CN116675259A - Composite sodium ion positive electrode precursor and preparation method thereof - Google Patents
Composite sodium ion positive electrode precursor and preparation method thereof Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 50
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 27
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000012266 salt solution Substances 0.000 claims abstract description 39
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 38
- 239000002002 slurry Substances 0.000 claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000011572 manganese Substances 0.000 claims abstract description 19
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 14
- 239000007921 spray Substances 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 150000002696 manganese Chemical class 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 150000002505 iron Chemical class 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000012216 screening Methods 0.000 claims abstract description 6
- 238000000975 co-precipitation Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- 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 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910000863 Ferronickel Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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
Composite sodium ion positive electrode precursor and preparation method thereof, wherein the general formula of the precursor is Na x Ni y1 Fe z1 Mn 1‑y1‑z1 (CO 3 ) 1+x/2+ a Ni y2 Fe z2 Mn 1‑y2‑z2 (OH) 2 . The preparation method comprises the following steps: preparing a mixed quaternary salt solution of nickel salt, iron salt and manganese salt by using an aqueous solution, and preparing a sodium carbonate precipitant solution; preparing a mixed ternary salt solution of nickel salt, iron salt and manganese salt; preparing ammonia water solution and sodium hydroxide solution; preparing carbonic acid quaternary material slurry in a first reaction kettle by adopting a spray method, and when the density of the slurry in the kettle reaches 1.35-1.5 g/cm 3 When the reaction is carried out as the initial base solution to a second reaction kettleWet coprecipitation reaction; feeding the ternary salt solution and the sodium hydroxide solution into a second reaction kettle in a lower liquid feeding mode to prepare a shell layer of the precursor; and sequentially carrying out centrifugal washing, drying and screening to remove iron on the product to obtain the composite sodium ion positive electrode precursor. The product of the invention is uniform, the shape is controllable, and the production cost is reduced.
Description
Technical Field
The invention relates to the field of battery materials, in particular to a composite sodium ion positive electrode precursor and a preparation method thereof.
Background
With the pursuit of cost and environmental benefits, the demand for sodium ion batteries is increasing, layered oxides, naNi x Fe y Mn z O 2 The advantages of environmental friendliness, low price and the like are considered as one of the most promising cathode materials. However, the prior art mainly adopts ternary precursor and sodium source (sodium carbonate or sodium hydroxide) to be physically mixed and then solid phase sintered to prepare ternary material, and the method has the defects of uneven mixing of ternary precursor and sodium source, high sintering temperature, uneven morphology and the like.
Therefore, how to solve the above-mentioned drawbacks of the prior art is a subject to be studied and solved by the present invention.
Disclosure of Invention
The invention aims to provide a composite sodium ion positive electrode precursor and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a ternary positive precursor of composite Na ion has the general formula Na x Ni y1 Fe z1 Mn 1-y1-z1 (CO 3 ) 1+x/2+ a Ni y2 Fe z2 Mn 1-y2-z2 (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein 0 is<x<1、0<y1<1、0<z1<1、0<y2<1、0<z2<1、0<y1+z1<1、0<y2+z2<1、0.1≤a≤10;
The composite sodium ion positive electrode precursor is of a core-shell structure, the core is a carbonic acid quaternary material, and the general formula is Na x Ni y1 Fe z1 Mn 1-y1-z1 (CO 3 ) 1+x/2 ;
The shell layer is made of ternary material and has a general formula of Ni y2 Fe z2 Mn 1-y2-z2 (OH) 2 。
According to a further technical scheme, the D50 of the precursor is 4.5-5.5 mu m, and the radius of the nucleus occupies 40-50% of the radius of the precursor; the tap density of the precursor is 1.30-1.60 g/m 3 Specific surface area of 15-25 m 2 /g。
In order to achieve the purpose, the technical scheme adopted in the method level of the invention is as follows:
a preparation method of a composite sodium ion positive electrode precursor comprises the following steps:
preparing a mixed quaternary salt solution of nickel salt, iron salt and manganese salt by using an aqueous solution, and preparing a sodium carbonate precipitant solution; preparing a mixed ternary salt solution of nickel salt, iron salt and manganese salt; preparing an ammonia water solution and a sodium hydroxide solution;
preparing carbonic acid quaternary material slurry in a first reaction kettle by adopting a spray method, wherein the reaction temperature is 40-70 ℃, after reacting for 1-2 hours, starting overflow and circulation of the first reaction kettle and a concentration device, and when the density of the slurry in the kettle reaches 1.35-1.5 g/cm 3 Stopping the reaction, wherein the slurry in the kettle is used as nuclear slurry, and the D50 of the slurry is 1.8-2.5 mu m;
step three, transferring the nuclear slurry serving as an initial base solution into a second reaction kettle for wet coprecipitation reaction; the ternary salt solution, the sodium hydroxide solution and the ammonia water solution are fed into a second reaction kettle in a liquid feeding mode, the reaction temperature in the kettle is controlled to be 40-70 ℃, the pH value in the kettle is controlled to be 8.6-9.55 through the sodium hydroxide solution, and the ammonia water solution is used as a complexing agent; the reaction process is carried out under the conditions of stirring and full-process nitrogen or inert gas introduction, a shell layer of the precursor is prepared, and the reaction is stopped until the slurry D50 grows to the target particle size;
and step four, sequentially performing centrifugal washing, drying and screening for iron removal on the product in the step three to obtain the composite sodium ion positive electrode precursor.
In the scheme, nitrogen or inert gas is introduced in the reaction process of the third step to avoid the oxidation of iron, and nitrogen or inert gas is also introduced to protect the ternary salt solution in the first step to avoid the oxidation of iron.
In a further technical scheme, in the first step, the aqueous solution is hydroxide precursor mother liquor wastewater, and the pH is regulated to 1-3 by sulfuric acid solution. If it is not within this pH range, the aging time becomes long and oxidation occurs.
According to a further technical scheme, the mother liquor wastewater is a mixed solution containing ammonia nitrogen and sodium sulfate, the pH value of the mother liquor wastewater is 10-13, the concentration of the sodium sulfate is 50-150 g/L, and the concentration of the ammonia nitrogen is 5-10 g/L.
In the first step, the molar concentration of metal ions of the quaternary salt solution is 1-2 mol/L, and the molar concentration of the sodium carbonate precipitant solution is 1-4 mol/L; the molar concentration of metal ions of the ternary salt solution is 1-2 mol/L.
In a further technical scheme, in the second step, the spraying method adopts a pneumatic spray head to spray the sodium carbonate precipitant solution into the quaternary salt solution in a spray mode to form the carbonic acid quaternary material slurry.
In a further technical scheme, in the second step, the liquid inlet speed of the quaternary salt solution is 100-500 ml/min, and the ratio of the liquid inlet flow of the sodium carbonate precipitant solution to the liquid inlet flow of the quaternary salt solution is 1-3:1.
In a further technical scheme, in the third step, the stirring rotation speed is 550-650 rpm.
According to a further technical scheme, the total reaction time of the second step and the third step is 10-34 hours.
In a further technical scheme, in the fourth step, the washing liquid is Na 2 CO 3 A solution.
The working principle and the advantages of the invention are as follows:
the invention provides a composite sodium ion positive electrode precursor and a preparation method thereof, which optimize the mixing uniformity of a sodium component and a ternary precursor, realize the mixing of the ternary precursor and sodium carbonate in a microscopic scale, form a composite ternary positive electrode precursor with uniform product and adjustable morphology, further reduce the cost problem of precursor production and positive electrode material production from the aspect of material design to process optimization, and improve the electrochemical performance of the product.
The invention is characterized in that:
1. the ternary salt solution and the sodium hydroxide solution of the invention are both in the following liquid feeding mode
The ferronickel manganese ternary salt solution and the sodium hydroxide solution are symmetrically fed, so that the ferronickel manganese ternary salt solution and the sodium hydroxide solution can be uniformly synthesized in the reaction kettle under the stirring of an angle. If one is upper liquid inlet and the other is lower liquid inlet, the solution of the upper liquid inlet is scattered at the moment of entering the reaction kettle, and in the whole reaction system, some of the solution falls into slurry and the other falls into aqueous solution, so that the micro powder phenomenon and uneven synthesis occur.
2. The invention adopts a spray method to prepare the carbonic acid quaternary material slurry
The sodium carbonate precipitant solution is atomized and then enters the reaction kettle, so that the water can be fully vaporized and uniformly sprayed in the quaternary salt solution, thereby being beneficial to forming uniform nuclear slurry. If the liquid is directly fed, the precipitant can be instantly combined with the quaternary salt solution, so that particle agglomeration is difficult to disperse, and the growth of a later-stage shell layer is not facilitated.
Drawings
FIG. 1 is a SEM image of a composite sodium ion positive electrode precursor of example 1 of the present invention;
FIG. 2 is an SEM image of a composite sodium ion positive electrode precursor of example 2 of the present invention;
FIG. 3 is an SEM image of a composite sodium ion positive electrode precursor of comparative example 1 of the present invention;
fig. 4 is an SEM image of a composite sodium ion positive electrode precursor of comparative example 2 of the present invention.
Description of the embodiments
The invention is further described below with reference to the accompanying drawings and examples:
the present invention will be described in detail with reference to the drawings, wherein modifications and variations are possible in light of the teachings of the present invention, without departing from the spirit and scope of the present invention, as will be apparent to those of skill in the art upon understanding the embodiments of the present invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the terms "comprising," "including," "having," and the like are intended to be open-ended terms, meaning including, but not limited to.
The term (terms) as used herein generally has the ordinary meaning of each term as used in this field, in this disclosure, and in the special context, unless otherwise noted. Certain terms used to describe the present disclosure are discussed below, or elsewhere in this specification, to provide additional guidance to those skilled in the art in connection with the description herein.
Examples
Preparing a mixed quaternary salt solution of sodium salt, nickel salt, ferric salt and manganese salt, wherein sodium: nickel: iron: the molar ratio of manganese is 1:1:1:1, and the total molar concentration of metal ions in the quaternary salt solution is 2mol/L.
Preparing a sodium carbonate precipitant solution, wherein the molar concentration of sodium carbonate is 4mol/L.
Controlling the flow ratio of the quaternary salt solution to the sodium carbonate precipitant solution to be 1:1, preparing carbonic acid quaternary material slurry in a first reaction kettle by adopting a spray method (spray drying method), and enabling the slurry to flow into a concentration device for concentration, wherein the density of the slurry reaches 1.50g/cm 3 Gradually transferring the slurry into a wet coprecipitation reaction kettle (a second reaction kettle) to serve as initial base solution; preparing a mixed ternary salt solution of nickel salt, iron salt and manganese salt, preparing an ammonia water solution and a sodium hydroxide solution, and pumping the mixed ternary salt solution into a second reaction kettle through a peristaltic pump, wherein the molar ratio of nickel to iron to manganese is 1:1:1, the concentration of the ternary salt solution is 2mol/L, the concentration of sodium hydroxide is 8mol/L, and the concentration of the ammonia water solution is 2mol/L. The ternary salt solution and the sodium hydroxide solution enter a reaction device in the same liquid feeding mode, the reaction temperature is controlled to be 60 ℃, the pH value is controlled to be 8.6-9.5, the ammonia concentration of slurry in a second reaction kettle is 0.2mol/L, and the reaction is carried outThe process is carried out under stirring and full-process nitrogen gas inlet, the reaction time is 32 hours, and the shell layer of the precursor is prepared.
And finally, sequentially performing centrifugal washing, drying, screening and deironing to obtain the composite sodium ion positive electrode precursor. Wherein the washing water is saturated Na 2 CO 3 A solution.
The nucleus of the quaternary precursor prepared in this example 1 had a particle size D50 of 2.3um and a morphology of spheroidal agglomerates (see fig. 1).
Examples
Preparing a mixed quaternary salt solution of sodium salt, nickel salt, ferric salt and manganese salt, wherein sodium: nickel: iron: the molar ratio of manganese is 1:1:1:1, and the molar concentration of metal ions in the quaternary salt solution is 2mol/L.
Preparing a sodium carbonate precipitant solution, wherein the molar concentration of sodium carbonate is 4mol/L.
Controlling the flow ratio of the quaternary salt solution to the sodium carbonate precipitant solution to be 1:3, preparing carbonic acid quaternary material slurry in a first reaction kettle by adopting a spray method (spray drying method), and enabling the slurry to flow into a concentration device for concentration, wherein the density of the slurry reaches 1.35g/cm 3 Gradually transferring the slurry into a wet coprecipitation reaction kettle (a second reaction kettle) to serve as initial base solution; preparing a mixed ternary salt solution of nickel salt, iron salt and manganese salt, preparing an ammonia water solution and a sodium hydroxide solution, and pumping the ammonia water solution and the sodium hydroxide solution into a reaction device through a peristaltic pump, wherein the nickel: iron: the molar ratio of manganese is 1:1:1, the concentration of ternary salt solution is 2mol/L, the concentration of sodium hydroxide is 8mol/L, and the concentration of ammonia water solution is 2mol/L. The ternary salt solution and the sodium hydroxide solution enter a reaction device in the same liquid feeding mode, the reaction temperature is controlled to be 60 ℃, the pH value is controlled to be 8.6-9.5, the ammonia concentration of slurry in the reaction kettle is 0.2mol/L, the reaction process is carried out under stirring and nitrogen gas is introduced in the whole process, the reaction time is 32 hours, and a shell layer of the precursor is prepared.
And finally, sequentially performing centrifugal washing, drying, screening and deironing to obtain the composite sodium ion positive electrode precursor. Wherein the washing water is saturated Na 2 CO 3 A solution.
The composite sodium ion positive electrode precursor prepared in the embodiment 2 has a granularity D50 of 4.6um and a morphology of cauliflower-like particles (see figure 2).
Comparative example 1:
the difference from example 2 is that: the ferronickel-manganese mixed ternary salt solution is in an upper liquid inlet mode, sodium hydroxide is in a lower liquid inlet mode, and the rest is completely the same as the embodiment 2, and the composite sodium ion positive electrode precursor is obtained through centrifugal washing, drying and screening for iron removal. As shown in fig. 3, the precursor primary particles of comparative example 1 were coarse and fine, and not uniform enough.
Table 1 shows the product data for the products obtained for each example.
From the data of each example and each comparative example in table 1, it can be seen that: in comparative example 1, the ferronickel manganese solution was fed in an upper feed mode, resulting in a reduction in the tap density of the precursor and a reduction in the electrical properties. The sodium ion positive electrode precursor prepared by the method has uniform shape, and the discharge capacities of the precursor materials in the example 1 and the example 2 after sintering and cycling for 50 times under the current density of 0.1C are 140.2mAh/g and 142.6mAh/g respectively.
Comparative example 2:
the difference from example 1 is that: the precipitant sodium carbonate was fed directly to the slurry without spraying to prepare a slurry of nuclei, the remainder being exactly the same as in example 1. As shown in FIG. 4, the morphology of the cores of comparative example 2 agglomerated and the morphology of the cores was not uniform.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (11)
1. A composite sodium ion positive electrode precursor, characterized in that: has the general formula of Na x Ni y1 Fe z1 Mn 1-y1-z1 (CO 3 ) 1+x/2+ a Ni y2 Fe z2 Mn 1-y2-z2 (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein 0 is<x<1、0<y1<1、0<z1<1、0<y2<1、0<z2<1、0<y1+z1<1、0<y2+z2<1、0.1≤a≤10;
The composite sodium ion positive electrode precursor is of a core-shell structure, the core is a carbonic acid quaternary material, and the general formula is Na x Ni y1 Fe z1 Mn 1-y1-z1 (CO 3 ) 1+x/2 ;
The shell layer is made of ternary material and has a general formula of Ni y2 Fe z2 Mn 1-y2-z2 (OH) 2 。
2. The composite sodium ion positive electrode precursor according to claim 1, wherein: the D50 of the precursor is 4.5-5.5 mu m, and the radius of the nucleus occupies 40-50% of the radius of the precursor; the tap density of the precursor is 1.30-1.60 g/m 3 Specific surface area of 15-25 m 2 /g。
3. A preparation method of a composite sodium ion positive electrode precursor is characterized by comprising the following steps: a method for preparing the composite sodium ion positive electrode precursor according to claim 1 or 2, the preparation method comprising:
preparing a mixed quaternary salt solution of nickel salt, iron salt and manganese salt by using an aqueous solution, and preparing a sodium carbonate precipitant solution; preparing a mixed ternary salt solution of nickel salt, iron salt and manganese salt; preparing an ammonia water solution and a sodium hydroxide solution;
preparing carbonic acid quaternary material slurry in a first reaction kettle by adopting a spray method, wherein the reaction temperature is 40-70 ℃, after reacting for 1-2 hours, starting overflow and circulation of the first reaction kettle and a concentration device, and when the density of the slurry in the kettle reaches 1.35-1.5 g/cm 3 Stopping the reaction, wherein the slurry in the kettle is used as nuclear slurry, and the D50 of the slurry is 1.8-2.5 mu m;
step three, transferring the nuclear slurry serving as an initial base solution into a second reaction kettle for wet coprecipitation reaction; the ternary salt solution, the sodium hydroxide solution and the ammonia water solution are fed into a second reaction kettle in a liquid feeding mode, the reaction temperature in the kettle is controlled to be 40-70 ℃, and the pH value in the kettle is controlled to be 8.6-9.55 through the sodium hydroxide solution; the reaction process is carried out under the conditions of stirring and full-process nitrogen or inert gas introduction, a shell layer of the precursor is prepared, and the reaction is stopped until the slurry D50 grows to the target particle size;
and step four, sequentially performing centrifugal washing, drying and screening for iron removal on the product in the step three to obtain the composite sodium ion positive electrode precursor.
4. A method of preparation according to claim 3, characterized in that: in the first step, the aqueous solution is hydroxide precursor mother liquor wastewater, and the pH is regulated to 1-3 by sulfuric acid solution.
5. The method of manufacturing according to claim 4, wherein: the mother liquor wastewater is a mixed solution containing ammonia nitrogen and sodium sulfate, the pH value of the mixed solution is 10-13, the concentration of the sodium sulfate is 50-150 g/L, and the concentration of the ammonia nitrogen is 5-10 g/L.
6. A method of preparation according to claim 3, characterized in that: in the first step, the molar concentration of metal ions of the quaternary salt solution is 1-2 mol/L, and the molar concentration of the sodium carbonate precipitant solution is 1-4 mol/L; the molar concentration of metal ions of the ternary salt solution is 1-2 mol/L.
7. A method of preparation according to claim 3, characterized in that: in the second step, the spraying method adopts a pneumatic spray head to spray the sodium carbonate precipitant solution into the quaternary salt solution in a spray mode to form the carbonic acid quaternary material slurry.
8. A method of preparation according to claim 3, characterized in that: in the second step, the liquid inlet speed of the quaternary salt solution is 100-500 ml/min, and the ratio of the liquid inlet flow of the sodium carbonate precipitant solution to the liquid inlet flow of the quaternary salt solution is 1-3:1.
9. A method of preparation according to claim 3, characterized in that: in the third step, the stirring rotation speed is 550-650 rpm.
10. A method of preparation according to claim 3, characterized in that: and the total reaction time of the second step and the third step is 10-34 h.
11. A method of preparation according to claim 3, characterized in that: in the fourth step, the washing liquid is Na 2 CO 3 A solution.
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