CN116102087A - Nickel-manganese binary precursor and preparation method and application thereof - Google Patents
Nickel-manganese binary precursor and preparation method and application thereof Download PDFInfo
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- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000002243 precursor Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 37
- 238000000975 co-precipitation Methods 0.000 claims abstract description 19
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 15
- -1 ammonium ions Chemical class 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 229940039748 oxalate Drugs 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000008139 complexing agent Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002595 magnetic resonance imaging Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 description 1
- KVGMATYUUPJFQL-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++] KVGMATYUUPJFQL-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a nickel-manganese binary precursor, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Adding nickel-manganese mixed solution, precipitant, ammonia water and oxalic acid source solution into base solution in parallel flow; (2) Controlling the concentration of oxalate and ammonium ions in the reaction system to carry out coprecipitation reaction to obtain the nickel-manganese binary precursor; the concentration of oxalate in the reaction system is 5-60 mmol/L, and the concentration of ammonium ion is 10-100 mmol/L, and the invention uses two complexing agents, and ensures nickel-manganese coprecipitation, avoids generation of impurity phases, and ensures sphericity of the material, thereby improving capacity of the material and cycle performance under high-rate discharge by accurately controlling the concentration of oxalate and ammonium ion in the reaction system.
Description
Technical Field
The invention belongs to the technical field of battery materials, and relates to a nickel-manganese binary precursor, a preparation method and application thereof.
Background
In recent years, research and industrialization of ternary material power batteries have been greatly advanced, and it is widely believed that NCM power batteries will become a mainstream choice for future electric vehicles in the industry. In general, three-way power cells mainly employ several families 333, 442, and 523, based on safety and cycling considerations. However, due to the limitation of cobalt resources, the cathode material is gradually developed towards the cobalt-free direction, so as to avoid the limitation of the shortage of the cobalt resources on the development of the cathode material. The nickel-manganese layered oxide also has high capacity, good capacity retention, low toxicity and lower raw material cost, so that the nickel-manganese layered hydroxide becomes a research hot spot of the anode material.
The current synthesis method of lithium nickel manganese oxide comprises the following steps: solid phase method, coprecipitation method, sol-gel method, etc. Compared with other methods, the coprecipitation method has simple manufacturing process and lower production cost. Is an important method for commercial production at present. However, the reaction conditions are not easy to control in the precursor preparation process, and agglomeration phenomenon exists between crystal nuclei in the nickel-manganese binary precursor reaction process, so that an interface is formed inside, and the lithium ion migration efficiency is affected.
CN104157872a discloses a preparation method of a low-cost high-capacity multiplying power type nickel-manganese precursor, which comprises the following steps: preparing a first solution, wherein the total concentration of nickel-containing manganese ions is 0.5-1 mol/L, and the content of complexing agent is 1.0-5.0g/L; wherein the concentration ratio of nickel and manganese ions is as follows: ni: mn=0.5 to 0.9:0.1 to 0.5; step two, preparing a second solution containing 2.0-10.0mol/L sodium hydroxide; step three, the first solution and the second solution are flowed into a reaction kettle, the flow rate of the first solution is controlled to be 100-250L/h, the reaction temperature is 25-40 ℃, the pH range is 9.00-12.00, and the stirring rotating speed is 200-400rpm; and (3) after the reaction is completed, the mixture enters an ageing kettle for constant-temperature ageing for 8-24 hours, is washed again, and is dried at the temperature of 100-200 ℃ to obtain the low-cost high-capacity multiplying power nickel-manganese precursor.
CN115477332a discloses a nickel-manganese binary precursor, a preparation method thereof, nickel-manganese binary precursor and a battery, wherein the crystal structure of the nickel-manganese binary precursor comprises a core and a shell stacked on the outer surface of the core, the core has a micropore structure, and the shell is formed by stacking strip structures.
The nickel-manganese binary material developed in China has poor performance, and the key reason is that the performance of the nickel-manganese binary precursor cannot meet the requirement, for example, the nickel-manganese binary precursor has poor cycle performance under high-rate discharge, so the nickel-manganese binary positive electrode material needs to be developed firstly. The morphology of the precursor is difficult to control in the reaction process along with the increase of the manganese content in the nickel-manganese binary precursor. After drying, the manganese tetraoxide crystal forms are easy to appear.
Disclosure of Invention
The invention aims to provide a nickel-manganese binary precursor, a preparation method and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a method for preparing a nickel-manganese binary precursor, which comprises the following steps:
(1) Adding nickel-manganese mixed solution, precipitant, ammonia water and oxalic acid source solution into base solution in parallel flow;
(2) Controlling the concentration of oxalate and ammonium ions in the reaction system to carry out coprecipitation reaction to obtain the nickel-manganese binary precursor;
wherein, the concentration of oxalate in the reaction system is 5-60 mmol/L, for example: 5mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 40mmol/L, 50mmol/L, 60mmol/L, etc., and the ammonium ion concentration is 10 to 100mmol/L, for example: 10mmol/L, 20mmol/L, 50mmol/L, 80mmol/L, 100mmol/L, etc.
According to the invention, two complexing agents (ammonia water and oxalic acid source) are used, so that the crystal structure of the nickel-manganese precursor in the reaction process can be effectively stabilized, and uniform coprecipitation of nickel-manganese can be realized by strictly controlling the molar concentration of oxalate ions and ammonium ions in the reaction system, so that the nickel-manganese precursor with single crystal form is obtained, and the crystal form of trimanganese tetroxide does not appear after drying.
In the preparation process of the nickel-manganese binary precursor, the concentration of oxalate and the concentration of ammonium ions in a reaction system are particularly important, the concentration of oxalate is controlled to be 5-60 mmol/L, the concentration of ammonium ions is controlled to be 10-100 mmol/L, the prepared nickel-manganese binary precursor cannot be in a trimanganese tetraoxide crystal form and has high sphericity, if the concentration of oxalate and the concentration of ammonium ions in the system are out of the range, agglomeration phenomenon exists between crystal nuclei in the reaction process of the nickel-manganese binary precursor, interfaces are formed inside, lithium ion migration efficiency is influenced, and other indexes such as sphericity, oxidation degree, primary particle thickness and the like are difficult to realize only aiming at the control of the compactness of a binary precursor stacking structure.
Preferably, the solute of the nickel-manganese mixed solution in step (1) comprises any one or a combination of at least two of sulfate, nitrate or chloride of nickel and manganese.
Preferably, the molar concentration of the nickel-manganese mixed solution is 1.5-2 mol/L, for example: 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L or 2mol/L, etc.
Preferably, the molar ratio of nickel ions to manganese ions in the nickel-manganese mixed solution is x:y, wherein x+y=1, and y is more than or equal to 0.6.
Preferably, the precipitant of step (1) comprises sodium hydroxide solution and/or potassium hydroxide solution.
Preferably, the molar concentration of the precipitant is 7 to 9mol/L, for example: 7mol/L, 7.5mol/L, 8mol/L, 8.5mol/L, 9mol/L, etc.
Preferably, the molar concentration of the ammonia water in the step (1) is 4.5-5 mol/L,4.5mol/L, 4.6mol/L, 4.7mol/L, 4.8mol/L, 4.9mol/L, 5mol/L or the like.
Preferably, the oxalic acid source solution comprises oxalic acid and/or sodium oxalate solution.
Preferably, the molar concentration of the oxalic acid source solution is 0.5 to 1mol/L, for example: 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, etc.
Preferably, the flow rate of the nickel-manganese mixed solution in the step (1) is 30-35L/h, for example: 30L/h, 31L/h, 32L/h, 33L/h, 34L/h, 35L/h, etc.
Preferably, the flow rate of the precipitant is 10.5 to 10.7L/h, for example: 10.5L/h, 10.55L/h, 10.6L/h, 10.65L/h, 10.7L/h, etc.
Preferably, the flow rate of the ammonia water is 0.1 to 1L/h, for example: 0.1L/h, 0.3L/h, 0.5L/h, 0.7L/h, 0.9L/h, 1L/h, etc.
Preferably, the flow rate of the oxalic acid source solution is 0.5 to 5L/h, for example: 0.5L/h, 1.5L/h, 2.5L/h, 3.5L/h, 4.5L/h, 5L/h, etc.
Preferably, the pH of the reaction system of step (2) is from 9.5 to 12, for example: 9.5, 10, 11 or 12, etc.
Preferably, stirring is performed during the reaction of the coprecipitation.
Preferably, the stirring speed is 200-400rpm, for example: 200rpm, 250rpm, 300rpm, 350rpm or 400rpm, etc.
Preferably, the temperature of the coprecipitation reaction is 40 to 65 ℃, for example: 40 ℃, 45 ℃, 50 ℃, 60 ℃ or 65 ℃ and the like.
Preferably, the coprecipitation reaction is followed by washing and drying.
Preferably, the washed detergent comprises hot water and/or liquid alkali.
In a second aspect, the present invention provides a nickel manganese binary precursor prepared by the method of the first aspect.
In a third aspect, the invention provides a binary positive electrode material prepared by mixing and sintering a nickel-manganese binary precursor and a lithium source according to the second aspect.
In a fourth aspect, the present invention provides a positive electrode sheet comprising the binary positive electrode material according to the third aspect.
In a fifth aspect, the present invention provides a lithium ion battery comprising the positive electrode sheet according to the fourth aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, a mode of feeding two complexing agents and nickel-manganese solution together is adopted, the proportion of the nickel-manganese solution, a precipitator and the complexing agent are prepared in advance and fed together, and a nickel-manganese precursor with a single crystal form is obtained after coprecipitation, and the crystal form of the manganic oxide is not generated after drying.
(2) According to the invention, by accurately controlling the concentration of oxalate and ammonium ions in the reaction system, nickel-manganese coprecipitation is ensured, meanwhile, the problem of precursor sphericity reduction caused by agglomeration among crystal nuclei in the reaction process due to high manganese content is avoided, and the capacity and the cycle performance of the material under high-rate discharge are improved.
Drawings
FIG. 1 is an SEM image of a nickel manganese binary precursor according to example 1 of the present invention.
Fig. 2 is an SEM image of a nickel manganese binary precursor according to comparative example 1 of the present invention.
Fig. 3 is an SEM image of a nickel manganese binary precursor according to comparative example 2 of the present invention.
Fig. 4 is an XRD pattern of a nickel manganese binary precursor according to example 1 of the present invention.
Fig. 5 is an XRD pattern of a nickel manganese binary precursor according to comparative example 1 of the present invention.
Fig. 6 is an XRD pattern of a nickel manganese binary precursor according to comparative example 2 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a nickel-manganese binary precursor, and the preparation method of the nickel-manganese binary precursor comprises the following steps:
(1) Preparing binary solution (sulfate) with the molar ratio of Ni, mn=0.4:0.6 (y=0.6) 1.77mol/L, sodium hydroxide solution with the concentration of 8mol/L, ammonia water with the concentration of about 4.7mol/L and oxalic acid radical with the concentration of about 0.8mol/L;
(2) And respectively controlling the flow rates of the binary liquid, the sodium hydroxide solution, the ammonia water and the oxalic acid solution to be 32L/h,10.7L/h, 0.2L/h and 2.8L/h, injecting into a stirrer, stirring at 380rpm and at 42 ℃, performing coprecipitation reaction (the concentration of oxalate in a reaction system is 49.1mmol/L, and the concentration of ammonium ions is 20.5 mmol/L), pumping the slurry into a centrifuge after the reaction, washing by adopting hot water and liquid alkali, drying filter residues obtained by centrifugal washing in an oven at 150 ℃, and finally obtaining a spherical-like nickel-manganese hydroxide precursor with single crystal form, wherein an SEM (SEM) graph of the obtained nickel-manganese binary precursor is shown in figure 1, and an XRD (X-ray diffraction) graph is shown in figure 4.
Example 2
The embodiment provides a nickel-manganese binary precursor, and the preparation method of the nickel-manganese binary precursor comprises the following steps:
(1) Preparing 1.8mol/L binary solution (sulfate) with Mn=0.3:0.7 (y=0.7), wherein the concentration of sodium hydroxide solution is 8.5mol/L, the concentration of ammonia water is about 4.8mol/L, and the concentration of oxalic acid radical is about 0.75mol/L;
(2) And respectively controlling the flow rates of the binary solution, the sodium hydroxide solution, the ammonia water and the oxalic acid solution to be 33L/h,10.6L/h, 0.16L/h and 2.6L/h, injecting into a stirrer, stirring at the speed of 390rpm, the temperature of 42 ℃, and the pH=11.3-11.5 to carry out coprecipitation reaction (the concentration of oxalate in a reaction system is 42.1mmol/L, and the concentration of ammonium ion is 16.6 mmol/L), pumping the slurry into a centrifuge after the reaction, washing by adopting hot water and liquid alkali, drying filter residues obtained by centrifugal washing in an oven at the temperature of 120 ℃, and finally obtaining the spherical-like nickel-manganese hydroxide precursor with single crystal form.
Comparative example 1
This comparative example differs from example 1 only in that oxalic acid was not added, other conditions and parameters were exactly the same as in example 1, and the SEM image of the obtained nickel manganese binary precursor is shown in fig. 2, and the XRD image is shown in fig. 5.
Comparative example 2
(1) Preparing 1.79mol/L binary solution (sulfate) with the molar ratio of Ni, mn=x and y (y=0.75), wherein the concentration of sodium hydroxide solution is 8mol/L, the concentration of ammonia water is about 4.7mol/L, and the concentration of oxalic acid radical is about 0.57mol/L;
(2) The molar ratio of Ni to Mn=x to y (y=0.75) binary liquid (sulfate) is respectively controlled, the flow rates of a sodium hydroxide solution, an ammonia water solution and an oxalic acid solution are 32L/h,10.5L/h, 1.2L/h and 1.5L/h are injected into a stirrer, the stirring speed is 400rpm, the temperature is 58 ℃, the pH=9.5-10 carries out coprecipitation reaction (the concentration of oxalate in a reaction system is 19.3mmol/L and the concentration of ammonium ion is 124.8 mmol/L), the slurry is pumped into a centrifuge after the reaction, hot water and liquid alkali are adopted for washing, filter residues obtained by centrifugal washing are dried in an oven at 150 ℃ to finally obtain a nickel-manganese hydroxide precursor, the SEM (magnetic resonance imaging) of the nickel-manganese binary precursor is shown in figure 3, and the XRD (magnetic resonance imaging) is shown in figure 6.
As can be seen from comparison of SEM images and XRD images of the nickel-manganese binary precursors prepared in the embodiment 1 and the comparative embodiment 1, the crystal form structure of the nickel-manganese binary precursor can be effectively stabilized in the reaction process by using two complexing agents; by adopting the original mature ammonia water coprecipitation process, the process transformation is reduced, the cost is reduced, the spherical-like crystal form single nickel-manganese precursor is obtained, and as can be seen from the comparison of figures 4-5, the morphology of the precursor is difficult to control in the reaction process along with the increase of the manganese content by using a single complexing agent, and a plurality of hetero phases (trimanganese tetroxide) are generated in the prepared precursor.
As can be seen from comparison of the embodiment 1 and the comparative example 2, in the preparation process of the nickel-manganese binary precursor, the concentration of oxalate and the concentration of ammonium ions in a reaction system are particularly important, the concentration of oxalate is controlled to be 5-60 mmol/L, the concentration of ammonium ions is controlled to be 10-100 mmol/L, the prepared nickel-manganese binary precursor cannot generate a trimanganese tetroxide crystal form and has high sphericity, if the concentration of oxalate and the concentration of ammonium ions in the system exceed the range, agglomeration phenomenon exists between crystal nuclei in the reaction process of the nickel-manganese binary precursor, an interface is formed inside, the migration efficiency of lithium ions is influenced, and the control of compactness of a binary precursor stacking structure is difficult to realize without influencing other indexes such as sphericity, oxidation degree, primary particle thickness and the like.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. The preparation method of the nickel-manganese binary precursor is characterized by comprising the following steps of:
(1) Adding nickel-manganese mixed solution, precipitant, ammonia water and oxalic acid source solution into base solution in parallel flow;
(2) Controlling the concentration of oxalate and ammonium ions in the reaction system to carry out coprecipitation reaction to obtain the nickel-manganese binary precursor;
wherein, the concentration of oxalate in the reaction system is 5-60 mmol/L, and the concentration of ammonium ion is 10-100 mmol/L.
2. The method of claim 1, wherein the solute of the nickel manganese mixed solution of step (1) comprises any one or a combination of at least two of sulfate, nitrate or chloride of nickel and manganese;
preferably, the molar concentration of the nickel-manganese mixed solution is 1.5-2 mol/L;
preferably, the molar ratio of nickel ions to manganese ions in the nickel-manganese mixed solution is x:y, wherein x+y=1, and y is more than or equal to 0.6.
3. The method of claim 1 or 2, wherein the precipitant of step (1) comprises sodium hydroxide solution and/or potassium hydroxide solution;
preferably, the molar concentration of the precipitant is 7-9 mol/L.
4. A process according to any one of claims 1 to 3, wherein the molar concentration of aqueous ammonia in step (1) is from 4.5 to 5mol/L;
preferably, the oxalic acid source solution comprises oxalic acid and/or sodium oxalate solution;
preferably, the molar concentration of the oxalic acid source solution is 0.5-1 mol/L.
5. The preparation method according to any one of claims 1 to 4, wherein the flow rate of the nickel-manganese mixed solution in the step (1) is 30 to 35L/h;
preferably, the flow rate of the precipitant is 10.5-10.7L/h;
preferably, the flow rate of the ammonia water is 0.1-1L/h;
preferably, the flow rate of the oxalic acid source solution is 0.5-5L/h.
6. The process according to any one of claims 1 to 5, wherein the pH of the reaction system in step (2) is 9.5 to 12;
preferably, stirring is performed during the reaction of the coprecipitation;
preferably, the stirring speed is 200-400rpm;
preferably, the temperature of the coprecipitation reaction is 40-65 ℃;
preferably, the coprecipitation reaction is followed by washing and drying treatment;
preferably, the washed detergent comprises hot water and/or liquid alkali.
7. A nickel manganese binary precursor, characterized in that it is produced by the method according to any one of claims 1-6.
8. A binary positive electrode material, wherein the binary positive electrode material is prepared by mixing and sintering the nickel-manganese binary precursor according to claim 7 and a lithium source.
9. A positive electrode sheet comprising the binary positive electrode material of claim 8.
10. A lithium ion battery comprising the positive electrode sheet of claim 9.
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