CN109437333A - A kind of nickel galaxite presoma and preparation method thereof and anode material for lithium-ion batteries - Google Patents
A kind of nickel galaxite presoma and preparation method thereof and anode material for lithium-ion batteries Download PDFInfo
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- CN109437333A CN109437333A CN201811245612.1A CN201811245612A CN109437333A CN 109437333 A CN109437333 A CN 109437333A CN 201811245612 A CN201811245612 A CN 201811245612A CN 109437333 A CN109437333 A CN 109437333A
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- nickel
- presoma
- galaxite
- lithium
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 62
- 229910001677 galaxite Inorganic materials 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000010405 anode material Substances 0.000 title claims abstract description 18
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 12
- 230000001376 precipitating effect Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 150000002815 nickel Chemical class 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000002816 nickel compounds Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 10
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 17
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000008139 complexing agent Substances 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000000875 high-speed ball milling Methods 0.000 description 4
- 102220043159 rs587780996 Human genes 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910006703 Li—Ni—Mn—O Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PNEFIWYZWIQKEK-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].OC(O)=O PNEFIWYZWIQKEK-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to field of lithium ion battery, it is related to a kind of nickel galaxite presoma and preparation method thereof and anode material for lithium-ion batteries.The nickel galaxite presoma has (MnO2)1‑x·(NiQ)xShown structure, wherein x is that 0.24~0.28, Q is the acid group that precipitating can be formed with nickel ion.Compared to nickel galaxite presoma conventional currently on the market, nickel lithium manganate cathode material made from nickel galaxite presoma of the invention has better cycle performance, and especially under the high temperature conditions, the promotion of cycle performance is more significant.
Description
Technical field
The invention belongs to field of lithium ion battery, more particularly, to it is a kind of for anode material for lithium-ion batteries before
Body is driven, more specifically to a kind of nickel manganese presoma and preparation method thereof for anode material for lithium-ion batteries, Yi Jiyou
The anode material for lithium-ion batteries of the nickel manganese precursor preparation.
Background technique
Lithium ion battery has many advantages, such as that energy density is high, cell voltage is high, storage life is long, is widely used to various
Portable electronic product and electric tool, especially electric car, hybrid-electric car and wind-powered electricity generation and solar energy storage power supply
Equal fields.The performance of lithium ion battery is heavily dependent on the property of positive electrode.
Current commercialized anode material for lithium-ion batteries mainly has cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4), phosphorus
Ferrous silicate lithium (LiFePO4) and ternary material (LiNi1-x-yCoxMnyO2) etc..But there is certain deficiency in these positive electrodes,
Cobalt acid lithium due to reasons in structure itself there are thermal stability it is poor, safety is poor the problems such as, be difficult to directly apply to power battery；
The low voltage (there was only 3.4V relative to lithium metal) of LiFePO4, LiMn2O4 reversible capacity is relatively low, the two material energies are close
It spends not high；Ternary material specific energy is higher, but cobalt resource is rare, cannot support the widespread demand of power battery.Therefore, compel to be essential
Developing one kind has high-energy-density, while being low cobalt or the positive electrode without cobalt again.
In recent years, equally with the nickel ion doped (LiNi of spinel crystal phase0.5Mn1.5O4) it is used as lithium ion cell positive material
Material, has very big progress especially as the research of power-type lithium ion battery, has higher discharge platform (relative to gold
Category lithium is 4.7V) and the advantages that higher energy density (up to 695Wh/Kg), just as power battery and energy-storage battery
Pole material has greater advantage, is the following large-scale plant, long-life, high security power lithium-ion battery product, especially newly
The important candidate positive electrode of energy automobile.
Nickel lithium manganate cathode material usually passes through following two step and is made: the first step is to prepare micron-sized nickel manganese hydrogen-oxygen
Compound or carbonate precursor；Second step is to be reacted the presoma, calcination processing with lithium source (lithium hydroxide, lithium carbonate)
Obtain Li-Ni-Mn-O positive electrode.
Industry it is believed that the preparation method and its performance of nickel manganese presoma to the performance of succeeding target product positive electrode
There is vital influence.Currently, synthesis nickel manganese presoma or the common methods of nickel manganese cobalt precursor have: microwave method, coprecipitated
Shallow lake method (wet process), sol-gel method, combustion method and solid phase method etc..Wherein many methods are since operation difficulty is high, the production cycle
It is long, it is difficult to industrial-scale production.Currently, have been commercialized technique for applying method is mainly using the antenatal drive of coprecipitation next life
Body.Specific technique is as follows: preparing nickel manganese presoma first, usually in the presence of complexing agent (ammonium hydroxide etc.), passes through precipitating reagent
Or the soluble-salt of nickel, manganese is converted to co-precipitation compound by neutralizer (alkali), and the mixing of nickel manganese is obtained after separation is dry
Then it is carried out solid phase mixing with lithium salts again, nickel ion doped is obtained after high-temperature calcination by carbonate or hydroxide precursor
Final product.Such as: CN105047900A discloses a kind of preparation method: water-soluble salt of nickel and manganese is configured to concentration and is
The stoichiometric ratio of the mixed solution of 0.5~4mol/L, nickel and manganese is Ni:Mn=0.5:1.5；By mixed solution and complexing agent one
It rises and is added continuously in reactive tank；Precipitating reagent is continuously added under the conditions of shear agitation with adjust the pH value of reaction system 11~
In 12 ranges；The complexing agent is the solution containing ammonium ion, and the precipitating reagent is sodium hydroxide or sodium carbonate liquor；Control reaction
Temperature obtains nickel manganese sediment at 40~70 DEG C, which is the presoma for preparing spinel nickel LiMn2O4, and gained nickel manganese is heavy
Starch drying obtains Ni, Mn oxide presoma.
The advantages of this coprecipitation method is that synthesis temperature is low, and raw material can be made to carry out molecular level contact, and product is thin
It is small uniform；But there are the settling rate of different elements differences, it is difficult to the composition and reaction rate of accurate control product, technique control
System requires the disadvantages of high；Therefore has the shortcomings that complicated for operation, poor reproducibility.In addition, this method is not only in industrialized production
Manufacturing cost height, low efficiency, and due to the use of complexing agent (ammonium hydroxide), a large amount of waste water and exhaust gas can be also generated, environment is protected
It is very unfavorable to protect.
In addition, in the prior art, many methods that nickel manganese presoma is prepared using solid phase method are also disclosed, such as:
CN108511737A, CN105655144B can be shown since raw material cannot be made to reach close grade contact in later period synthesis
The disadvantages of apparent structural defect causes cycle life short, and capacity attenuation amplitude is larger.
As it can be seen that the method for preparing nickel manganese presoma in the prior art haves the defects that various kinds, therefore, a kind of new system is found
The method of standby nickel lithium manganate cathode material is very necessary.
Summary of the invention
The technical problem to be solved by the present invention is to overcome synthesis process existing in the prior art is long, need to make using ammonium hydroxide
The disadvantages of for complexing agent, provide a kind of simple process, it is easy to operate, at low cost, easy to industrialized production, environmental-friendly, be not necessarily to
Using complexing agents such as ammonium hydroxide, the usage amount of alkali in neutralization reaction can be greatly reduced, and can effectively improve positive electrode performance
The preparation method of nickel galaxite presoma；The present invention also provides the high performance Li-Ni-Mn-O spinelles obtained by this method
Positive electrode has excellent cycle performance under the high temperature conditions.
To achieve the goals above, the first aspect of the present invention provides a kind of nickel galaxite presoma, the nickel manganese point
Spar presoma has (MnO2)1-x·(NiQ)xShown structure, wherein x is 0.24~0.28, Q heavy for that can be formed with nickel ion
The acid group in shallow lake；Preferably hydroxyl, carbonate, oxalate, bicarbonate radical.The nickel galaxite presoma can be single acid
(the MnO of root2)1-x·(NiQ)x, i.e., a kind of nickel galaxite presoma, or (MnO of a variety of acid groups2)1-x·
(NiQ)x, i.e., the mixture of a variety of nickel galaxite presomas.
In accordance with the present invention it is preferred that the nickel galaxite presoma is negative and is loaded with the titanium dioxide of NiQ nickel compound particle
Manganese block.
The second aspect of the present invention provides a kind of preparation method of nickel galaxite presoma, comprising the following steps:
(1) suspending liquid A containing nickel ion and manganese dioxide particle is obtained:
(2) under agitation, titrating solution B is added in the suspending liquid A, forms the nickel ion in suspending liquid A
Precipitating continues stirring to fully reacting；The titrating solution B is the aqueous slkali or weak acid solution that nickel ion can be made to precipitate；
(3) reaction product obtained by step (2) is washed, separates, is dry, obtains the nickel galaxite presoma.
According to the present invention, in step (1), the relative usage of nickel source and manganese dioxide is according to institute in nickel galaxite presoma
The content of nickel and manganese is needed to determine, it is generally preferred that in suspending liquid A, the molar ratio of nickel and manganese based on the element is 1:2.6-3.1.
One of key of the invention is to control the granularity of manganese dioxide particle in suspending liquid A, particularly preferably, described two
The D50 of manganese oxide particle is between 0.5~50 μm, and further preferably 1~20 μm.In preparation process, manganese dioxide can be with
Nickel salt, which is co-mulled and made into, reaches required granularity, can also first be ground to required granularity and mix again with nickel source.Specifically, following two be can be used
One of kind mode obtains the suspending liquid A containing nickel ion and manganese dioxide ultra-fine grain:
Mode one: nickel salt and manganese dioxide and water are co-mulled and made into, and nickel salt sufficiently dissolves, and the suspending liquid A is made；
Mode two: manganese dioxide powder is mixed with water, the sufficiently solution dissolved with nickel salt, the suspending liquid A is made.Its
In, the manganese dioxide powder is the manganese dioxide that ground fineness meets the requirements, and manganese dioxide powder and water can be jointly with two
The form of manganese oxide suspension provides.
Milling apparatus and specific grinding condition is not particularly limited in the present invention, and grinding can be in any conventional grinding machine
It carries out, such as high speed ball mill.Specific grinding condition, such as milling time, are subject to required grain graininess.
The additional amount of water is not particularly limited in the present invention, as long as can reach grinding effect.Generally, the addition of water
Amount is so that nickel ion concentration is 1.0-1.5mol/L in suspending liquid A.
The nickel salt is not particularly limited in the present invention, and specifically, the nickel source is can solution nickel salt；Preferably sulfuric acid
Nickel.
In method of the invention, the purpose of titrating solution B is added, is to make the nickel ion in suspending liquid A that neutralization reaction, shape occur
At precipitating, and it is deposited on the manganese dioxide particle surface.Titrating solution B can be aqueous slkali, be also possible to send out with Ni ion
Raw reaction, generates the weak acid of precipitating.Specifically, the aqueous slkali is selected from sodium hydroxide solution, sodium carbonate liquor and bicarbonate
At least one of sodium solution, preferably sodium hydroxide and/or sodium carbonate liquor；The weak acid solution is oxalic acid solution.
To precipitate nickel ion as far as possible completely, titrating solution B can be slightly excessive, can be according to working as in actual fabrication process
Amount determines the dosage of titrimetric substance for 1.02-1.10 times of nickel ion, and is configured to concentration aqueous solution appropriate, forms titrating solution B.For
Make nickel ion precipitating uniformly, titrating solution B is preferably added in suspending liquid A in a manner of being slowly added dropwise.
Manganese dioxide is not particularly limited in the present invention, specifically, electrolytic manganese dioxide or chemical manganese bioxide can be used.
According to the method for the present invention, titrating solution B is added in the suspending liquid A in step (2) and continues to stir to anti-
Complete temperature is answered to be not particularly limited, it is preferable that the temperature of two steps is kept at < 90 DEG C.Tool of the present invention to stirring
Concrete conditions in the establishment of a specific crime is not particularly limited, and can be determined according to reaction kettle size.
According to the method for the present invention, the washing in step (3), separation, the dry behaviour that this field routine can be used
Make condition.
The third aspect of the present invention provides the nickel galaxite presoma as made from above-mentioned preparation method.
The fourth aspect of the present invention provides a kind of anode material for lithium-ion batteries, and the anode material for lithium-ion batteries is by above-mentioned
Nickel galaxite precursor preparation obtains.Nickel manganese presoma of the invention can be directly as preparing anode material for lithium-ion batteries
Presoma.
Specifically, the anode material for lithium-ion batteries is prepared by method comprising the following steps: by nickel galaxite
Presoma is uniformly mixed with lithium-containing compound, then gained mixture is calcined under the conditions of logical oxygen, obtains the lithium ion battery
Positive electrode；The nickel galaxite presoma uses above-mentioned nickel galaxite presoma, and the lithium-containing compound is preferably selected from
Lithium hydroxide and/or lithium carbonate.
The condition of this field routine can be used in anode material for lithium-ion batteries preparation process of the invention, and according to the present invention one
Kind specific embodiment, the anode material for lithium-ion batteries pass through method comprising the following steps and prepare: before above-mentioned nickel manganese
It drives body and is uniformly mixed with lithium-containing compound according to excessive 2%~10% mole of the proportion of theoretical calculation lithium, then mixture is placed in
Calcining furnace obtains the positive electrode of lithium battery with 400-1000 DEG C of calcining 10-24h under the conditions of logical oxygen.
Further, the thermal synthesis step calcined can be divided into two sections of progress, and first segment: being warming up to 400-500 DEG C,
Constant temperature 4-8 hours；Second segment: it is warming up to 850-1000 DEG C, constant temperature 8-15 hours again.
The X-Ray map of high-voltage lithium nickel manganate product of the invention as shown in Figure 1, kiss completely with standard LiMn2O4 map
It closes.
Compared with the prior art, the advantages of the present invention are as follows:
1, during precursor preparation of the present invention, due to the raw material MnO of selection2In, manganese is with the object of+4 valence metal ions
State occurs, and Mn4+With great stability, keep insoluble, this avoid in coprecipitation process, since two kinds of metals are heavy
The difference of reduction of speed rate and caused by component deviation；Test proves, as long as manganese dioxide granularity is controlled in suitable range, instead
It answers the nickel compound of middle generation to precipitate the surface that particle will equably be coated on manganese dioxide, forms nickel manganese granular precursor.
2, the overall process of preparation method of the present invention does not use ammonium hydroxide not only, but also with conventional method comparatively, also significantly
The dosage for reducing the precipitating reagents such as sodium hydroxide or sodium carbonate is approximately the 1/4 of conventional method dosage.
3, the surface of manganese oxide is deposited in the form of fine particle due to nickel hydroxide, by adding lithium high temperature firing, is made
Nickel galaxite positive electrode, observed through XPS, it is found that formed a kind of superficial layer nickel content it is higher, from surface to center
Nickel content is in the spinel of concentration gradient.The spinel superficial layer manganese ion concentration is lower, in battery high-temperature condition
The meltage of manganese is reduced when lower charge and discharge cycles, so that nickel ion doped high temperature cyclic performance is improved.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Detailed description of the invention
Exemplary embodiment of the invention is described in more detail in conjunction with the accompanying drawings, it is of the invention above-mentioned and its
Its purpose, feature and advantage will be apparent.
Fig. 1 shows the comparison X- of nickel manganese presoma and standard LiMn2O4 obtained according to an embodiment of the present invention
Ray map, wherein upper figure is the map of LiMn2O4 made from the embodiment of the present invention 2, and the following figure is the map of standard LiMn2O4.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred implementations of the invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by the embodiments set forth herein.
Embodiment 1
The present embodiment is for illustrating nickel galaxite presoma and preparation method thereof of the invention.
Weigh 260.7 grams of electrolytic manganese dioxide (MnO2) and 262.7 grams of nickel sulfate (NiSO4·6H2O), it is packed into high speed ball milling
Machine adds 500 milliliters of water, high speed ball milling 2 hours, dissolves nickel sulfate sufficiently, and manganese dioxide is fully ground, and is formed and is suspended
Liquid, D50=5.6 μm of manganese dioxide grain graininess after grinding.Suspension is transferred in reaction kettle, at 50 DEG C, uses hydrogen-oxygen
Change sodium solution to be titrated.Equivalent is calculated, so that the Ni in suspension2+Ion generates Ni (OH) completely2.After the completion of titration, after
Continuous insulated and stirred 24 hours.Cleaning, filtering, drying, obtain nickel galaxite presoma (MnO2)0.75·(Ni(OH)2)0.25.It should
D50=6.2 μm of granularity of nickel galaxite presoma.
Embodiment 2
The present embodiment is used to illustrate the preparation of nickel lithium manganate cathode material of the invention.
1 167.8 grams of resulting presoma of Example, is mixed evenly using high-speed mixer by 37.0 grams of lithium carbonate.
Mixture is moved into crucible, enters furnace and carries out thermal synthesis.Thermal synthesis process is divided to two sections, first segment: being warming up to 450 DEG C, constant temperature 6 is small
When；Second segment: it is warming up to 880 DEG C, constant temperature 12 hours again.Nickel lithium manganate cathode material S1 is obtained, and is tested.
Embodiment 3
(1) nickel galaxite presoma is prepared:
Weigh 260.7 grams of electrolytic manganese dioxide (MnO2) and 262.7 grams of nickel sulfate (NiSO4·6H2O), it is packed into high speed ball milling
Machine adds 500 milliliters of water, high speed ball milling 2 hours, dissolves nickel sulfate sufficiently, and manganese dioxide is fully ground, and is formed and is suspended
Liquid, D50=4.8 μm of manganese dioxide grain graininess after grinding.Suspension is transferred in reaction kettle, at 40 DEG C, with excess
Concentration be 1mol/L sodium carbonate liquor titrated.Equivalent is calculated, so that the Ni in suspension2+Ion generates completely
NiCO3.After the completion of titration, continue insulated and stirred 24 hours.Cleaning, drying, obtain nickel galaxite presoma (MnO2)0.75·
(NiCO3)0.25.D50=5.4 μm of granularity of the nickel galaxite presoma.
(2) mixed carbonic acid lithium prepares nickel lithium manganate cathode material:
Weigh 184.2 grams of above-mentioned gained nickel galaxite presoma (MnO2)0.75·(NiCO3)0.25With 37.0 grams of lithium carbonates
Li2CO3, according to the method for embodiment 2, nickel lithium manganate cathode material S2 is made, and tested.
Comparative example 1
170.9 grams of presoma of outsourcing nickel galaxite are taken, 37.0 grams of lithium carbonate, is mixed using high-speed mixer equal
It is even.Mixture is moved into crucible, enters furnace and carries out thermal synthesis.Thermal synthesis process is divided to two sections, first segment: being warming up to 450 DEG C, constant temperature 6
Hour；Second segment: it is warming up to 880 DEG C, constant temperature 12 hours again.Nickel lithium manganate cathode material D1 is obtained, and carries out contrast test.
Test case
Electric performance test is carried out to the nickel lithium manganate cathode material that embodiment 2-3 and comparative example 1 are obtained, as a result such as 1 institute of table
Show.
Table 1
As can be seen from Table 1, compared to nickel galaxite presoma conventional currently on the market, nickel galaxite of the invention
Nickel lithium manganate cathode material made from presoma has better cycle performance, especially under the high temperature conditions, cycle performance
It is promoted more significant.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (10)
1. a kind of nickel galaxite presoma, the nickel galaxite presoma has (MnO2)1-x·(NiQ)xShown structure,
In, x is that 0.24~0.28, Q is the acid group that precipitating can be formed with nickel ion；Preferably hydroxyl, carbonate, oxalate, carbonic acid
Hydrogen radical.
2. nickel galaxite presoma according to claim 1, wherein the nickel galaxite presoma, which is negative, to be loaded with
The manganese dioxide block of NiQ nickel compound particle.
3. a kind of preparation method of nickel galaxite presoma, comprising the following steps:
(1) suspending liquid A containing nickel ion and manganese dioxide particle is obtained:
(2) under agitation, titrating solution B is added in the suspending liquid A, the nickel ion in suspending liquid A is made to form precipitating,
Continue stirring to fully reacting；The titrating solution B is the aqueous slkali or weak acid solution that nickel ion can be made to precipitate；
(3) reaction product obtained by step (2) is washed, separates, is dry, obtains the nickel galaxite presoma.
4. the preparation method of nickel galaxite presoma according to claim 3, wherein using one of following two mode
Obtain the suspending liquid A containing nickel ion and manganese dioxide particle:
Mode one: nickel salt and manganese dioxide and water are co-mulled and made into, and dissolve nickel salt sufficiently, and the suspending liquid A is made；
Mode two: manganese dioxide powder is mixed with water, the sufficiently solution dissolved with nickel salt, the suspending liquid A is made.
5. the preparation method of nickel galaxite presoma according to claim 3 or 4, wherein in suspending liquid A, nickel and manganese
Molar ratio based on the element is 1:2.6-3.1.
6. the preparation method of nickel galaxite presoma according to claim 3 or 4, wherein the manganese dioxide particle
D50 be 0.5-50 μm, preferably 1-20 μm.
7. the preparation method of nickel galaxite presoma according to claim 3 or 4, wherein the nickel salt is solubility
Nickel salt；Preferably nickel sulfate；
The aqueous slkali is selected from least one of sodium hydroxide solution, sodium carbonate liquor and sodium bicarbonate solution, preferably hydrogen
Sodium oxide molybdena and/or sodium carbonate liquor；The weak acid solution is oxalic acid solution.
8. nickel galaxite presoma made from the preparation method as described in any one of claim 3-7.
9. a kind of anode material for lithium-ion batteries, the anode material for lithium-ion batteries is by any one of claim 1-2 and 8 institute
The nickel galaxite precursor preparation stated obtains.
10. anode material for lithium-ion batteries according to claim 9, wherein the anode material for lithium-ion batteries passes through
Method comprising the following steps preparation: nickel galaxite presoma is uniformly mixed with lithium-containing compound, then by gained mixture
It is calcined under the conditions of logical oxygen, obtains the anode material for lithium-ion batteries；
The nickel galaxite presoma is using nickel galaxite presoma described in any one of claim 1-2 and 8, institute
It states lithium-containing compound and is preferably selected from lithium hydroxide and/or lithium carbonate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113044892A (en) * | 2021-03-10 | 2021-06-29 | 福建省云智新材料科技有限公司 | Preparation method of nickel manganese oxide |
| CN114388812A (en) * | 2022-03-23 | 2022-04-22 | 宜宾锂宝新材料有限公司 | Nickel-manganese spinel type positive electrode material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103855372A (en) * | 2012-11-29 | 2014-06-11 | 北京有色金属研究总院 | High-manganese composite cathode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103855372A (en) * | 2012-11-29 | 2014-06-11 | 北京有色金属研究总院 | High-manganese composite cathode material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113044892A (en) * | 2021-03-10 | 2021-06-29 | 福建省云智新材料科技有限公司 | Preparation method of nickel manganese oxide |
| CN114388812A (en) * | 2022-03-23 | 2022-04-22 | 宜宾锂宝新材料有限公司 | Nickel-manganese spinel type positive electrode material and preparation method and application thereof |
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