CN117800410A - Positive electrode material precursor for sodium ion battery and preparation method thereof - Google Patents
Positive electrode material precursor for sodium ion battery and preparation method thereof Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 77
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 37
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011164 primary particle Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000011163 secondary particle Substances 0.000 claims abstract description 28
- IREHHCMIJCTSKK-UHFFFAOYSA-H [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] IREHHCMIJCTSKK-UHFFFAOYSA-H 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 113
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 59
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 56
- 229910052751 metal Inorganic materials 0.000 claims description 47
- 239000002184 metal Substances 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 46
- 230000032683 aging Effects 0.000 claims description 44
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 36
- 239000011572 manganese Substances 0.000 claims description 33
- 239000012266 salt solution Substances 0.000 claims description 24
- 238000000975 co-precipitation Methods 0.000 claims description 23
- 238000010899 nucleation Methods 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 21
- 230000006911 nucleation Effects 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 229910021529 ammonia Inorganic materials 0.000 claims description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 17
- 229910052748 manganese Inorganic materials 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 26
- 239000002135 nanosheet Substances 0.000 abstract description 6
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 238000009831 deintercalation Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 54
- 239000007788 liquid Substances 0.000 description 32
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 description 24
- 239000002002 slurry Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000003513 alkali Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012716 precipitator Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 238000010903 primary nucleation Methods 0.000 description 2
- 229960003351 prussian blue Drugs 0.000 description 2
- 239000013225 prussian blue Substances 0.000 description 2
- 238000010900 secondary nucleation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- -1 NCM series hydroxides Chemical class 0.000 description 1
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- KEBVLXZBNYKBFW-UHFFFAOYSA-J iron(2+);manganese(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Fe+2] KEBVLXZBNYKBFW-UHFFFAOYSA-J 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of sodium ion batteries, and provides a positive electrode material precursor for a sodium ion battery and a preparation method thereof. The nickel-iron-manganese hydroxide prepared by the invention is spheroid secondary particles assembled by primary crystal grains, the primary particles are hexagonal nano sheets with a (001) surface being dominant, and the secondary particles are formed by orderly stacking or disordered cross-bonding of the primary particles. In the process, the thickness of primary particles of the precursor spherical inner core is increased, the orientation is improved, the crystallization performance is optimized, the structural stability of the precursor end is improved, rich (001) crystal faces are provided, and rich sodium ion deintercalation active sites can be provided for the sintered positive electrode material.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a positive electrode material precursor for a sodium ion battery and a preparation method thereof.
Background
In recent years, with the proposal of carbon peak and carbon neutralization concepts, the electric automobile and the hybrid power battery land, and the new energy industry is rapidly developed. In order to meet huge market demands of power batteries, energy storage, 3C products and the like, the electrode material with high performance is developed and prepared. At present, although the lithium ion battery is rapidly developed in the field of new energy automobiles and rapidly occupies the market of traditional automobiles, the lithium resource generated by the lithium ion battery is tense, and the price of raw materials of metal nickel salt and lithium salt is high, so that the cost of the lithium ion battery is further increased, a new field capable of being separated from a court of the lithium ion battery is imperative, and the sodium ion battery is generated under the background.
The sodium ion battery has the advantages of cost because the sodium ion is used for replacing lithium ion, and the positive electrode material of the sodium ion battery mainly comprises three routes: prussian blue/albino compound, polyanion compound and lamellar oxide, wherein the lamellar oxide and ternary material are similar in overall preparation process, and co-precipitation reaction is adopted, so that experimental instruments and line facilities are easy to transfer or share, and therefore, the Prussian blue/albino compound, polyanion compound and lamellar oxide are widely paid attention to.
However, most of the preparation of layered oxides of sodium ion batteries at present is still in a laboratory stage, the products of mass production machines are fewer, the preparation of the layered oxides is based on nickel-iron-manganese-based precursors, and similar to NCM series hydroxides, nickel-iron-manganese hydroxides are grown from nano-scale primary particles in an oriented manner, and are stacked and agglomerated into spherical secondary particles. The difference is that the nickel-iron-manganese hydroxide is realized by coprecipitation under the alkaline condition of divalent nickel, iron and manganese ions, but the solubility products of the nickel-iron-manganese hydroxide and the iron-manganese hydroxide are inconsistent, the coprecipitation is not satisfied, and although the complexation of ammonia can promote the coprecipitation, the balance constant of the coprecipitation reaction of the divalent iron is larger than the gap between the divalent nickel and the manganese, so that the nickel-iron-manganese hydroxide precursor has poorer crystallinity and lower density, and the stable sintering of the structural support anode material can not be provided.
Disclosure of Invention
The invention aims to solve the technical problems and provide a novel positive electrode material precursor for a sodium ion battery and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a positive electrode material precursor for a sodium ion battery, which comprises a primary particle (hexagonal nano-plate) nucleation and growth process and a secondary particle (micron-sized particle) growth process, wherein an aging process is arranged at the primary particle nucleation and growth initial stage. Aging refers to a process operation in which the feed is stopped at some stage, the environment of the original system is maintained or slightly adjusted, for a period of time. By setting the aging process, the nucleation of continuous crystals in the early stage of the reaction is interrupted, and in order to exist stably in the slurry system, part of the formed crystal nuclei and unstable primary particles are dissociated into solute ions or ion groups for reducing the specific surface energy of the primary particles, and then adsorbed to the surface of the stable primary particles for recrystallization. Since no new solute ions enter the slurry system, the supersaturation will be slightly reduced during the dissociation and recrystallization of the crystals, and the dissociated recrystallized solute ions will be more prone to adsorb to the primary particle surface for crystal growth rather than re-nucleation. The quantity of crystal nucleus in the reaction system is reduced and the thickness of primary particles which exist stably is increased through a period of aging process, so that Fe can be optimized 2+ Relative to Ni 2+ With Mn 2+ The problem of inconsistent precipitation rate is that the precursor ball core is more compact, the core primary particle thickness is more consistent, and more ordered growth orientation and stacking order are provided for the growth of the outer primary particles.
Preferably, the method specifically comprises the following steps:
(1) Preparing a mixed metal salt solution containing nickel, iron and manganese;
(2) Preparing a base solution;
(3) Feeding is started under inert atmosphere, mixed metal salt solution is introduced into base solution for coprecipitation reaction to initially nucleate, and primary particles nucleate at the moment;
(4) Stopping feeding after initial nucleation for a certain time, and aging for a certain time;
(5) And (3) continuing feeding after the aging is finished, introducing the mixed metal salt solution into a reaction system to perform coprecipitation reaction for secondary particle growth, reacting to the final particle size D50, and performing aftertreatment to obtain the precursor nickel-iron-manganese hydroxide of the positive electrode material for sodium ions.
Preferably, in the step (1), the molar ratio of metals in the mixed metal salt solution of nickel, iron and manganese is x: y:1-x-y, wherein x is more than or equal to 0.2 and less than or equal to 0.4,0.2 and y is more than or equal to 0.4; the chemical formula of the obtained nickel-iron-manganese hydroxide precursor is Ni x Fe y Mn 1-x-y (OH) 2 ，0.2≤x≤0.4，0.2≤y≤0.4。
Preferably, the total concentration of metals in the mixed metal salt solution of nickel, iron and manganese in the step (1) is 1.0-2.2 mol/L.
Preferably, the configuration of the mixed metal salt in the step (1) comprises dissolving divalent metal sulfate of nickel, iron and manganese in water to prepare a divalent metal sulfate solution of nickel, iron and manganese with a certain proportion of 1.0-2.2 mol/L.
Preferably, the temperature of the bottom solution in the step (2) is 50-70 ℃, the pH is 11.00-11.70, and the ammonia content is 3-10 g/L; more preferably, the pH is regulated by sodium hydroxide, and the ammonia amount is regulated by ammonia water.
Preferably, the adding amount of the base solution in the step (2) is 50% -100% of the volume of the reaction kettle.
Preferably, the configuration of the bottom solution in the step (2) may be: adding 50-100L pure water into a 100L reaction kettle, starting a stirrer turbine at 900-1100 rpm, and introducing 0.4-1.0 m 3 Heating the reaction kettle to 50-70 ℃ in inert atmosphere of/h; adding sodium hydroxide solution and ammonia water solution with certain concentration into a reaction kettle, controlling the pH value of the solution in the reaction kettle to be 11.00-11.70, and controlling the ammonia content to be 3-10 g/L.
Preferably, in the step (2), the turbine of the reactor stirrer is one or two of a 4-6-blade 60-90-degree straight-blade disc turbine and a 4-6-blade 30-60-degree inclined-blade opening turbine, and the number of turbine layers is 1-3.
Preferably, all of the steps (1) to (5) are carried out under an inert atmosphere, and the flow rate of the inert atmosphere in the steps (3) to (5) is preferably 0.4 to 1.0m 3 Preferably, the inert atmosphere is at least one of nitrogen, helium and argon.
Preferably, the flow rate of the mixed metal salt solution in the step (3) is 1-10% of the volume of the reaction kettle per hour, the initial nucleation time is 0.5-2 h of the initial feeding, the pH of the initial nucleation process is 11.00-11.70, the ammonia content of the process is 3-10 g/L, the temperature is 50-70 ℃, and the rotation speed of the stirrer is 900-1100 rpm; the reaction pH is regulated by adding a precipitant.
Preferably, the precipitant used in the coprecipitation reaction in the step (3) is sodium hydroxide, and the complexing agent is ammonia water; more preferably, the sodium hydroxide is prepared as a solution with a concentration of 2 to 10mol/L and the ammonia water with a concentration of 5 to 10mol/L.
Preferably, in the step (4), the aging temperature is 50-70 ℃, the rotation speed of the stirrer is 350-900 rpm, the pH is 11.00-11.70, the ammonia content is 3-10 g/L, and the aging duration is 0.5-15 h. Under the condition of the rotating speed, the solute can be uniformly dispersed, and meanwhile, agglomeration in the recrystallization process is effectively avoided.
Preferably, when the feeding is continued in the step (5), the flow rate of the metal salt solution is 5% -10% of the volume of the reaction kettle per hour, the reaction pH in the growth period of the secondary particles is 10.20-11.00, the ammonia content is 3-10 g/L, the temperature is 50-70 ℃, and the rotating speed of the stirrer is 350-900 rpm.
Preferably, D in the step (5) 50 Is 2-10 mu m.
Preferably, the post-treatment comprises conventional treatment steps of aging, washing, filtering, drying, sieving and the like.
Preferably, the method specifically comprises the following steps:
dissolving divalent metal sulfate of nickel, iron and manganese in water to prepare a divalent metal sulfate solution of nickel, iron and manganese with a certain proportion of 1.0-2.2 mol/L;
adding 50-100L pure water into a 100L reaction kettle, and starting 900-1100 rpmIs introduced into the stirrer turbine of 0.4 to 1.0m 3 Heating the reaction kettle to 50-70 ℃ by inert gas per hour;
adding sodium hydroxide solution and ammonia water solution with certain concentration into a reaction kettle, controlling the pH value of the solution in the reaction kettle to be 11.00-11.70 and the ammonia content to be 3-10 g/L;
the mixed metal salt solution is put into a reaction kettle, mixed with sodium hydroxide solution and ammonia water solution, and subjected to coprecipitation reaction; the flow of the metal salt is 1-10% of the volume of the reaction kettle per hour, the pH of the initial nucleation period reaction is 11.00-11.70, the rotating speed of the stirrer is 900-1100 rpm,
after the initial nucleation period is finished, stopping feeding and performing an aging process, wherein the aging temperature is 50-70 ℃, the rotation speed of a stirrer is 350-900 rpm, the pH is 11.00-11.70, and the aging duration is 0.5-15 h;
after aging, secondary particle growth is carried out, metal salt solution, ammonia water and liquid alkali are continuously fed, the flow rate of the metal salt solution is linearly increased to 5-10% of the volume of the reaction kettle per hour, the flow rates of the liquid alkali and the ammonia water are synchronously increased, the pH value of a reaction system is controlled to be 10.20-11.00, the reaction kettle is kept stable, the temperature of the reaction kettle is 50-70 ℃, and the flow rate of inert gas is 0.4-1.0 m 3 And (h) linearly reducing the rotating speed of the stirrer to 350-900 rpm, continuously growing precursor secondary particles, and reaching a reaction end point D 50 Stopping feeding after reaching the target granularity to obtain the nickel-iron-manganese hydroxide precursor.
The invention also provides the positive electrode material precursor for the sodium ion battery, which is prepared by the preparation method. The nickel-iron-manganese hydroxide prepared by the invention is a spheroid secondary particle assembled by primary grains, the primary particles are hexagonal nano sheets with a (001) surface being dominant, and the secondary particles are micron-sized particles formed by orderly stacking or disordered crossing of the primary particles. The abundant (001) crystal face provides abundant sodium ion deintercalation active sites for the sintered positive electrode material.
In the invention, in the nickel, iron and manganese sulfate solution, ferrous ions are easily oxidized in the air, and ferrous ions and manganous ions are easily oxidized in the reaction process, so that inert gas is continuously introduced or sealed in the configuration and storage processes of the sulfate solution, and the coprecipitation reaction needs a good sealing effect of a reaction kettle to prevent air from entering.
In the invention, the coprecipitation reaction nucleation period comprises a primary nucleation period and a secondary nucleation period, wherein the primary nucleation period is within the first 0.5-2 h of starting feeding, and the secondary nucleation penetrates through the whole precursor particle growth process under the supersaturation condition. Generally, the (001) crystal plane of the hexagonal nanoplatelets is less active than the (100) crystal plane and the (010) crystal plane, and crystals preferentially grow along the (100) and (010) planes, so that a two-dimensional layered nanoplatelet structure is formed. Under high-temperature and high-frequency stirring, the slurry system is violent in reaction, the nano sheet layer does not grow sufficiently along [001] and a series of agglomeration behaviors such as collision, bonding, interface solidification and the like already occur, and the behavior is more prominent for divalent nickel-manganese elements and divalent iron elements with larger coprecipitation equilibrium constant difference. The premature formation of the secondary particles prevents the precursor particles from forming a tight, stable core, primary particle growth and orientation of the stack, and the sphericity of the secondary particles is affected.
Therefore, the invention provides a preparation method of a positive electrode material precursor for a sodium ion battery, which comprises the steps of stopping feeding when an initial nucleation period is finished by setting a reaction early-stage aging process, keeping the temperature, atmosphere and pressure in a kettle stable, aging at a certain stirrer rotating speed, temperature and aging duration, continuing feeding reaction to a final point granularity after the duration is finished, aging, washing, filtering, drying and sieving to obtain a target product;
according to the aging process, after initial nucleation is finished, feeding is stopped, and the whole reaction system is in a state of supersaturation of solute ions. Hexagonal nano-sheets (primary particles) are easy to aggregate into spheroids (secondary particles) under the condition that the growth in the [001] direction is insufficient, the primary particles are thinner and unstable, and the surfaces of the secondary particles are filled with more gaps; after stopping feeding, no nucleated metal salt solute ions are continuously provided, in the original solute ion system, formed crystal nuclei or unstable nano sheets are dissolved for the purpose of reducing specific surface energy of the self-body to be stably existing in the system, the solute ions are adsorbed and recrystallized along stable hexagonal nano sheet crystal bodies, the (001) crystal face adsorbs the solute ions through intermolecular force to continue to crystallize, and the (010) crystal face and the (100) crystal face with higher chemical activity have no continuous solute ion input, so that the growth speed is greatly reduced, and the thickness of primary particles is increased. The gaps on the surfaces of the secondary particles are more likely to absorb solute ions for crystallization, so that the gaps are filled. The increase of the primary particle size and the filling of the gaps on the surface of the secondary particles enable the secondary particles to be more compact.
After the aging is finished, the coprecipitation reaction is continued, under the condition of reducing the supersaturation degree, the nucleation rate is reduced, the growth rate is increased, solute ions re-entering the reaction system are adsorbed to the surface of the aged secondary particles, the growth is continued, the aged secondary particles become more compact, the density of the precursor spherical core is increased, the stacking orientation of primary particles is better, and the thickness of the crystals in the [001] direction is increased and the consistency is better.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a precursor of a positive electrode material for a sodium ion battery and a preparation method thereof, wherein an aging stage is arranged before a secondary particle growth stage, so that primary particles of the precursor ball fully grow along the [001] direction, and gaps of the secondary particles are reduced, thereby being beneficial to obtaining the precursor ball with compact inner core and better primary particle orientation of crystals, and providing stable crystal structure and good crystallization performance for sintering the positive electrode material. Has wide market application prospect. Meanwhile, the preparation method is simple and convenient to operate, mild in condition and suitable for industrial mass production and application.
Drawings
FIG. 1 is a drawing of Ni prepared in example 1 of the present invention 0.33 Fe 0.33 Mn 0.33 (OH) 2 XRD pattern of precursor;
FIG. 2 is a drawing of Ni prepared in comparative example 1 of the present invention 0.33 Fe 0.33 Mn 0.33 (OH) 2 XRD pattern of precursor;
FIG. 3 is a drawing of Ni prepared in example 1 of the present invention 0.33 Fe 0.33 Mn 0.33 (OH) 2 Scanning Electron Microscope (SEM) cross-section of the precursor at 50000 times;
FIG. 4 is a drawing of Ni prepared in example 1 of the present invention 0.33 Fe 0.33 Mn 0.33 (OH) 2 Scanning Electron Microscope (SEM) images of the precursor at 20000 x;
FIG. 5 is Ni prepared in comparative example 1 of the present invention 0.33 Fe 0.33 Mn 0.33 (OH) 2 Scanning Electron Microscope (SEM) cross-section of the precursor at 50000 times;
FIG. 6 is a Ni film produced in comparative example 1 of the present invention 0.33 Fe 0.33 Mn 0.33 (OH) 2 Scanning Electron Microscope (SEM) images of the precursor at 20000 x.
Detailed Description
For the convenience of understanding, the technical solution and embodiments of the present invention will be further described in detail, fully and explicitly with reference to the accompanying drawings, and it should be understood that the embodiments described herein are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but only some, but not all, of the embodiments of the present invention, and the described embodiments are merely for illustrating and explaining the present invention, and are not limited to the present invention. All other embodiments, which can be made by those skilled in the art without making any inventive effort, are intended to be within the scope of the present invention, based on the examples herein.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and the materials, reagents, etc. used in the examples are commercially available unless otherwise specified.
Example 1
The invention provides a preparation method of a precursor nickel-iron-manganese hydroxide of a positive electrode material for a sodium ion battery, wherein the chemical formula of the precursor nickel-iron-manganese hydroxide is Ni 0.33 Fe 0.33 Mn 0.33 (OH) 2 The method comprises the following steps:
dissolving divalent metal sulfate of nickel, iron and manganese in water to prepare a metal sulfate solution with a certain concentration and proportion, wherein the molar ratio of the metal salts of nickel, iron and manganese is 1:1:1, and the total concentration of feed liquid is 1.8mol/L;
adding full kettle pure water into a 100L reaction kettle, starting a stirrer turbine, wherein the stirrer turbine is three layers, the lower layer is a 6-blade 90-degree straight-blade disc turbine, the middle layer and the upper layer are both 4-blade 45-degree inclined-blade start turbines, the rotating speed is 1000rpm, and introducing 0.6m 3 And (3) taking nitrogen as protective atmosphere, sealing the kettle body, controlling a valve, keeping positive pressure in the kettle, and circularly discharging the liquid by using a thickener in the whole process.
Heating a reaction kettle to 55 ℃, taking 8mol/L ammonia water as a complexing agent, taking 10mol/L sodium hydroxide solution as a precipitator, putting the sodium hydroxide solution and the ammonia water solution into the reaction kettle to prepare a reaction base solution with pH of 11.50 and ammonia content of 8g/L, putting a metal salt solution into the reaction kettle, mixing with the sodium hydroxide and the ammonia solution, and performing coprecipitation reaction.
Initial nucleation is carried out 1.5h before the reaction, the pH and ammonia content of the slurry of the coprecipitation system are controlled to be stable, the flow rate of the metal salt solution is 1% of the volume of the reaction kettle per hour in the first 1.5h, the stirring is continuously carried out at the rotating speed of 1000rpm, and the feeding is stopped after 1.5 h;
the pH of the slurry is kept at 11.50, the temperature of the reaction kettle is 55 ℃, and the nitrogen flow is 0.6m 3 And/h, closing the concentrator, discharging, opening the internal circulation of the reactor, reducing the rotating speed of the reactor to 600rpm, and continuously stirring for 2h to perform precursor aging reaction.
After aging, the flow rate of the feed liquid is linearly increased to 5 percent of the volume of the reaction kettle per hour (taking a 100L reaction kettle as an example, the flow rate of the feed liquid is increased from 1L/h to 5L/h after 1.5h, the flow rate of the feed liquid is increased by 1L/h every 4h, and the total flow rate of the feed liquid is 16 h), the flow rates of liquid alkali and ammonia water are synchronously increased, the pH of a reaction system is controlled to be 10.90, the reaction kettle is kept stable, the temperature of the reaction kettle is 55 ℃, and the flow rate of nitrogen is 0.6m 3 Preferably, the rotation speed of the stirrer is 1000rpm and is linearly reduced to 600rpm at 20rpm/h, and the precursor secondary particle growth is continuously carried out until the reaction end point D 50 Stopping feeding after 5.5 μm;
aging the obtained precursor particles, adding liquid alkali into an aging kettle to prepare precursor slurry containing 1mol/LNaOH,the stirrer speed was 300rpm. Pumping the aged slurry into a centrifuge, washing with 300L of hot pure water with the temperature of 70 ℃, centrifuging by the centrifuge, drying the materials in a baking oven with the temperature of 130 ℃, and sieving by a 400-mesh screen to obtain a target product D50 of 5.5 mu m of precursor Ni for the positive electrode of the sodium ion battery 0.33 Fe 0.33 Mn 0.33 (OH) 2 。
Example 2
The invention provides a preparation method of a precursor nickel-iron-manganese hydroxide of a positive electrode material for a sodium ion battery, wherein the chemical formula of the precursor nickel-iron-manganese hydroxide is Ni 0.33 Fe 0.33 Mn 0.33 (OH) 2 The method comprises the following steps:
dissolving divalent metal sulfate of nickel, iron and manganese in water to prepare a metal sulfate solution with a certain concentration and proportion, wherein the molar ratio of the metal salts of nickel, iron and manganese is 1:1:1, and the total concentration of feed liquid is 1.8mol/L;
adding full kettle pure water into a 100L reaction kettle, starting a stirrer turbine, wherein the stirrer turbine is three layers, the lower layer is a 6-blade 90-degree straight-blade disc turbine, the middle layer and the upper layer are both 4-blade 45-degree inclined-blade start turbines, the rotating speed is 900rpm, and introducing 0.6m 3 And (3) taking nitrogen as protective atmosphere, sealing the kettle body, controlling a valve, keeping positive pressure in the kettle, and circularly discharging the liquid by using a thickener in the whole process.
Heating a reaction kettle to 55 ℃, taking a certain amount of ammonia water with the concentration of 8mol/L as a complexing agent and a 10mol/L sodium hydroxide solution as a precipitator, putting the sodium hydroxide solution and the ammonia water solution into the reaction kettle to prepare a reaction base solution with the pH of 11.40 and the ammonia content of 8g/L, putting a metal salt solution into the reaction kettle, mixing with the sodium hydroxide and the ammonia solution, and performing coprecipitation reaction.
Initial nucleation is carried out 1h before the reaction, the pH and ammonia content of the slurry of the coprecipitation system are controlled to be stable, the flow rate of the metal salt solution is 1% of the volume of the reaction kettle per hour in the first 1.5h, the stirring is continuously carried out at the rotating speed of 900rpm, and the feeding is stopped after 1 h;
the pH of the slurry is kept at 11.40, the temperature of the reaction kettle is 55 ℃, and the nitrogen flow is 0.6m 3 And/h, closing the thickener to clear, opening the internal circulation of the kettle, reducing the rotating speed of the reaction kettle to 600rpm, and continuing stirringAnd (5) stirring for 1h to perform precursor aging reaction.
After aging, the flow rate of the feed liquid is linearly increased to 5% of the volume of the reaction kettle per hour (taking a 100L reaction kettle as an example, the flow rate of the feed liquid is increased from 1L/h to 5L/h after 1.5h, the flow rate of the feed liquid is increased by 1L/h after 4h, the total flow rate of the feed liquid is 16 h), the flow rates of liquid alkali and ammonia water are synchronously increased, the pH of a reaction system is controlled to be 10.90, the reaction system is kept stable after the pH of the reaction system is reduced to 10.80 after the D50 is as long as 6 mu m, the temperature of the reaction kettle is 55 ℃, and the flow rate of nitrogen is 0.6m 3 And/h, the rotation speed of the stirrer is 900rpm and linearly decreases to 600rpm, the growth of the precursor secondary particles is continuously carried out, and the reaction end point D is reached 50 Stopping feeding after 10.0 μm;
and (3) aging the obtained precursor particles, adding liquid alkali into an aging kettle to prepare precursor slurry containing 1mol/LNaOH, and rotating a stirrer at 300rpm. Pumping the aged slurry into a centrifuge, washing with 300L of hot pure water with the temperature of 70 ℃, centrifuging by the centrifuge, drying the materials in a baking oven with the temperature of 130 ℃, and sieving by a 400-mesh screen to obtain a target product D50 of 10.0 mu m of precursor Ni for the positive electrode of the sodium ion battery 0.33 Fe 0.33 Mn 0.33 (OH) 2 。
Example 3
The invention provides a preparation method of a precursor nickel-iron-manganese hydroxide of a positive electrode material for a sodium ion battery, wherein the chemical formula of the precursor nickel-iron-manganese hydroxide is Ni 0.33 Fe 0.33 Mn 0.33 (OH) 2 The method comprises the following steps:
dissolving divalent metal sulfate of nickel, iron and manganese in water to prepare a metal sulfate solution with a certain concentration and proportion, wherein the molar ratio of the metal salts of nickel, iron and manganese is 1:1:1, and the total concentration of feed liquid is 1.8mol/L;
adding full kettle pure water into a 100L reaction kettle, starting a stirrer turbine, wherein the stirrer turbine is three layers, the lower layer is a 6-blade 90-degree straight-blade disc turbine, the middle layer and the upper layer are both 4-blade 45-degree inclined-blade start turbines, the rotating speed is 1000rpm, and introducing 0.6m 3 And (3) taking nitrogen as protective atmosphere, sealing the kettle body, controlling a valve, keeping positive pressure in the kettle, and circularly discharging the liquid by using a thickener in the whole process.
Heating a reaction kettle to 55 ℃, taking a certain amount of 8mol/L ammonia water as a complexing agent, taking 10mol/L sodium hydroxide solution as a precipitator, putting the sodium hydroxide solution and the ammonia water solution into the reaction kettle to prepare a reaction base solution with pH of 11.50 and ammonia content of 6g/L, putting a metal salt solution into the reaction kettle, mixing with the sodium hydroxide and the ammonia solution, and carrying out coprecipitation reaction.
Initial nucleation is carried out 2 hours before the reaction, the pH and ammonia content of the slurry of the coprecipitation system are controlled to be stable, the flow rate of the metal salt solution in the first 2 hours is 1 percent of the volume of the reaction kettle per hour, the stirring is continuously carried out at the rotating speed of 1000rpm, and the feeding is stopped after 2 hours;
the pH of the slurry is kept at 11.50, the temperature of the reaction kettle is 55 ℃, and the nitrogen flow is 0.6m 3 And/h, closing the concentrator, discharging, opening the internal circulation of the kettle, keeping the rotating speed of the reaction kettle at 600rpm, and continuously stirring for 12h to perform precursor aging reaction.
After aging, the flow rate of the feed liquid is linearly increased to 5 percent of the volume of the reaction kettle per hour (taking a 100L reaction kettle as an example, the flow rate of the feed liquid is increased from 1L/h to 5L/h after 1.5h, the flow rate of the feed liquid is increased by 1L/h every 4h, and the total flow rate of the feed liquid is 16 h), the flow rates of liquid alkali and ammonia water are synchronously increased, the pH of a reaction system is controlled to be 10.90, the reaction kettle is kept stable, the temperature of the reaction kettle is 55 ℃, and the flow rate of nitrogen is 0.6m 3 And/h, maintaining the rotation speed of the stirrer at 900rpm to the reaction end point, and continuously carrying out secondary particle growth of the precursor until the reaction end point D 50 Stopping feeding after 3.5 μm;
and (3) aging the obtained precursor particles, adding liquid alkali into an aging kettle to prepare precursor slurry containing 1mol/LNaOH, and rotating a stirrer at 300rpm. Pumping the aged slurry into a centrifuge, washing with 300L of hot pure water with the temperature of 70 ℃, centrifuging by the centrifuge, drying the materials in a baking oven with the temperature of 130 ℃, and sieving by a 400-mesh screen to obtain a target product D50 of 10.0 mu m of precursor Ni for the positive electrode of the sodium ion battery 0.33 Fe 0.33 Mn 0.33 (OH) 2 。
Comparative example 1
The invention provides a preparation method of a precursor nickel-iron-manganese hydroxide of a positive electrode material for a sodium ion battery, wherein the chemical formula of the precursor nickel-iron-manganese hydroxide is Ni 0.33 Fe 0.33 Mn 0.33 (OH) 2 The method comprises the following steps:
dissolving divalent metal sulfate of nickel, iron and manganese in water to prepare a metal sulfate solution with a certain concentration and proportion, wherein the molar ratio of the metal salts of nickel, iron and manganese is 1:1:1, and the total concentration of feed liquid is 1.8mol/L;
adding full kettle pure water into a 100L reaction kettle, starting a stirrer turbine, wherein the stirrer turbine is three layers, the lower layer is a 6-blade 90-degree straight-blade disc turbine, the middle layer and the upper layer are both 4-blade 45-degree inclined-blade start turbines, the rotating speed is 1000rpm, and introducing 0.6m 3 And (3) taking nitrogen as protective atmosphere, sealing the kettle body, controlling a valve, keeping positive pressure in the kettle, and circularly discharging the liquid by using a thickener in the whole process.
Heating a reaction kettle to 55 ℃, taking a certain amount of ammonia water with the concentration of 8mol/L as a complexing agent and a 10mol/L sodium hydroxide solution as a precipitator, putting the sodium hydroxide solution and the ammonia water solution into the reaction kettle to prepare a reaction base solution with the pH of 11.50 and the ammonia content of 8g/L, putting a metal salt solution into the reaction kettle, mixing with the sodium hydroxide and the ammonia solution, and performing coprecipitation reaction.
Initial nucleation is carried out 1.5h before the reaction, the pH and ammonia content of the slurry of the coprecipitation system are controlled to be kept stable, the flow rate of the metal salt solution in the first 1.5h is 1% of the volume of the reaction kettle per hour, the stirring is continuously carried out at the rotating speed of 1000rpm, the flow rate of the feed liquid is linearly increased to 5% of the volume of the reaction kettle per hour after 1.5h (taking a 100L reaction kettle as an example, the flow rate of the feed liquid is increased from 1L/h to 5L/h after 1.5h, and the flow rate of the feed liquid is increased by 1L/h every 4h and is 16h in total), the alkali and ammonia water flow rates are synchronously increased, the pH of the reaction system is controlled to be kept stable after 10.90, the temperature of the reaction kettle is 55 ℃ and the nitrogen flow rate is 0.6m 3 And/h, the rotation speed of the stirrer is 1000rpm and linearly decreases to 600rpm, the growth of the precursor secondary particles is continuously carried out, and the reaction end point D is reached 50 Stopping feeding after 5.5 μm;
and (3) aging the obtained precursor particles, adding liquid alkali into an aging kettle to prepare precursor slurry containing 1mol/LNaOH, and rotating a stirrer at 300rpm. Pumping the aged slurry into a centrifuge, washing with 300L of hot pure water with the temperature of 70 ℃, centrifuging by the centrifuge, drying the materials in a baking oven with the temperature of 130 ℃, and sieving by a 400-mesh screen to obtain a target product D50 of 5.5 mu m before the positive electrode of the sodium ion battery is usedNi as a precursor 0.33 Fe 0.33 Mn 0.33 (OH) 2 。
TABLE 1 Ni prepared in inventive examples 1-3 and comparative example 1 0.33 Fe 0.33 Mn 0.33 (OH) 2 Physicochemical data of precursor
Comparing the prepared precursor sample example 1 with comparative example 1, wherein the D50 of the precursor sample is 5.5 μm, and the comparative example 1 is not subjected to aging process, the cross-section SEM shown in FIG. 5 shows that the precursor ball core has finer primary particles, more gaps exist, the primary particle orientation and thickness uniformity are poor, and the tap density is 1.47g/cm 3 BET of 19.96m 2 And/g, the overall density is smaller, and the surface is provided with more gaps. Fig. 2 is an XRD pattern of comparative example 1, which shows that the (001) peak intensity is low, indicating that the (001) crystal plane orientation and number are small, and that more impurity peaks appear on the refined image, indicating that the crystallinity of the crystal is poor. Example 1 dissolution and recrystallization of core unstable crystals were promoted before rapid growth of precursor spheres along the periphery by an aging process, the crystals being allowed to follow [001]]Fully grows in the direction, the inner core of the aged precursor ball is compact, primary particles are closely stacked, the uniformity is better, and the tap density is 1.68g/cm 3 BET of 13.58m 2 And/g, compared with comparative example 1, has higher tap density and smaller specific surface area, which shows that the precursor core after aging treatment is beneficial to improving the overall density of the precursor ball, reducing the surface gap and enhancing the structural stability of the precursor ball. FIG. 1 shows the XRD pattern of example 1, which shows that the (001) peak intensity is higher, the intensity of the three strong peaks is higher than that of comparative example 1, and the finishing pattern has no impurity peak, so that the crystal has relatively rich (001) crystal plane orientation and the overall crystallization degree is higher.
The precursors of the embodiment 2 and the embodiment 3 with the specification of 10 mu m and 3.5 mu m show that the aging process can be suitable for preparing the precursor of the multi-scale nickel-iron-manganese hydroxide, and the ideal effect can be achieved on the premise of saving the cost by designing the corresponding aging time according to the target specification.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the invention in any way, but other variations and modifications are possible without exceeding the technical solutions described in the claims.
Claims (10)
1. The preparation method of the positive electrode material precursor for the sodium ion battery is characterized by comprising a primary particle nucleation and growth process and a secondary particle growth process, and an aging process is arranged at the primary particle nucleation and growth initial stage.
2. The method for preparing the positive electrode material precursor for the sodium ion battery according to claim 1, which is characterized by comprising the following steps:
(1) Preparing a mixed metal salt solution containing nickel, iron and manganese;
(2) Preparing a base solution;
(3) Feeding is started under inert atmosphere, mixed metal salt solution is introduced into base solution for coprecipitation reaction to initially nucleate, and primary particles nucleate at the moment;
(4) Stopping feeding after initial nucleation for a certain time, and aging for a certain time;
(5) And (3) continuing feeding after the aging is finished, introducing the mixed metal salt solution into a reaction system to perform coprecipitation reaction for secondary particle growth, reacting to the final particle size D50, and performing aftertreatment to obtain the precursor nickel-iron-manganese hydroxide of the positive electrode material for sodium ions.
3. The method for preparing a precursor of a positive electrode material for a sodium ion battery according to claim 2, wherein the concentration of the mixed metal salt solution in the step (1) is 1.0-2.2 mol/L, and the molar ratio of divalent nickel, iron and manganese metal ions in the mixed metal salt is x: y:1-x-y, x is more than or equal to 0.2 and less than or equal to 0.4,0.2, and y is more than or equal to 0.4.
4. The method for preparing the positive electrode material precursor for the sodium ion battery according to claim 2, wherein the reaction kettle stirrer turbine in the step (2) is one or two of a 4-6-blade 60-90-degree straight-blade disc turbine and a 4-6-blade 30-60-degree inclined-blade opening turbine, and the number of turbine layers is 1-3.
5. The method for preparing a precursor of a positive electrode material for a sodium ion battery according to claim 1, wherein the temperature of the base solution in the step (2) is 50-70 ℃, the pH is 11.00-11.70, the ammonia content is 3-10 g/L, and the addition amount of the base solution is 50% -100% of the volume of the reaction kettle.
6. The method for preparing a precursor of a positive electrode material for a sodium ion battery according to claim 1, wherein the flow rate of the mixed metal salt solution in the step (3) is 1% -10% of the volume of the reaction kettle per hour, the initial nucleation time is 0.5-2 h of initial feeding, the pH of the initial nucleation process is 11.00-11.70, the ammonia content is 3-10 g/L, the temperature is 50-70 ℃, and the rotation speed of the stirrer is 900-1100 rpm.
7. The method according to claim 1, wherein the aging temperature in the step (4) is 50-70 ℃, the rotational speed of the stirrer is 350-900 rpm, the pH is 11.00-11.70, and the aging duration is 0.5-15 h.
8. The method for preparing a precursor of a positive electrode material for a sodium ion battery according to claim 1, wherein the flow rate of the metal salt solution is 5% -10% of the volume of the reaction kettle per hour, the reaction pH in the growth period of the secondary particles is 10.20-11.00, the temperature is 50-70 ℃, and the rotation speed of the stirrer is 350-900 rpm when the feeding is continued in the step (5).
9. According to claim 1The preparation method of the positive electrode material precursor for the sodium ion battery is characterized by comprising the following step (5) 50 Is 2-10 mu m.
10. A positive electrode material precursor for sodium ion batteries prepared by the preparation method according to any one of claims 1 to 9.
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