CN109461893B - Novel lithium ion battery anode material and preparation method thereof - Google Patents
Novel lithium ion battery anode material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- 239000010405 anode material Substances 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 70
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 34
- 239000002019 doping agent Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000002344 surface layer Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 77
- 238000006243 chemical reaction Methods 0.000 claims description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229910007822 Li2ZrO3 Inorganic materials 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 21
- 229910052723 transition metal Inorganic materials 0.000 claims description 18
- 230000008859 change Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 150000003624 transition metals Chemical class 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000007774 positive electrode material Substances 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- -1 transition metal salt Chemical class 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 235000006708 antioxidants Nutrition 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 claims description 2
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 229940001607 sodium bisulfite Drugs 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 229940116269 uric acid Drugs 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 59
- 239000002245 particle Substances 0.000 abstract description 26
- 229910052726 zirconium Inorganic materials 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- 229910003684 NixCoyMnz Inorganic materials 0.000 abstract description 2
- 229910052772 Samarium Inorganic materials 0.000 abstract description 2
- 229910052796 boron Inorganic materials 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 229910052758 niobium Inorganic materials 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 229910052721 tungsten Inorganic materials 0.000 abstract description 2
- 229910052720 vanadium Inorganic materials 0.000 abstract description 2
- 229910052727 yttrium Inorganic materials 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 43
- 239000013078 crystal Substances 0.000 description 15
- 239000010406 cathode material Substances 0.000 description 14
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 10
- 229940044175 cobalt sulfate Drugs 0.000 description 10
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 10
- 229940099596 manganese sulfate Drugs 0.000 description 10
- 239000011702 manganese sulphate Substances 0.000 description 10
- 235000007079 manganese sulphate Nutrition 0.000 description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 10
- 229940053662 nickel sulfate Drugs 0.000 description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910013716 LiNi Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 description 1
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
- H01M4/362—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
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a novel lithium ion battery anode material and a preparation method thereof, wherein the material has the average composition as follows: li0.6+δNixCoyMnzO2·EηDelta is more than or equal to 0 and less than or equal to 0.6, x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.4, η is more than or equal to 0 and less than or equal to 0.1, E is Li2‑kMO3‑k/2K is more than or equal to 0 and less than or equal to 1.8, wherein M is one or more of La, Cr, Mo, Ca, Fe, Hf, Zr, Zn, Ti, Y, Zr, W, Nb, Sm, V, Mg, B and Al, and the content of the dopant E continuously increases from the particle core to the surface and is enriched on the surface layer. The invention can effectively improve the cycle life and the safety of the high-nickel material by controlling the content of each element in the material and the reasonable distribution of the gradient dopant, and has simple material preparation process, continuous controllability and low cost.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a novel lithium ion battery anode material and a preparation method thereof.
Background
At present, the electric vehicle is developed rapidly and is combined with lithium cobaltate LiCoO2Spinel lithium manganate LiMn2O4And lithium iron phosphate LiFePO4Compared with the three materials, the commercial lithium ion battery cathode material LiNixCoyMn1-x-yO2The reversible capacity of the nickel-based composite material is increased along with the increase of the content of the Ni element in the material, namely, the nickel-based composite material can provide higher specific capacity and specific energy and becomes an electric motorThe preferred material for vehicles. According to the characteristics of the ternary material, when the Ni content is increased to x =0.80, the reversible capacity of the material can reach 190mAh g-1Above, when x is less than 0.5, the material is highly safe but has a slightly low capacity, and in short, the high capacity characteristics, rate capability, cycle capability, safety performance, and the like of the material cannot satisfy the requirements at the same time. How to improve the cycle performance and safety of high-capacity and high-rate materials is one of the key problems to be solved urgently.
High nickel ternary materials provide high capacity and high rate, but the capacity of the material decays relatively fast, mainly due to: (1) when the battery is subjected to a cycle test, the high nickel material subjected to multiple phase changes exists, and irreversible phase changes occurring in the crystal structure of the high nickel material cause the crystal structure to collapse, so that the normal insertion and extraction of lithium ions are prevented, the impedance of the battery is increased, and the service life of the battery is shortened; (2) the lithium ions in the anode material are unevenly distributed and Li/Ni is mixed, so that the crystal structure of the material is not stable enough, the problem of overcharge and discharge in the material is caused, and the cycle life of the material is influenced; (3) ni exists on the surface of the charged high-nickel ternary material4+Leading to the oxidation of the electrolyte and the generation of gas, thereby affecting the comprehensive performance of the material.
How to improve the crystal structure and interface stability of the anode material and improve the rate capability, cycle performance and safety performance of the anode material, the prior art means are mainly divided into the following three types: surface coating, bulk phase doping, and controlling particle size, etc. Li prepared by Chinese patent CN103265071B2ZrO3A material which has electrochemical activity but has a narrow electrochemical window and cannot be used independently as an active material. Chinese patent CN105470455A prepares a surface-coated Li2ZrO3LiNi of (2)0.8Co0.15Al0.05O2The transition metal oxide is used as an anode active substance, the material with the high lithium ion conductivity and the high conductivity coating layer has good cycle performance and rate capability, but the surface coating cannot be stabilized on the surface of the material for a long time, and the stress strain generated after multiple reactions causes the coating layer to fall off, so that the comprehensive performance of the material is poor.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a novel lithium ion battery anode material and a preparation method thereof, the method can provide a material with a stable crystal structure, and can effectively improve the cycle life and safety of a nickel-rich material by controlling the content of each element in the material and the reasonable distribution of gradient dopants, and the material has simple preparation process and low cost.
In order to achieve the purpose, the invention discloses a novel lithium ion battery anode material, which has the average composition as follows: li0.6+δNixCoyMnzO2·EηDelta is more than or equal to 0 and less than or equal to 0.6, x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.4, η is more than or equal to 0 and less than or equal to 0.1, E is Li2-kMO3-k/2K is more than or equal to 0 and less than or equal to 1.8, wherein M is one or more of La, Cr, Mo, Ca, Fe, Hf, Zr, Zn, Ti, Y, Zr, W, Nb, Sm, V, Mg, B and Al, and the content of the dopant E in the cathode material is gradually increased from the particle core to the surface and is enriched on the surface layer.
On the other hand, in order to achieve the purpose of the invention, the invention also provides a preparation method of the novel lithium ion battery anode material, and the specific technical scheme comprises the following steps:
(1) ni, Co and Mn transition metal soluble salt is used as a raw material, a transition metal salt mixed solution is prepared according to a certain proportion and added into a raw material tank, and the proportion of each transition metal ion in the anode material is adjusted by adding transition metal salt solutions with different concentrations;
(2) using two or more different concentrations of Li2ZrO3Separating sol into tanks, and adding low-concentration Li2ZrO3Adding sol into dopant tank by controlling Li2ZrO3Regulating and controlling the dopant in the dopant master tank by the flow rate of the sol and the volume of liquid in the dopant master tank so as to control Li in the material2ZrO3The element content is gradually increased, when the reaction is finished, the addition of transition metal salt solution is stopped, the concentration change in the adulterant main tank is stopped, and the reaction is carried out for a period of time to reach the endThe effect of surface enrichment of dopants;
(3) continuously adding the solution in the raw material tank, the solution in the dopant master tank, a precipitator and a complexing agent into the reactor in a parallel flow manner, and controlling the content of the dopant to be gradually increased; under the condition of introducing inert gas, controlling the temperature of the reactor to be 30-70 ℃, the pH value to be 8.0-12.5, and continuously reacting for 5-40 h;
(4) taking out the product obtained in the step (3), washing with water, carrying out solid-liquid separation, and drying to obtain a precursor;
(5) and mixing the precursor with a lithium source material in a certain stoichiometric ratio, placing the mixture into an atmosphere sintering furnace for sintering, controlling the temperature to be 300-900 ℃ and the time to be 5-40 h, and screening the sintered product to obtain the novel lithium ion battery anode material.
In the preparation method, the total concentration of Ni, Co and Mn in the transition metal salt mixed solution in the step (1) is 0.5-3.5 mol/L.
In the preparation method, the precipitator in the step (3) is one or more of sodium hydroxide, potassium hydroxide or lithium hydroxide; the complexing agent is one or more of ammonia water, ammonium sulfate, ammonium nitrate and ammonium chloride; the inert gas is one or two of nitrogen and argon.
In the preparation method, the co-current flow mode in the step (3) is continuously added into a reactor with stirring through a precision feeding system, the pH value is monitored to be 9.5-12 in real time, and the temperature of the reaction system is 30-65 ℃.
In the preparation method, the surfactant in the step (3) is one or more of polyvinylpyrrolidone, polyvinyl alcohol and sodium dodecyl sulfate.
In the preparation method, the co-current feeding in the step (3) into the reactor further comprises an antioxidant, wherein the antioxidant is one or more of ascorbic acid, sodium bisulfite and uric acid.
In the preparation method, an ion monitoring washing system is adopted in the washing process in the step (4), a filter pressing, suction filtration or centrifugal device is adopted for solid-liquid separation, and the drying temperature is 80-140 ℃.
In the preparation method, the adding amount of the lithium source in the step (5) is that the molar ratio of Li/(Ni + Co + Mn) is = 0.90-1.10, and the temperature is controlled at 0-50 ℃;
in the above production method, Li as described in step (6)2ZrO3Gradient doped high nickel multi-element anode material D 505 to 20 μm, and a specific surface area of 0.1 to 1.0m2The tap density reaches 1.5 to 3.0g/cm3。
The principle of the invention is as follows: aiming at the problems of unstable structure, difficult synthesis and the like existing in the high-nickel multi-element material, by adding a Li-containing dopant with gradient change, lithium ions in the material can be reasonably distributed in the synthesis process, and the lithiation reaction is promoted; in addition, the dopant is enriched on the surface and interface of the material to generate a coating effect, so that the structural stability and safety of the material are enhanced.
Compared with the prior art, the invention has the following beneficial effects:
(1) the variety, content and doping mode of the dopant are controllable, gradient doping among primary crystal grains of the precursor can be realized, partial lithium ion transmission channels can be provided while doping, and the aim of stabilizing the crystal structure of the material is fulfilled.
(2) The gradient doping among the crystal grains of the precursor can promote the complete growth of the crystal structure and support the crystal grain gaps in the high-temperature synthesis process of the material, and simultaneously accelerate the transmission of lithium ions, so that the lithiation reaction of a lithium source is easier to perform during the preparation of the anode material; and the dopant enters the inactive site of the material, which is beneficial to maintaining the high capacity characteristic of the high nickel material.
(3) The gradient doping and surface enrichment can generate double functions of doping and coating, enhance the structural stability and interface stability of the material, and control the residual alkali amount on the surface of the material so as to improve the rate capability, cycle performance and safety of the material.
Description of the drawings:
fig. 1 is an XRD test pattern of the cathode material in example 1.
FIG. 2 is an SEM test chart of a cross section of the precursor in example 1.
FIG. 3 is an SEM test chart of a cross section of the cathode material in example 1.
Fig. 4 is a graph showing the tendency of Zr element change in the positive electrode material of example 1.
Fig. 5 is an ion sectional view of the positive electrode materials of example 1 and comparative example 1.
Fig. 6 is a graph of the cycling performance of the button cells of the positive electrode materials in example 1, comparative example 1, and comparative example 2.
Detailed Description
The present invention will be described in further detail below with reference to examples.
In the examples, the performance (discharge capacity, rate capability, cycle performance) of a battery prepared by gradient doping a high nickel cathode material to a lithium ion battery prepared by the method of the present invention was confirmed.
The crystal structure of the materials prepared in the examples was measured by X-ray diffraction.
Button cells were made as follows:
firstly, mixing a gradient doped positive electrode active substance, acetylene black and polyvinylidene fluoride (PVDF) for a non-aqueous electrolyte secondary battery according to a mass ratio of 92% to 4%, coating the mixture on an aluminum foil, drying the aluminum foil, performing press forming by using 100Mpa pressure to form a positive electrode plate with a diameter of 12mm and a thickness of 120 mu m, and then putting the positive electrode plate into a vacuum drying box to dry for 12 hours at 120 ℃.
The negative electrode uses a Li metal sheet with the diameter of 17mm and the thickness of 1 mm; the separator used was a polyethylene porous film having a thickness of 25 μm; the electrolyte used was LiPF at 1 mol/L6An equal amount of a mixture of Ethylene Carbonate (EC) and diethyl carbonate (DEC) as electrolytes.
And then assembling the positive pole piece, the diaphragm, the negative pole piece and the electrolyte into a 2025 type button cell in an Ar gas glove box with the water content and the oxygen content of less than 5 ppm.
For the performance evaluation of the button cells made, the cycle performance test is defined as follows:
the initial discharge specific capacity is that the button cell is placed for 24h after being manufactured, after the open-circuit voltage is stable, the current density of the anode is charged to be 4.3V of cut-off voltage in a mode of 20mA/g, the anode is charged for 30min at a constant voltage of 4.3V, then the anode is discharged to be 3.0V of cut-off voltage in the same current density, the discharging is repeated again in the same mode, and the battery at the moment is used as an activated battery.
The cycle performance was tested as follows: the high-temperature capacity retention rate of the material is examined by using an activated battery and using a voltage interval of 3.0-4.3V as a current density of 1C and a temperature of 55 ℃ for 100 cycles.
The following examples will help to understand the present invention, but do not limit the contents thereof.
Example 1
Li2ZrO3The gradient doped high-nickel multi-element cathode material comprises the initial metal ion ratio of Ni to Co to Mn =0.90 to 0.05 and the dopant Li2ZrO3The content is continuously increased from the core of the particle to the surface of the particle, the change rule is 0-0.02, meanwhile, the content of Mn element is continuously reduced from the center to the surface, the change rule is 0.05-0.03, and the total amount of the adulterant and the Mn element is kept to be 0.05. The average composition of the resulting material was LiNi0.9Co0.05Mn0.04O2·(Li2ZrO3)0.01Having an average particle diameter of about 12.0 μm and a tap density of about 2.6 g/cm3。
The preparation method comprises the following steps:
preparing a 1.5mol/L mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with the molar ratio of 0.90:0.05:0.05, marking as a solution (1), putting the solution into a branch tank R1, preparing a 1.5mol/L mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with the molar ratio of 0.92:0.051:0.029, marking as a solution (2), putting the solution into a branch tank R2, and then adding the solution in the branch tank R2 into R1 with stirring at the flow rate of 0.2L/h to obtain a solution (3) with gradient change. Preparing a solution containing a lithium zirconate sol stabilizer, marking as a solution (4), putting the solution into a branch tank R3, preparing a 2mol/L solution of lithium zirconate sol, marking as a solution (5), and putting the solution into a branch tank R4. Adding the solution split into tanks of R4 into the stirred R3 at the flow rate of 0.1L/h to obtain a gradient solution (6), and then adding a transition metal salt solution (3), a lithium zirconate gradient doping solution (6), 6mol/L NaOH and 4mol/L NH3·H2Slowly adding O into a stirred reaction kettle, and controlling the reaction system in the processThe pH value is 11.0, the temperature of the whole system is controlled at 55 ℃, and the reaction is carried out at N2And (3) performing crystallization growth reaction in air, stopping adding the transition metal solution when the particle size grows to 11.0 mu m, adding the dopant, reacting for a certain time, stopping all reactions, and performing water washing, filtering, drying and other treatment on the material to obtain the Mn element compensation lithium zirconate gradient doped high-nickel spherical precursor.
Mixing the precursor with lithium hydroxide, and uniformly mixing in a mixing kettle, wherein the mass ratio of Li: (Ni + Co + Mn) =1.05, sintering is carried out for 15 hours at 750 ℃ in an oxygen atmosphere, and the Mn element compensated lithium zirconate gradient-doped spherical high-nickel anode LiNi is obtained0.9Co0.05Mn0.04O2·(Li2ZrO3)0.01A material. As shown in FIG. 1, the obtained cathode material has a crystal structure conforming to the R-3m hexagonal system and has a complete layered structure. As shown in fig. 2, the crystal structure inside the obtained spherical precursor material has directional growth and no hollow phenomenon. As shown in fig. 3, the crystal structure inside the obtained spherical positive electrode material has directional growth, which is beneficial to improving the material performance. The results shown in fig. 4 were obtained by testing the cross-sectional view of fig. 3 using EPMA, and the obtained dopant in the positive electrode material was in accordance with the gradient and the design value. As can be seen from comparison of the brightness of each crystal grain in fig. 5, the difference in brightness of the positive electrode material particles in example 1 is small, while the difference in brightness of the positive electrode material particles in comparative example 1 is large, which indicates that there is a difference in material conductivity, i.e., the positive electrode material in example 1 with a small difference in brightness has better conductivity.
Example 2
Li2ZrO3The gradient doped high-nickel multi-element cathode material comprises the initial metal ion ratio of Ni to Co to Mn =0.80 to 0.10 and the dopant Li2ZrO3The content is continuously increased from the core of the particle to the surface of the particle, the change rule is 0-0.04, meanwhile, the content of Mn element is continuously reduced from the center to the surface, the change rule is 0.10-0.06, and the total amount of the adulterant and the Mn element is kept to be 0.10. The average composition of the resulting material was LiNi0.8Co0.10Mn0.08O2·(Li2ZrO3)0.02Having an average particle diameter of about 8 μm and a tap density of about 2.6 g/cm3。
The preparation method comprises the following steps:
preparing a 1.5mol/L mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with the molar ratio of 0.80:0.10:0.10, marking as a solution (1), putting the solution into a branch tank R1, preparing a 1.5mol/L mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with the molar ratio of 0.834:0.104:0.059, marking as a solution (2), putting the solution into a branch tank R2, and then adding the solution in the branch tank R2 into R1 with stirring at the flow rate of 0.2L/h to obtain a solution (3) with gradient change. Preparing a solution containing a lithium zirconate sol stabilizer, marking as a solution (4), putting the solution into a branch tank R3, preparing a 2mol/L solution of lithium zirconate sol, marking as a solution (5), and putting the solution into a branch tank R4. Adding the solution split into tanks of R4 into the stirred R3 at the flow rate of 0.2L/h to obtain a gradient solution (6), and then adding a transition metal salt solution (3), a lithium zirconate gradient doping solution (6), 6mol/L NaOH and 4mol/L NH3·H2Slowly adding O into a stirred reaction kettle, controlling the pH value in the reaction system to be 11.0 in the process, controlling the temperature of the whole system to be 55 ℃, and reacting in N2And (3) performing crystallization growth reaction in air, stopping the reaction until the particle size grows to 12.0 mu m, and performing water washing, filtering, drying and other treatment on the material to obtain the Mn element compensated lithium zirconate gradient doped high nickel spherical precursor.
Mixing the precursor with lithium hydroxide, and uniformly mixing in a mixing kettle, wherein the mass ratio of Li: (Ni + Co + Mn) =1.05, sintering is carried out for 15 hours at 800 ℃ in an oxygen atmosphere, and the Mn element compensated lithium zirconate gradient-doped spherical high-nickel anode LiNi is obtained0.8Co0.10Mn0.08O2·(Li2ZrO3)0.02A material.
Example 3
Li2ZrO3The gradient doped high-nickel multi-element cathode material comprises the initial metal ion ratio of Ni to Co to Mn =0.60 to 0.20 and the dopant Li2ZrO3The content is continuously increased from the core of the particle to the surface of the particle, the change rule is 0-0.06, and simultaneously, the content of Mn element is not increased from the center to the surfaceThe breaking rate is reduced, the change rule is 0.20-0.14, and the total amount of the dopant and the Mn element is kept to be 0.20. The average composition of the resulting material was LiNi0.6Co0.20Mn0.17O2·(Li2ZrO3)0.03Having an average particle diameter of about 11.0 μm and a tap density of about 2.5 g/cm3。
The preparation method comprises the following steps:
preparing a 1.5mol/L mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with the molar ratio of 0.60:0.20:0.20, marking as a solution (1), putting the solution into a branch tank R1, preparing a 1.5mol/L mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with the molar ratio of 0.638:0.213:0.149, marking as a solution (2), putting the solution into a branch tank R2, and then adding the solution in the branch tank R2 into a stirred R1 at the flow rate of 0.2L/h to obtain a gradient-changed solution (3). Preparing a solution containing a lithium zirconate sol stabilizer, marking as a solution (4), putting the solution into a branch tank R3, preparing a 2mol/L solution of lithium zirconate sol, marking as a solution (5), and putting the solution into a branch tank R4. Adding the solution split into tanks of R4 into the stirred R3 at the flow rate of 0.3L/h to obtain a gradient solution (6), and then adding the solution of the transition metal salt (3), the gradient doping solution of the lithium zirconate (6), 6mol/L NaOH and 4mol/L NH3·H2Slowly adding O into a stirred reaction kettle, controlling the pH value in the reaction system to be 11.5 in the process, controlling the temperature of the whole system to be 55 ℃, and reacting in N2And (3) performing crystallization growth reaction in air, stopping the reaction until the particle size grows to 10.0 mu m, and performing water washing, filtering, drying and other treatment on the material to obtain the Mn element compensated lithium zirconate gradient doped high nickel spherical precursor.
Mixing the precursor with lithium hydroxide, and uniformly mixing in a mixing kettle, wherein the mass ratio of Li: (Ni + Co + Mn) =1.05, sintering is carried out for 15 hours at 850 ℃ in an oxygen atmosphere, and the Mn element compensated lithium zirconate gradient-doped spherical high-nickel anode LiNi is obtained0.6Co0.20Mn0.17O2·(Li2ZrO3)0.03A material.
Example 4
Li2ZrO3The gradient doped high-nickel multi-element cathode material comprises the following initial metal ion ratios of Ni to Co:mn =0.60:0.20:0.20, dopant Li2ZrO3The content of the Mn-doped iron-based composite material is continuously increased from the core of the particles to the surface of the particles, the change rule is 0-0.16, the content of the Mn element is continuously reduced from the center to the surface, the change rule is 0.20-0.04, and the total amount of the dopant and the Mn element is kept to be 0.20. The average composition of the resulting material was LiNi0.6Co0.20Mn0.12O2·(Li2ZrO3)0.08Having an average particle diameter of about 11.0 μm and a tap density of about 2.5 g/cm3。
The preparation method comprises the following steps:
preparing a 1.5mol/L mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with the molar ratio of 0.60:0.20:0.20, marking as a solution (1), putting the solution into a branch tank R1, preparing a 1.5mol/L mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with the molar ratio of 0.672:0.224:0.104, marking as a solution (2), putting the solution into a branch tank R2, and then adding the solution in the branch tank R2 into a stirred R1 at the flow rate of 0.2L/h to obtain a solution (3) with gradient change. Preparing a solution containing a lithium zirconate sol stabilizer, marking as a solution (4), putting the solution into a branch tank R3, preparing a 2mol/L solution of lithium zirconate sol, marking as a solution (5), and putting the solution into a branch tank R4. Adding the solution split into tanks of R4 into the stirred R3 at the flow rate of 0.8L/h to obtain a gradient solution (6), and then adding a transition metal salt solution (3), a lithium zirconate gradient doping solution (6), 6mol/L NaOH and 4mol/L NH3·H2Slowly adding O into a stirred reaction kettle, controlling the pH value in the reaction system to be 11.5 in the process, controlling the temperature of the whole system to be 55 ℃, and reacting in N2And (3) performing crystallization growth reaction in air, stopping the reaction until the particle size grows to 10.0 mu m, and performing water washing, filtering, drying and other treatment on the material to obtain the Mn element compensated lithium zirconate gradient doped high nickel spherical precursor.
Mixing the precursor with lithium hydroxide, uniformly mixing in a mixing kettle, sintering Li/(Ni + Co + Mn) =1.05 at 850 ℃ for 15h in an oxygen atmosphere to obtain Mn element compensated lithium zirconate gradient doped spherical high-nickel anode LiNi0.6Co0.20Mn0.12O2·(Li2ZrO3)0.08A material.
Comparative example 1
The high-nickel multi-element cathode material comprises transition metal ions of Ni, Co and Mn =0.90, 0.05 and 0.05. The average composition of the resulting material was LiNi0.9Co0.05Mn0.05O2Having an average particle diameter of about 12.0 μm and a tap density of about 2.6 g/cm3。
The preparation method comprises the following steps:
a1.5 mol/L mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with the molar ratio of 0.90:0.05:0.05 is prepared and recorded as a solution (1). The transition metal salt solution (1), 6mol/L NaOH and 4mol/L NH are then mixed3·H2Slowly adding O into a stirred reaction kettle, controlling the pH value in the reaction system to be 11.0 in the process, controlling the temperature of the whole system to be 55 ℃, and reacting in N2And (3) performing crystallization growth reaction in air, stopping the reaction until the particle size grows to 11.0 mu m, and performing water washing, filtering, drying and other treatment on the material to obtain the high-nickel spherical precursor.
Mixing the precursor with lithium hydroxide, uniformly mixing in a mixing kettle, sintering Li/(Ni + Co + Mn) =1.06 at 750 ℃ for 15h in an oxygen atmosphere to obtain the spherical high-nickel anode LiNi0.9Co0.05Mn0.05O2A material.
Comparative example 2
The Zr-doped high-nickel multi-element cathode material has the initial metal ion ratio of Ni to Co to Mn =0.909 to 0.0505 to 0.0414, the Zr content of a dopant is kept constant from the particle core to the particle surface by 0.01, and the total amount of the dopant and Ni, Co and Mn elements is kept to be 1. The average composition of the resulting material was LiNi0.9Co0.05Mn0.04Zr0.01O2Having an average particle diameter of about 12.0 μm and a tap density of about 2.6 g/cm3。
The preparation method comprises the following steps:
preparing a 1.5mol/L mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate with the molar ratio of 0.909:0.0505:0.0414, marking as a solution (1), and putting the solution into a branch tank. Preparing 2mol/L solution of zirconium sol, marking as solution (2) and putting the solution into a branch tank. Then the transition metal salt solution (1) and the zirconium sol ladder are mixedDoping solution (2), 6mol/L NaOH and 4mol/L NH3·H2Slowly adding O into a stirred reaction kettle, controlling the pH value in the reaction system to be 11.0 in the process, controlling the temperature of the whole system to be 55 ℃, and reacting in N2And (3) performing crystallization growth reaction in air, stopping the reaction until the grain size grows to 11.0 mu m, and performing water washing, filtering, drying and other treatment on the material to obtain the zirconium-doped nickelic spherical precursor.
Mixing the precursor with lithium hydroxide, and uniformly mixing in a mixing kettle, wherein the mass ratio of Li: (Ni + Co + Mn) =1.05, sintering is carried out for 15 hours at 750 ℃ in an oxygen atmosphere, and zirconium-doped spherical high-nickel cathode LiNi is obtained0.9Co0.05Mn0.04Zr0.01O2A material. As shown in fig. 6, the cycle performance of the cathode material obtained in example 1 is higher than that of the cathode materials in comparative examples 1 and 2, which shows that the effect of gradient doping of Mn-compensated lithium zirconate on the improvement of the material performance is more excellent.
Finally, it is to be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: it is to be understood that modifications may be made to the technical solutions described in the foregoing embodiments, or some or all of the technical features may be equivalently replaced, and the modifications or the replacements may not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. A preparation method of a lithium ion battery anode material is characterized by comprising the following steps:
(1) ni, Co and Mn transition metal soluble salt is used as a raw material, a transition metal salt mixed solution is prepared according to a certain proportion and added into a raw material tank, and the proportion of each transition metal ion in the anode material is adjusted by adding transition metal salt solutions with different concentrations;
(2) using two or more different concentrations of Li2ZrO3Separating sol into tanks, and adding low-concentration Li2ZrO3Doping by sol additionTotal canister of material by controlling Li2ZrO3Regulating and controlling the dopant in the dopant master tank by the flow rate of the sol and the volume of liquid in the dopant master tank so as to control Li in the material2ZrO3The element content is gradually increased, when the reaction is carried out to the end, the addition of the transition metal salt solution is stopped, the concentration change in the dopant total tank is stopped, and the reaction is carried out for a period of time to achieve the effect of surface layer enrichment;
(3) continuously adding the solution in the raw material tank, the solution in the dopant master tank, a precipitator and a complexing agent into the reactor in a parallel flow manner, and controlling the content of the dopant to be gradually increased; controlling the temperature of the reactor to be 30-70 ℃, the pH value to be 8.0-12.5 and the continuous reaction time to be 5-40 h under the condition of introducing nitrogen or argon;
(4) taking out the product obtained in the step (3), washing with water, carrying out solid-liquid separation, and drying to obtain a precursor;
(5) mixing the precursor with a lithium source material in a certain stoichiometric ratio, placing the mixture into an atmosphere sintering furnace for sintering, controlling the temperature to be 300-900 ℃ and the time to be 5-40 h, and screening the sintered product to obtain a novel lithium ion battery anode material;
in the step (1), the total concentration of Ni, Co and Mn in the transition metal salt mixed solution is 0.5-3.5 mol/L;
in the step (5), the molar ratio of the lithium source material in terms of lithium element contained therein to the precursor in terms of transition metal elements of Ni, Co and Mn contained therein used in the mixing treatment is 0.90 to 1.10, and the temperature is controlled to be 0 to 50 ℃.
2. The method according to claim 1, wherein the precipitant in step (3) is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide; the complexing agent is one or more of ammonia water, ammonium sulfate, ammonium nitrate and ammonium chloride.
3. The method according to claim 1, wherein the concurrent flow in step (3) is continuously fed into the stirred reactor through a precision feeding system, the pH value is monitored in real time to be 9.5-12, and the temperature of the reaction system is monitored to be 30-65 ℃.
4. The process of claim 1, wherein said co-current addition to the reactor in step (3) further comprises an antioxidant, wherein the antioxidant is one or more of ascorbic acid, sodium bisulfite, and uric acid.
5. The method according to claim 1, wherein an ion monitoring washing system is adopted in the washing process in the step (4), a filter pressing, suction filtration or centrifugal device is adopted for solid-liquid separation, and the drying temperature is 80-140 ℃.
6. Novel lithium ion battery positive electrode material prepared by the method of any one of claims 1 to 5, characterized in that the positive electrode material D505 to 20 μm, and a specific surface area of 0.1 to 1.0m2The tap density reaches 1.5 to 3.0g/cm3。
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| KR20170075915A (en) * | 2015-12-23 | 2017-07-04 | 주식회사 포스코 | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
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