CN116216796A - Modified nickel-manganese binary precursor and preparation method and application thereof - Google Patents
Modified nickel-manganese binary precursor and preparation method and application thereof Download PDFInfo
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- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical class [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000002243 precursor Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 37
- 239000002585 base Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 238000000975 co-precipitation Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003607 modifier Substances 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 19
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 abstract description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 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
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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
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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
- H01M4/52—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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- 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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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/32—Spheres
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- C01P2006/11—Powder tap density
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- C01P2006/40—Electric properties
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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
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Abstract
The invention provides a modified nickel-manganese binary precursor, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Mixing water, a modifier, alkali liquor and ammonia water to obtain a base solution; (2) Adding nickel-manganese binary salt solution, alkali liquor and ammonia water into a base solution in parallel flow, and performing coprecipitation reaction to obtain the modified nickel-manganese binary precursor; the modifier comprises ethylene glycol, and the modifier is added into the reaction base solution in advance, so that the crystal form of the binary nickel-manganese precursor can be controlled, the problems that in the existing preparation method of the nickel-manganese binary precursor, the primary crystal form is easy to separate out trimanganese tetroxide and the morphology is relatively loose are avoided, and the primary crystal form of the prepared nickel-manganese hydroxide is relatively compact.
Description
Technical Field
The invention belongs to the technical field of battery materials, and relates to a modified 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.
Due to the limitation of cobalt resources, the anode material is gradually developed towards the cobalt-free direction, so that the limitation of the shortage of the cobalt resources on the development of the anode material is avoided. 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.
CN115477332a discloses a nickel-manganese binary precursor, the crystal structure of which comprises a core and a shell stacked on the outer surface of the core, the core has a microporous structure, and the shell is formed by stacking strip structures.
CN113603158A discloses a cobalt-free positive electrode material precursor, and the preparation method thereof comprises the following steps: preparing a mixed salt solution containing nickel and manganese and doping elements; adding pure water into the reaction kettle as base solution, and then adding ammonia water to control the concentration of the ammonia water in the base solution to be 2-6g/L; introducing nitrogen into the reaction kettle, and adding the mixed salt solution, the precipitator and the ammonia water into the reaction kettle for stirring reaction; finally adding ZrSO into the reaction kettle 4 And (NH) 4 ) 2 SO 4 Continuing the reaction, filtering, washing and drying after the reaction is finished to obtain the cobalt-free positive electrode material precursor.
The precursor prepared by the scheme has the following characteristics thatThe following problems are that in the first charging process, the structure of the lithium-rich nickel-manganese layered oxide positive electrode material is obviously changed, mainly caused by an activating component, and in the subsequent charging and discharging process, the structure of the lithium-rich nickel-manganese layered oxide positive electrode material is continuously changed, and the capacity and the discharging platform voltage of the lithium-rich nickel-manganese layered oxide positive electrode material are continuously reduced due to the change; the first coulombic efficiency of the lithium-rich nickel-manganese layered oxide cathode material is low. From the microstructure, part of Li at the time of first charging + By Li 2 O is released, and the resulting vacancies are filled with transition metal ions, so that lithium ions cannot return to the original position in the discharge process, and the material has larger irreversible capacity, namely lower initial coulomb efficiency; the lithium-rich nickel-manganese layered oxide positive electrode material has high charging voltage, so that electrolyte is decomposed in the charging and discharging process, the concentration of HF in the electrolyte is further improved, the surface of the lithium-rich nickel-manganese layered oxide positive electrode material is damaged, the stability of the material structure in the charging and discharging process is finally influenced, and the cycle performance is not ideal.
Disclosure of Invention
The invention aims to provide a modified 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 modified nickel-manganese binary precursor, which comprises the following steps:
(1) Mixing water, a modifier, alkali liquor and ammonia water to obtain a base solution;
(2) Adding nickel-manganese binary salt solution, alkali liquor and ammonia water into a base solution in parallel flow, and performing coprecipitation reaction to obtain the modified nickel-manganese binary precursor;
wherein the modifier comprises ethylene glycol.
In the preparation process of the modified nickel-manganese binary precursor, the modifier is added in the base solution in advance, so that the crystal form structure of the nickel-manganese precursor can be effectively stabilized when the seed crystal is generated in the early stage of the reaction; the original mature ammonia water coprecipitation procedure can be adopted, the process transformation is reduced, the cost is reduced, and the spherical-like crystal form single nickel-manganese precursor is obtained.
Preferably, the mass ratio of the water and the modifier in the step (1) is (20-25): 1, for example: 20:1, 21:1, 22, 23:1, 24:1, or 25:1, etc.
Preferably, the lye of step (1) comprises sodium hydroxide solution and/or potassium hydroxide solution.
Preferably, the base concentration in the base liquid is 5-12 g/L, for example: 5g/L, 6g/L, 8g/L, 10g/L, 12g/L, etc.
Preferably, the ammonia concentration in the base liquid is 1.5-4 g/L, for example: 1.2g/L, 2g/L, 2.5g/L, 3g/L, 4g/L, etc.
Preferably, the concentration of the nickel manganese binary salt solution in the step (2) 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 to manganese in the nickel-manganese binary salt solution is (1-4): (6-9), for example: 1:9, 2:8, 3:7 or 4:6, etc.
Preferably, the concentration of the lye is 6 to 10mo/L, for example: 6mo/L, 7mo/L, 8mo/L, 9mo/L, 10mo/L, etc.
Preferably, the concentration of the ammonia water is 4.5 to 5mol/L, for example: 4.5mo/L, 4.6mo/L, 4.7mo/L, 4.8mo/L, 5mo/L, etc.
Preferably, the flow rate of the nickel manganese binary salt solution is 2-4L/h, for example: 2L/h, 2.5L/h, 3L/h, 3.5L/h, 4L/h, etc.
Preferably, the flow rate of the lye is 0.8 to 1.2L/h, for example: 0.8L/h, 0.9L/h, 1L/h, 1.1L/h, 1.2, etc.
Preferably, the flow rate of the ammonia water is 0.1 to 0.3L/h, for example: 0.1L/h, 0.15L/h, 1.2L/h, 0.25L/h, or 0.3L/h, etc.
Preferably, the temperature of the coprecipitation reaction in step (2) is 40 to 65 ℃, for example: 40 ℃, 45 ℃, 48 ℃, 50 ℃ or 60 ℃ and the like.
Preferably, the stirring speed of the coprecipitation reaction is 400 to 700rpm, for example: 400rpm, 450rpm, 500rpm, 600rpm or 700rpm, etc.
Preferably, the pH of the coprecipitation reaction is 9.5 to 11, for example: 9.5, 9.8, 10, 10.5 or 11, etc.
Preferably, the coprecipitation reaction of step (2) is followed by centrifugal washing and drying.
Preferably, the centrifugally washed detergent comprises hot water and a liquid base.
Preferably, the temperature of the drying treatment is 90 to 150 ℃, for example: 90 ℃, 100 ℃, 110 ℃, 130 ℃ or 150 ℃ and the like.
In a second aspect, the present invention provides a modified nickel manganese binary precursor prepared by the method of the first aspect.
In a third aspect, the invention provides a binary positive electrode material, which is obtained by mixing and sintering the modified nickel-manganese binary precursor according to the second aspect and a lithium source.
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) In the preparation process of the modified nickel-manganese binary precursor, the modifier is added in the base solution in advance, so that the crystal form structure of the nickel-manganese precursor can be effectively stabilized when the seed crystal is generated in the early stage of the reaction; the original mature ammonia water coprecipitation procedure can be adopted, the process transformation is reduced, the cost is reduced, and the spherical-like crystal form single nickel-manganese precursor is obtained.
(2) The modified nickel-manganese binary precursor has the advantages of uniform particle size distribution, stable crystal form, and small approximate variation of the inner diameter distance distribution and tap density of the material.
Drawings
FIG. 1 is an SEM image of a nickel manganese binary precursor prepared according to example 1 of the present invention.
FIG. 2 is an XRD pattern of a nickel manganese binary precursor prepared according to the method of example 1 of the present invention.
FIG. 3 is an SEM image of a nickel manganese binary precursor prepared according to example 3 of the present invention.
FIG. 4 is an SEM image of a nickel manganese binary precursor prepared according to example 4 of the present invention.
FIG. 5 is an SEM image of a nickel manganese binary precursor prepared according to comparative example 1 of the present invention.
FIG. 6 is an SEM image of a nickel manganese binary precursor prepared according to comparative example 1 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) Adding 12L of pure water into a reaction kettle, adding 0.5L of absolute ethyl alcohol, sodium hydroxide solution and ammonia water to obtain a base solution, and controlling the alkali concentration in the base solution to be 8.5g/L and the ammonia concentration to be 3.5g/L;
(2) Respectively controlling the molar ratio of Ni to Mn=x to y (y=0.6) binary liquid (sulfate), injecting sodium hydroxide solution and ammonia water into a base liquid at the flow rates of 3L/h,1L/h and 0.2L/h, and performing coprecipitation reaction for 30h at the stirring rate of 700rpm and the temperature of 58 ℃ and at the pH value of 10-10.6;
(3) And (3) pumping the slurry into a centrifuge, washing by adopting hot water and liquid alkali, drying filter residues obtained by centrifugal washing in an oven at 120 ℃, and finally obtaining the spherical-like nickel-manganese hydroxide precursor with single crystal form, wherein an SEM (scanning electron microscope) diagram of the nickel-manganese binary precursor is shown in figure 1, and an XRD (X-ray diffraction) diagram of the nickel-manganese binary precursor is shown in figure 1.
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) Adding 12L of pure water into a reaction kettle, adding 0.545L of absolute ethyl alcohol, sodium hydroxide solution and ammonia water to obtain a base solution, and controlling the alkali concentration in the base solution to be 8.2g/L and the ammonia concentration to be 3.6g/L;
(2) Controlling the mole ratio of Ni to Mn=x to y (y=0.6) binary liquid (sulfate), injecting sodium hydroxide solution and ammonia water at the flow rate of 3.2L/h,1.1L/h and 0.25L/h into the base solution, and performing coprecipitation reaction for 32h at the stirring rate of 650rpm and the temperature of 60 ℃ and the pH value of 10.2-10.8;
(3) And (3) pumping the slurry into a centrifuge, washing by adopting hot water and liquid alkali, and drying filter residues obtained by centrifugal washing in an oven at 130 ℃ to finally obtain the spherical-like nickel-manganese hydroxide precursor with single crystal form.
Example 3
The embodiment provides a nickel-manganese binary precursor, and the preparation method of the nickel-manganese binary precursor comprises the following steps:
(1) Adding 12L of pure water into a reaction kettle, adding 0.75L of absolute ethyl alcohol, sodium hydroxide solution and ammonia water to obtain a base solution, and controlling the alkali concentration in the base solution to be 8.5g/L and the ammonia concentration to be 3.5g/L;
(2) Respectively controlling the molar ratio of Ni to Mn=x to y (y=0.6) binary liquid (sulfate), injecting sodium hydroxide solution and ammonia water into a base liquid at the flow rates of 3L/h,1L/h and 0.2L/h, and performing coprecipitation reaction for 30h at the stirring rate of 700rpm and the temperature of 58 ℃ and at the pH value of=9.6-10.6;
(3) And (3) pouring the slurry into a centrifuge, washing by adopting hot water and liquid alkali, drying filter residues obtained by centrifugal washing in an oven at 120 ℃, and finally obtaining a spherical-like nickel-manganese hydroxide precursor, wherein an SEM (scanning electron microscope) diagram of the spherical-like nickel-manganese hydroxide precursor is shown in fig. 3, and the precursor has slightly bad appearance.
Example 4
The embodiment provides a nickel-manganese binary precursor, and the preparation method of the nickel-manganese binary precursor comprises the following steps:
(1) Adding 12L of pure water into a reaction kettle, adding 0.4L of absolute ethyl alcohol, sodium hydroxide solution and ammonia water to obtain a base solution, and controlling the alkali concentration in the base solution to be 8.5g/L and the ammonia concentration to be 3.5g/L;
(2) Respectively controlling the molar ratio of Ni to Mn=x to y (y=0.6) binary liquid (sulfate), injecting sodium hydroxide solution and ammonia water into a base liquid at the flow rates of 3L/h,1L/h and 0.2L/h, and performing coprecipitation reaction for 30h at the stirring rate of 700rpm and the temperature of 58 ℃ and at the pH value of=9.6-10.6;
(3) And (3) pouring the slurry into a centrifuge, washing by adopting hot water and liquid alkali, drying filter residues obtained by centrifugal washing in an oven at 120 ℃, and finally obtaining a spherical-like nickel-manganese hydroxide precursor with single crystal form, wherein an SEM (scanning electron microscope) diagram of the spherical-like nickel-manganese hydroxide precursor is shown in fig. 4.
Comparative example 1
The comparative example provides a nickel-manganese binary precursor, and the preparation method of the nickel-manganese binary precursor comprises the following steps:
(1) Adding 12L of pure water into a reaction kettle, adding sodium hydroxide solution and ammonia water to obtain a base solution, and controlling the alkali concentration in the base solution to be 8.5g/L and the ammonia concentration to be 3.5g/L;
(2) Respectively controlling the molar ratio of Ni to Mn=x to y (y=0.6) binary liquid (sulfate), injecting sodium hydroxide solution and ammonia water into a base liquid at the flow rates of 3L/h,1L/h and 0.2L/h, and performing coprecipitation reaction for 30h at the stirring rate of 700rpm and the temperature of 58 ℃ and at the pH value of=9.6-10.6;
(3) And (3) pumping the slurry into a centrifuge, washing by adopting hot water and liquid alkali, and drying filter residues obtained by centrifugal washing in an oven at 120 ℃ to finally obtain the spherical-like nickel-manganese hydroxide precursor with single crystal form.
The SEM image of the nickel-manganese binary precursor is shown in fig. 5, and the XRD image of the nickel-manganese binary precursor is shown in fig. 6.
Performance test:
the nickel manganese hydroxide precursors obtained in examples and comparative examples were subjected to particle size and tap density tests, and the test results are shown in table 1:
TABLE 1
| (D90-D10)/D50 | Tap density (g/cm) 3 ) | |
| Example 1 | 0.633 | 1.2 |
| Example 2 | 0.635 | 1.22 |
| Example 3 | 0.621 | 1.36 |
| Example 4 | 0.651 | 1.08 |
| Comparative example 1 | 0.877 | 0.85 |
As can be seen from Table 1, according to examples 1-2, the particle size distribution of the modified nickel-manganese binary precursor is relatively uniform, the crystal form is relatively stable, and the inner diameter distance distribution and the tap density of the material are relatively close to each other and slightly changed.
As can be obtained by comparing the embodiment 1 with the embodiment 3-4 and combining the figures 3-4, in the preparation process of the modified nickel-manganese binary precursor, the effect of the addition amount of the modifier in the base solution on the performance of the modified nickel-manganese binary precursor is quite obvious, the mass ratio of pure water to the modifier is controlled at (20-25): 1, the prepared modified nickel-manganese binary precursor has better performance, if the addition amount of the modifier is too large, the diameter distance is further reduced, the tap density is too high, but the morphology is approaching to a seamless sphere, if the addition amount of the modifier is too small, the diameter distance is further increased, the tap density is reduced, and the morphology tends to be loose.
The invention can be obtained by comparing the example 1 with the comparative example 1, and in the preparation process of the modified nickel-manganese binary precursor, the modifier is added in the base solution in advance, so that the crystal form structure of the nickel-manganese precursor can be effectively stabilized when the seed crystal is generated in the early stage of the reaction; the original mature ammonia water coprecipitation procedure can be adopted, the process transformation is reduced, the cost is reduced, and the spherical-like crystal form single nickel-manganese precursor is obtained.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. The preparation method of the modified nickel-manganese binary precursor is characterized by comprising the following steps of:
(1) Mixing water, a modifier, alkali liquor and ammonia water to obtain a base solution;
(2) Adding nickel-manganese binary salt solution, alkali liquor and ammonia water into a base solution in parallel flow, and performing coprecipitation reaction to obtain the modified nickel-manganese binary precursor;
wherein the modifier comprises ethylene glycol.
2. The process according to claim 1, wherein the mass ratio of the water to the modifier in the step (1) is (20 to 25): 1.
3. The process according to claim 1 or 2, wherein the lye of step (1) comprises sodium hydroxide solution and/or potassium hydroxide solution;
preferably, the alkali concentration in the base solution is 5-12 g/L;
preferably, the concentration of ammonia in the base liquid is 1.5-4 g/L.
4. The preparation method according to any one of claims 1 to 3, wherein the concentration of the nickel manganese binary salt solution in the step (2) is 1.5 to 2mol/L;
preferably, the molar ratio of nickel to manganese in the nickel-manganese binary salt solution is (1-4): (6-9);
preferably, the concentration of the alkali liquor is 6-10 mo/L;
preferably, the concentration of the ammonia water is 4.5-5 mol/L;
preferably, the flow rate of the nickel-manganese binary salt solution is 2-4L/h;
preferably, the flow rate of the alkali liquor is 0.8-1.2L/h;
preferably, the flow rate of the ammonia water is 0.1-0.3L/h.
5. The method of any one of claims 1-4, wherein the temperature of the coprecipitation reaction in step (2) is 40-65 ℃;
preferably, the stirring speed of the coprecipitation reaction is 400-700 rpm;
preferably, the pH of the coprecipitation reaction is 9.5 to 11.
6. The method according to any one of claims 1 to 5, wherein the coprecipitation reaction in step (2) is followed by centrifugal washing and drying treatment;
preferably, the centrifugally washed detergent comprises hot water and a liquid base;
preferably, the temperature of the drying treatment is 90 to 150 ℃.
7. A modified 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 obtained by mixing and sintering the modified 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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