonate, lithium acetate or lithium hydroxide or a combination of at least two thereof.
3. The method according to claim 1 or 2, wherein the multistage firing of step (2) includes a first-stage firing and a second-stage firing;
preferably, the atmosphere of the multi-stage roasting is oxygen.
4. The preparation method of claim 3, wherein the temperature of the primary roasting is 300-500 ℃;
preferably, the time for the first-stage roasting is 3-6 hours.
5. The preparation method according to claim 3, wherein the temperature of the secondary roasting is 700-750 ℃;
preferably, the secondary roasting time is 20-30 h.
6. The production method according to any one of claims 1 to 5, wherein the atmosphere of the freezing treatment in the step (2) is an oxygen atmosphere.
7. The method according to any one of claims 1 to 5, wherein the temperature of the freezing treatment in the step (2) is from-10 ℃ to-20 ℃;
preferably, the end point of the freezing process is the reduction of the material temperature to room temperature.
8. A positive electrode solid solution material prepared by the method according to any one of claims 1 to 7, characterized in that it has the chemical formula LiNixCoyMn0.95-x-yA0.05O2Wherein, x + y<0.95, a + b + c + d + e is 1, and a is at least five of Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Mg, Ca, Ru, Sn, Sb, W, Al, Mo, Y, Nb, La, Ce, Eu, or Er.
9. A positive electrode sheet, characterized in that it comprises the positive electrode solid solution material according to claim 8.
10. A lithium ion battery comprising the positive electrode sheet of claim 9.
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