CN115893526A - Nickel-iron-manganese layered hydroxide precursor for sodium ion battery, and preparation method and application thereof - Google Patents
Nickel-iron-manganese layered hydroxide precursor for sodium ion battery, and preparation method and application thereof Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 56
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 27
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000002245 particle Substances 0.000 claims abstract description 58
- 239000000243 solution Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 44
- 230000008569 process Effects 0.000 claims abstract description 27
- 239000012266 salt solution Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000000975 co-precipitation Methods 0.000 claims abstract description 13
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 239000012716 precipitator Substances 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 5
- 150000002696 manganese Chemical class 0.000 claims abstract description 5
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000011572 manganese Substances 0.000 claims description 28
- 229910052742 iron Inorganic materials 0.000 claims description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- -1 ammonium ions Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 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 description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000007772 electrode material Substances 0.000 claims description 4
- 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 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000005347 demagnetization Effects 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 25
- 239000002585 base Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- 238000005086 pumping Methods 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910002551 Fe-Mn Inorganic materials 0.000 description 2
- 229910013724 M(OH)2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 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
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
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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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- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a nickel-iron-manganese layered hydroxide precursor for a sodium ion battery, a preparation method and application, and relates to the technical field of sodium ion batteries. Introducing a mixed metal salt solution consisting of nickel salt, ferrous salt and manganese salt, a precipitator and a complexing agent into a reaction kettle with a prepared base solution for coprecipitation reaction, controlling the reaction temperature and the rotation speed, and continuously introducing inert gas in the reaction process; controlling the concentration of the mixed metal salt solution to be less than or equal to 2.0mol/L, the concentration of the precipitator to be less than or equal to 8.0mol/L and the concentration of the complexing agent to be less than or equal to 6.0mol/L; the reaction is continued until the particle size of the product reaches the target particle size. The nickel-iron-manganese layered hydroxide precursor prepared by the method provided by the invention basically has no small balls in the growth process, can smoothly grow to a target granularity, does not need to add a reducing agent, has good sphericity, is suitable for industrial mass production, and is excellent in electrochemical performance.
Description
Technical Field
The invention relates to the technical field of sodium-ion batteries, in particular to a nickel-iron-manganese layered hydroxide precursor, a preparation method and application.
Background
The key material of the sodium ion battery is the positive electrode material, and the cost of the positive electrode material is one of the main factors determining the cost of the sodium ion battery. The layered transition metal oxide has the advantages of low cost, wide raw material source, simple synthesis process, convenience for large-scale industrial production, high energy density, high voltage platform, excellent comprehensive performance and the like, and is the mainstream research direction of the anode material of the sodium-ion battery at present.
Just like the nickel-cobalt-manganese layered hydroxide precursor for lithium ion batteries, the nickel-iron-manganese layered hydroxide precursor for sodium ion batteries is mainly produced industrially by a liquid-phase coprecipitation method. However, due to the particularity of iron ions, the problems that globules are easy to appear in the growth process, particles are difficult to grow further and the like exist when the nickel-iron-manganese hydroxide precursor is prepared by a liquid-phase coprecipitation method, and the problems are more serious when the particles of the precursor are larger, and are more obvious when the content of iron is higher.
This is because Fe ion cannot be complexed with ammonia but directly reacts with OH - Precipitation of Ni 2+ 、Mn 2+ Solubility product constant (K) sp ) Are respectively 10 -14.7 And 10 -10.4 After complexation with aqueous ammonia, K sp Are respectively 10 -9.11 And 10 -9.23 If it is Fe 3+ Of which K is sp About 2.79 x 10 -39 Very easily precede Ni 2+ 、Mn 2+ Precipitation occurs, thus spontaneous nucleation of small balls is realized, and the grains are difficult to continue to grow; and if it is Fe 2+ Of which K is sp About 4.87 x 10 -17 Inert gas protection is necessary, even reducing agents are added to prevent the material liquid from being oxidized into Fe 3+ Thereby directly preceding Ni 2+ 、Mn 2+ Precipitation occurs, thereby suppressing Fe in the feed liquid 2+ Oxidation and control of ordered precipitation of Fe ions are of great importance, so there are currently no numerous reports on coprecipitation schemes for large-particle, high-iron content nickel-iron-manganese layered hydroxide precursors for sodium ion batteries.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a simple preparation method of a nickel-iron-manganese layered hydroxide precursor, which can control the nickel-iron-manganese layered hydroxide precursor with large particles and high iron content to basically avoid small balls in the growth process without adding any reducing agent, can smoothly grow to a target granularity, has good sphericity and is suitable for industrial mass production.
The invention is realized in the following way:
in a first aspect, the invention provides a preparation method of a nickel-iron-manganese layered hydroxide precursor, which comprises the following steps:
introducing a mixed metal salt solution consisting of nickel salt, ferrous salt and manganese salt, a precipitator and a complexing agent into a reaction kettle which is prepared with a base solution to carry out coprecipitation reaction, controlling the concentration of the mixed metal salt solution to be less than or equal to 2.0mol/L, the concentration of the precipitator to be less than or equal to 8.0mol/L and the concentration of the complexing agent to be less than or equal to 6.0mol/L, controlling the reaction temperature and the rotation speed, continuously introducing inert gas in the reaction process, and continuously reacting until the granularity of a product reaches a target granularity.
The inventor finds that when ammonia water is used as a complexing agent and sodium hydroxide is used as a precipitator, the problems that the nickel-iron-manganese hydroxide precursor prepared by a liquid-phase coprecipitation method is easy to form small balls in the growth process, particles are difficult to grow continuously and the like exist, and the larger the particles of the precursor are, the more serious the problems are, and the higher the iron content is, the more obvious the problems are.
In order to solve the problems that when a liquid-phase coprecipitation method is used for preparing a nickel-iron-manganese hydroxide precursor with large particles and high iron content, small balls are easy to appear in the growth process, and the particles are difficult to grow further, the inventor finds that:
the mixed metal salt solution consisting of nickel salt, ferrous salt and manganese salt is fed together, which is beneficial to ensuring Ni 2+ 、Fe 2+ 、Mn 2 + Better dispersion uniformity in the feed liquid system, and the mixed metal salt solution can be integrally prepared by adding acid during preparation so as to inhibit Fe 2+ Oxidation of (2).
In order to better control the pH and NH in the reaction kettle 4 + The concentration of metal salt solution, complexing agent solution and precipitator solution is effectively diluted by the inventor, which is beneficial to improving Ni 2+ 、Fe 2 + 、Mn 2+ 、OH - 、NH 4 + The diffusivity of plasma in a solution system in the reaction kettle prevents adverse factors such as pH mutation and slow ion diffusion caused by overhigh local concentration, and further generates small balls in the growth process.
Defined in terms of supersaturation (S): s = ([ M) (=) 2+ ][OH - ] 2 )/K sp,M(OH)2 (K sp,M(OH)2 Is M (OH) 2 Solubility product of [ M ] 2+ ]And [ OH - ]Is free metal ion (Ni) in the system 2+ 、Fe 2+ 、Mn 2+ ) Concentration and hydroxyl concentration), when the supersaturation degree S is in the low range, the system is dominated by growth. Timely and staged fine adjustment of pH and NH according to actual growth condition of particles in the growth process 4 + The process parameters are equal, thereby being beneficial to controlling free M in the system 2+ And OH - The concentration is controlled to regulate the supersaturation degree of the system, prevent the generation of small balls in the growth process and keep the normal fluctuation of particles.
The method provided by the invention has universal applicability, can be expanded to the preparation of other nickel-iron-manganese ternary precursors with large particles and high iron content, is also suitable for the preparation of nickel-iron-manganese ternary precursors with small and medium particles and different iron contents, and the nickel-iron-manganese layered oxide anode material of the sodium ion battery prepared by the method has excellent electrochemical performance.
In the preferred embodiment of the present invention, when the target particle size of the product is less than or equal to 5.0 μm, the pH in the reaction kettle is controlled to be a first pH value, ammonium ion (NH) 4 + ) Is the first ammonium value, and the reaction is continued until the particle size D50 of the product reaches the target particle size of 1-5.0 μm.
For example, the temperature is controlled at 60 ℃ and the rotation speed is 500r/min, and the reaction is continued until the particle size D50 of the product reaches 1-5.0 μm. Therefore, the nickel-iron-manganese precursor with small particles (less than or equal to 5 um) can be prepared.
In a preferred embodiment of the present invention, when the target particle size of the product is greater than 5.0 μm, the pH in the reaction kettle is first controlled to be the first pH value, the concentration of ammonium ions is the first ammonium value, and the reaction is continued until the particle size D50 of the product reaches the first target particle size of 5.0 μm; then controlling the pH value in the reaction kettle to be a second pH value, controlling the concentration of ammonium ions to be a second ammonium value, further controlling the pH value to be an x pH value according to the growth condition, controlling the concentration of the ammonium ions to be the x ammonium value, wherein x is more than or equal to 3, and 12.50> a first pH value > a second pH value > the x pH value >9.50,0.1mol/L < the first ammonium value < the second ammonium value < the x ammonium value <0.5mol/L, and continuously reacting until the granularity D50 of the product reaches a second target granularity of 5.0-20.0 mu m. Thus, the nickel-iron-manganese precursor with medium and large particles (> 5 um) can be prepared.
D50 refers to the particle size corresponding to the cumulative percent particle size distribution of a sample at 50%.
Timely and staged fine adjustment of pH and NH according to actual growth condition of particles in the growth process 4 + The process parameters are equal, thereby being beneficial to controlling free M in the system 2+ And OH - The concentration is controlled to regulate the supersaturation degree of the system, prevent the generation of small balls in the growth process and keep the normal fluctuation of particles. The nickel-iron-manganese ternary precursor with large particles and high iron content obtained by the process method basically has no small balls in the growth process, can smoothly grow to the target granularity of 5.0 mu m or more, has better sphericity and is suitable for industrial mass production.
In an alternative embodiment, the target particle size D50 is 5 to 20 μm;
in an alternative embodiment, the target particle size D50 is from 5 to 10 μm.
In the preferred embodiment of the present invention, the molar ratio of nickel, iron and manganese in the mixed metal salt solution can be any ratio, i.e. the chemical formula of Ni x Fe y Mn 1-x-y (OH) 2 Wherein x may have a value of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, etc., and y may have a value of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, etc. For example, the molar ratio of nickel element, iron element and manganese element is 0.20.
In an alternative embodiment, the inert gas is nitrogen. The inert gas can protect Fe 2+ To prevent it from being oxidized to Fe in the feed liquid 3+ Result in prior to Ni 2+ 、Mn 2+ Precipitation occurs, and pellets are produced.
In an alternative embodiment, after the particle size of the product reaches the target particle size, the product is sequentially subjected to aging, centrifugation, drying, sieving and demagnetizing operations.
In a second aspect, the invention also provides a simple preparation method of the nickel-iron-manganese layered hydroxide precursor, and the particle size D50 of the prepared nickel-iron-manganese layered hydroxide precursor is 1-20 μm.
In a third aspect, the invention also provides a preparation method of the nickel-iron-manganese layered oxide material, which comprises the following steps: the nickel-iron-manganese layered hydroxide precursor prepared by the preparation method of the nickel-iron-manganese layered hydroxide precursor is respectively and uniformly mixed with a sodium source and then fed at high temperatureCalcining to obtain the layered Ni-Fe-Mn oxide material Na (Ni) x Fe y Mn 1-x-y )O 2 ，(0<x<1，0<y<1)。
In a fourth aspect, the present invention also provides an electrode material for a sodium ion battery, the electrode material comprising: the sodium-ion battery anode material prepared by the preparation method of the nickel-iron-manganese layered oxide material.
In a fifth aspect, the invention further provides a sodium-ion battery, which comprises the positive pole piece of the sodium-ion battery.
The invention has the following beneficial effects:
the inventor feeds mixed metal salt solution consisting of nickel salt, ferrous salt and manganese salt together, which is beneficial to ensuring Ni 2+ 、Fe 2+ 、Mn 2+ Better dispersion uniformity in the feed liquid system, and the mixed metal salt solution can be integrally prepared by adding acid during preparation so as to inhibit Fe 2+ Is oxidized into Fe 3+ (ii) a The concentrations of the metal salt solution, the complexing agent solution and the precipitator solution are effectively diluted, so that the pH and NH in the reaction kettle can be better controlled 4 + The fluctuation of the Ni content, the reduction of the viscosity of the feed liquid in the reaction kettle and the contribution to the improvement of the Ni content 2+ 、Fe 2+ 、Mn 2+ 、OH - 、NH 4 + The diffusivity of plasma in a solution system in the reaction kettle prevents adverse factors such as pH mutation and slow ion diffusion caused by overhigh local concentration, and further generates small balls in the growth process.
Therefore, the preparation method of the nickel-iron-manganese layered hydroxide precursor provided by the invention can ensure that the nickel-iron-manganese layered hydroxide precursor with large particles and high iron content basically does not generate small balls in the growth process, keeps the normal fluctuation of the granularity, can quickly grow to the required target granularity, does not need to add a reducing agent, has better sphericity, and is suitable for industrial mass production. In addition, the method has universal applicability, can be expanded to the preparation of other nickel-iron-manganese ternary precursors with large particles and high iron content, is also suitable for the preparation of nickel-iron-manganese precursors with small and medium particles and different iron contents, and the nickel-iron-manganese layered oxide positive electrode material of the sodium ion battery prepared by the method has excellent electrochemical performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is a flow chart of the preparation of a layered nickel-iron-manganese hydroxide precursor;
FIG. 2 shows Ni prepared in example 1 0.20 Fe 0.40 Mn 0.40 (OH) 2 SEM picture of (1);
FIG. 3 shows Ni prepared in example 2 0.28 Fe 0.36 Mn 0.36 (OH) 2 SEM picture of (1);
FIG. 4 shows Ni prepared in example 3 0.10 Fe 0.30 Mn 0.60 (OH) 2 SEM picture of (1);
FIG. 5 shows Ni prepared in comparative example 1 0.20 Fe 0.40 Mn 0.40 (OH) 2 SEM picture of (1);
FIG. 6 shows Ni prepared in comparative example 2 0.20 Fe 0.40 Mn 0.40 (OH) 2 SEM picture of (g);
FIG. 7 shows Ni prepared in example 1 0.20 Fe 0.40 Mn 0.40 (OH) 2 SEM images of the corresponding positive electrode materials;
FIG. 8 shows Ni prepared in example 1 0.20 Fe 0.40 Mn 0.40 (OH) 2 Corresponding electrochemical performance diagram of the anode material.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a nickel-iron-manganese layered hydroxide precursor (the preparation flow is shown in fig. 1), which specifically includes the following steps:
s1: adding pure water into a reaction kettle, heating to 50 ℃, introducing nitrogen at the flow rate of 30L/h, then adding an ammonia water solution to adjust the ammonium radical of the base solution to 0.20mol/L, then adding a prepared liquid alkali solution to adjust the pH value of the base solution to 11.50, uniformly mixing stirring blades in the reaction kettle at the rotating speed of 500r/min, and preparing to obtain the base solution for the coprecipitation reaction.
S2: simultaneously pumping 1.5mol/L of nickel-iron-manganese mixed salt solution, 6.0mol/L of liquid caustic soda solution and 5.0mol/L of ammonia water solution into a reaction kettle, controlling the molar ratio of nickel, iron and manganese to be 20.
S3: after the nucleation task is completed, the growth process is switched, the pH value of the reaction kettle is gradually reduced to 10.80, the ammonium radical is increased to 0.30mol/L, the temperature is increased to 60 ℃, and the reaction is continued until the particle size of the product reaches 5.0 mu m.
S4: after 5.0 mu m, the growth process is further adjusted, the pH value of the reaction kettle is reduced to 10.30, the ammonium radical is continuously increased to 0.36mol/L, the temperature is kept unchanged, and the reaction is continued until the grain diameter of the product reaches 10.0 mu m.
S5: pumping the slurry into an aging tank through a discharge port, aging, centrifuging, drying, screening, demagnetizing and packaging the obtained product to obtain the nickel-iron-manganese ternary precursor, wherein a scanning electron microscope image of the precursor is shown in figure 2.
Example 2
The embodiment provides a preparation method of a nickel-iron-manganese layered hydroxide precursor (the preparation flow is shown in fig. 1), which specifically includes the following steps:
s1: adding pure water into a reaction kettle, heating to 50 ℃, introducing nitrogen at the flow rate of 30L/h, then adding an ammonia water solution to adjust the ammonium radical of the base solution to 0.20mol/L, then adding a prepared liquid alkali solution to adjust the pH value of the base solution to 11.50, uniformly mixing stirring blades in the reaction kettle at the rotating speed of 500r/min, and preparing to obtain the base solution for the coprecipitation reaction.
S2: simultaneously pumping 1.5mol/L of nickel-iron-manganese mixed salt solution, 6.0mol/L of liquid caustic soda solution and 5.0mol/L of ammonia water solution into a reaction kettle, controlling the molar ratio of nickel, iron and manganese to be 28.
S3: after the nucleation task is finished, the growth process is switched, the pH value of the reaction kettle is gradually reduced to 10.80, the ammonium radical is increased to 0.30mol/L, the temperature is increased to 60 ℃, and the reaction is continued until the particle size of the product reaches 5.0 mu m.
S4: after 5.0 μm, the growth process is further adjusted, the pH value of the reaction kettle is reduced to 10.30, the ammonium radical is continuously increased to 0.36mol/L, the temperature is kept unchanged, and the reaction is continued until the particle size of the product reaches 10.0 μm.
S5: and pumping the slurry into an aging tank through a discharge port, aging, centrifuging, drying, screening, demagnetizing and packaging the obtained product to obtain the nickel-iron-manganese ternary precursor, wherein a scanning electron microscope image of the precursor is shown in FIG. 3.
Example 3
The embodiment provides a preparation method of a nickel-iron-manganese layered hydroxide precursor (the preparation flow is shown in fig. 1), which specifically includes the following steps:
s1: adding pure water into a reaction kettle, heating to 50 ℃, introducing nitrogen at the flow rate of 30L/h, then adding an ammonia water solution to adjust the ammonium radical of the base solution to 0.20mol/L, then adding a prepared liquid alkali solution to adjust the pH value of the base solution to 11.50, uniformly mixing stirring blades in the reaction kettle at the rotating speed of 500r/min, and preparing to obtain the base solution for the coprecipitation reaction.
S2: simultaneously pumping 1.5mol/L of nickel-iron-manganese mixed salt solution, 6.0mol/L of liquid caustic soda solution and 5.0mol/L of ammonia water solution into a reaction kettle, controlling the molar ratio of nickel, iron and manganese to be 10.
S3: after the nucleation task is finished, the growth process is switched, the pH value of the reaction kettle is gradually reduced to 10.80, the ammonium radical is increased to 0.30mol/L, the temperature is increased to 60 ℃, and the reaction is continued until the particle size of the product reaches 5.0 mu m.
S4: after 5.0 μm, the growth process is further adjusted, the pH value of the reaction kettle is reduced to 10.30, the ammonium radical is continuously increased to 0.36mol/L, the temperature is kept unchanged, and the reaction is continued until the particle size of the product reaches 10.0 μm.
S5: and pumping the slurry into an aging tank through a discharge port, aging, centrifuging, drying, screening, demagnetizing and packaging the obtained product to obtain the nickel-iron-manganese ternary precursor, wherein a scanning electron microscope image of the precursor is shown in FIG. 4.
Comparative example 1
The embodiment provides a preparation method of a nickel-iron-manganese layered hydroxide precursor, which specifically comprises the following steps:
s1: adding pure water into a reaction kettle, heating to 50 ℃, then adding an ammonia water solution to adjust the ammonium radical of the base solution to 0.20mol/L, then adding the prepared liquid alkali solution to adjust the pH value of the base solution to 11.50, uniformly mixing stirring blades in the reaction kettle at a rotating speed of 500r/min, and preparing to obtain the base solution for the coprecipitation reaction.
S2: 1.3mol/L of nickel-manganese mixed salt solution and 1.4mol/L of FeSO 4 Simultaneously pumping the solution, 11.0mol/L liquid caustic soda solution and 8.0mol/L ammonia water solution into a reaction kettle, controlling the molar ratio of nickel, iron and manganese to be 20.
S3: after the nucleation task is completed, the growth process is switched, the pH value of the reaction kettle is gradually reduced to 10.80, the ammonium radical is increased to 0.30mol/L, the temperature is increased to 60 ℃, and the reaction is continued until the particle size of the product reaches 10.0 mu m.
S4: and pumping the slurry into an aging tank through a discharge port, aging, centrifuging, drying, screening, demagnetizing and packaging the obtained product to obtain the nickel-iron-manganese ternary precursor, wherein a scanning electron microscope image of the precursor is shown in FIG. 5.
As can be seen from comparison of fig. 2, fig. 3 and fig. 4, if the ferrite is added alone, the concentration of the precipitant (sodium hydroxide) exceeds 8M, the concentration of the complexing agent exceeds 6M, and the adjustment of the process step S4 is omitted, a large amount of small balls are generated in the growth process of the prepared nickel-iron-manganese (NFM) ternary precursor with large particles (10 μ M) and high iron content (40 mol%), and the primary particles are seriously "pulverized", and the particle size of the final product is only about 7 μ M, and the final product cannot grow to the target particle size of 10 μ M.
Comparative example 2
The embodiment provides a preparation method of a nickel-iron-manganese layered hydroxide precursor, which specifically comprises the following steps:
s1: adding pure water into a reaction kettle, heating to 50 ℃, then adding an ammonia water solution to adjust the ammonium radical of the base solution to 0.20mol/L, then adding the prepared liquid alkali solution to adjust the pH value of the base solution to 11.50, uniformly mixing stirring blades in the reaction kettle at a rotating speed of 500r/min, and preparing to obtain the base solution for the coprecipitation reaction.
S2: simultaneously pumping 2.0mol/L of nickel-iron-manganese mixed salt solution, 8.0mol/L of liquid caustic soda solution and 6.0mol/L of ammonia water solution into a reaction kettle, controlling the molar ratio of nickel, iron and manganese to be 20.
S3: after the nucleation task is finished, the growth process is switched, the pH value of the reaction kettle is gradually reduced to 10.80, the ammonium radical is increased to 0.30mol/L, the temperature is increased to 60 ℃, and the reaction is continued until the particle size of the product reaches 10.0 mu m.
S4: and pumping the slurry into an aging tank through a discharge port, aging, centrifuging, drying, screening, demagnetizing and packaging the obtained product to obtain the nickel-iron-manganese ternary precursor, wherein a scanning electron microscope image of the precursor is shown in FIG. 6.
As can be seen from comparison of fig. 2, fig. 3 and fig. 4, the lack of the adjustment of the process step S4 only results in the generation of some small balls in the prepared ternary nickel-iron-manganese (NFM) precursor with large particles (10 μm) and high iron content (40 mol%), but no pulverization of primary particles, and the particles can finally grow to the target particle size of 10 μm.
Experimental example 1
The inventors formed the Ni-Fe-Mn layer prepared in example 1The preparation method of the cathode material comprises the following steps of completely and uniformly mixing the nickel-iron-manganese ternary precursor obtained in the example 1 and sodium hydroxide in a mortar, and calcining at 880 ℃ for 12 hours to obtain the cathode material Na (Ni) of the sodium-ion battery 0.20 Fe 0.40 Mn 0.40 )O 2 As shown in fig. 7, electrochemical performance tests are performed on the prepared cathode material at 2.0-4.05V and 0.2C, and as a result, as shown in fig. 8, the specific discharge capacity is 114.6mAh/g, and as can be seen from fig. 8, the cathode material prepared based on the nickel-iron-manganese layered hydroxide precursor has excellent electrochemical performance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a nickel-iron-manganese layered hydroxide precursor for a sodium ion battery is characterized by comprising the following steps:
introducing a mixed metal salt solution consisting of nickel salt, ferrous salt and manganese salt, a precipitator and a complexing agent into a reaction kettle which is mixed with a base solution to carry out coprecipitation reaction, controlling the concentration of the mixed metal salt solution to be less than or equal to 2.0mol/L, the concentration of the precipitator to be less than or equal to 8.0mol/L and the concentration of the complexing agent to be less than or equal to 6.0mol/L, controlling the reaction temperature and the rotation speed, continuously introducing inert gas in the reaction process, and continuously reacting until the granularity of the product reaches the target granularity.
2. The method for preparing the layered nickel-iron-manganese hydroxide precursor according to claim 1, wherein when the target particle size of the product is less than or equal to 5.0 μm, the pH in the reaction kettle is controlled to be a first pH value, the concentration of ammonium ions is a first ammonium value, and the reaction is continued until the particle size D50 of the product reaches the target particle size of 1-5.0 μm;
when the target particle size of the product is larger than 5.0 mu m, firstly controlling the pH value in the reaction kettle to be a first pH value, controlling the concentration of ammonium ions to be a first ammonium value, and continuously reacting until the particle size D50 of the product reaches the first target particle size of 5.0 mu m; then controlling the pH value in the reaction kettle to be a second pH value, controlling the concentration of ammonium ions to be a second ammonium radical value, further controlling the pH value to be an xth pH value according to the growth condition, controlling the concentration of the ammonium ions to be an xth ammonium radical value, wherein x is more than or equal to 3, 12.50, the first pH value, the second pH value, the xth pH value is more than 9.50,0.1mol/L < the first ammonium radical value < the second ammonium radical value < the xth ammonium radical value <0.5mol/L, and continuously reacting until the granularity D50 of a product reaches a second target granularity of 5.0-20.0 mu m.
3. The method for preparing a layered hydroxide precursor of nickel, iron and manganese according to any one of claims 1 to 2, wherein the precipitant is sodium hydroxide or potassium hydroxide, the complexing agent is ammonia water, the temperature is 40 to 60 ℃, the rotation speed is 250 to 500r/min, and the inert gas is nitrogen or argon.
4. The method according to claim 3, wherein the inert gas is nitrogen, the complexing agent is ammonia, and the precipitating agent is sodium hydroxide.
5. The method of preparing a nickel-iron-manganese layered hydroxide precursor according to any of claims 1-2, wherein the mixed metal salt solution has the following general chemical formula: ni x Fe y Mn 1-x-y (OH) 2 Wherein x has a value of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, y has a value of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9.
6. The method for preparing a layered nickel-iron-manganese hydroxide precursor according to any one of claims 1-2, wherein after the particle size of the product reaches a target particle size, the product is subjected to aging, centrifugation, drying, sieving and demagnetization in sequence.
7. A layered nickel-iron-manganese hydroxide precursor, obtainable by the process for its preparation according to any one of claims 1 to 6, having a particle size D50 of from 1 to 20 μm.
8. The preparation method of the nickel-iron-manganese layered oxide material is characterized by comprising the following steps of: respectively and uniformly mixing the nickel-iron-manganese layered hydroxide precursor prepared by the preparation method of any one of claims 1 to 6 with a sodium source, and then calcining at high temperature to obtain a nickel-iron-manganese layered oxide material Na (Ni) x Fe y Mn 1-x-y )O 2 ，(0<x<1，0<y<1)。
9. An electrode material for a sodium-ion battery, the electrode material comprising: the positive electrode material of the sodium-ion battery prepared by the preparation method of the nickel-iron-manganese layered oxide material as claimed in claim 8.
10. A sodium-ion battery comprising the positive electrode sheet of the sodium-ion battery of claim 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116443955A (en) * | 2023-06-14 | 2023-07-18 | 宜宾光原锂电材料有限公司 | Nickel-iron-copper-manganese precursor, preparation method thereof, positive electrode material and battery |
| CN116462238A (en) * | 2023-04-10 | 2023-07-21 | 宁夏中色金辉新能源有限公司 | Application of alcohol as precursor antioxidant and precursor preparation method |
| CN117105285A (en) * | 2023-08-25 | 2023-11-24 | 河北省科学院能源研究所 | Doped sodium ion battery positive electrode material precursor and preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013212959A (en) * | 2012-04-03 | 2013-10-17 | National Institute Of Advanced Industrial Science & Technology | Lithium manganese-based composite oxide and method for producing the same |
| CN108565457A (en) * | 2018-07-19 | 2018-09-21 | 东北大学秦皇岛分校 | A kind of sodium-ion battery positive material, preparation method and sodium-ion battery |
| WO2019037459A1 (en) * | 2017-08-25 | 2019-02-28 | 湖南杉杉能源科技股份有限公司 | High-voltage lithium nickel manganese cobalt oxide precursor, preparation method therefor, and high-voltage lithium nickel manganese cobalt oxide positive electrode material |
| US20190312265A1 (en) * | 2018-04-08 | 2019-10-10 | Microvast Power Systems Co., Ltd. | Method for preparing cathode particles and cathode active materials having same |
| CN111628164A (en) * | 2020-05-22 | 2020-09-04 | 兰州理工大学 | Sodium ion battery positive electrode material and preparation method thereof |
| CN111717941A (en) * | 2020-06-22 | 2020-09-29 | 华友新能源科技（衢州）有限公司 | Nickel-cobalt-manganese hydroxide of needle-shaped whisker and preparation method thereof |
| CN113651368A (en) * | 2021-08-16 | 2021-11-16 | 合肥工业大学 | Method for preparing sodium ion battery anode materials with different crystal forms through lithium doping regulation and control |
| CN113860379A (en) * | 2021-09-29 | 2021-12-31 | 蜂巢能源科技有限公司 | Positive electrode material precursor, positive electrode material, and preparation method and application thereof |
| CN114349068A (en) * | 2021-12-03 | 2022-04-15 | 宜宾光原锂电材料有限公司 | Preparation method of large-particle-size nickel-cobalt-aluminum ternary cathode material precursor |
| CN114920306A (en) * | 2022-06-29 | 2022-08-19 | 荆门市格林美新材料有限公司 | Positive electrode material precursor, positive electrode material, preparation method of positive electrode material and sodium ion battery |
| CN114956202A (en) * | 2022-04-28 | 2022-08-30 | 南通金通储能动力新材料有限公司 | Precursor of sodium ion positive electrode material, preparation method and positive electrode material |
| CN115072805A (en) * | 2022-07-21 | 2022-09-20 | 多氟多新材料股份有限公司 | Sodium-ion battery positive electrode material precursor, preparation method thereof and preparation method of sodium-ion battery positive electrode material |
-
2022
- 2022-12-21 CN CN202211650852.6A patent/CN115893526B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013212959A (en) * | 2012-04-03 | 2013-10-17 | National Institute Of Advanced Industrial Science & Technology | Lithium manganese-based composite oxide and method for producing the same |
| WO2019037459A1 (en) * | 2017-08-25 | 2019-02-28 | 湖南杉杉能源科技股份有限公司 | High-voltage lithium nickel manganese cobalt oxide precursor, preparation method therefor, and high-voltage lithium nickel manganese cobalt oxide positive electrode material |
| US20190312265A1 (en) * | 2018-04-08 | 2019-10-10 | Microvast Power Systems Co., Ltd. | Method for preparing cathode particles and cathode active materials having same |
| CN108565457A (en) * | 2018-07-19 | 2018-09-21 | 东北大学秦皇岛分校 | A kind of sodium-ion battery positive material, preparation method and sodium-ion battery |
| CN111628164A (en) * | 2020-05-22 | 2020-09-04 | 兰州理工大学 | Sodium ion battery positive electrode material and preparation method thereof |
| CN111717941A (en) * | 2020-06-22 | 2020-09-29 | 华友新能源科技（衢州）有限公司 | Nickel-cobalt-manganese hydroxide of needle-shaped whisker and preparation method thereof |
| CN113651368A (en) * | 2021-08-16 | 2021-11-16 | 合肥工业大学 | Method for preparing sodium ion battery anode materials with different crystal forms through lithium doping regulation and control |
| CN113860379A (en) * | 2021-09-29 | 2021-12-31 | 蜂巢能源科技有限公司 | Positive electrode material precursor, positive electrode material, and preparation method and application thereof |
| CN114349068A (en) * | 2021-12-03 | 2022-04-15 | 宜宾光原锂电材料有限公司 | Preparation method of large-particle-size nickel-cobalt-aluminum ternary cathode material precursor |
| CN114956202A (en) * | 2022-04-28 | 2022-08-30 | 南通金通储能动力新材料有限公司 | Precursor of sodium ion positive electrode material, preparation method and positive electrode material |
| CN114920306A (en) * | 2022-06-29 | 2022-08-19 | 荆门市格林美新材料有限公司 | Positive electrode material precursor, positive electrode material, preparation method of positive electrode material and sodium ion battery |
| CN115072805A (en) * | 2022-07-21 | 2022-09-20 | 多氟多新材料股份有限公司 | Sodium-ion battery positive electrode material precursor, preparation method thereof and preparation method of sodium-ion battery positive electrode material |
Non-Patent Citations (2)
| Title |
|---|
| 刘苏宁;孙宁磊;王霄;秦丽娟;: "共沉淀法制备镍钴锰三元材料前驱体的研究进展与趋势", 中国有色冶金, no. 03, 28 June 2018 (2018-06-28) * |
| 苏继桃;苏玉长;赖智广;: "制备镍、钴、锰复合氢氧化物的热力学分析", 电池工业, no. 01, 25 February 2008 (2008-02-25) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116462238A (en) * | 2023-04-10 | 2023-07-21 | 宁夏中色金辉新能源有限公司 | Application of alcohol as precursor antioxidant and precursor preparation method |
| CN116443955A (en) * | 2023-06-14 | 2023-07-18 | 宜宾光原锂电材料有限公司 | Nickel-iron-copper-manganese precursor, preparation method thereof, positive electrode material and battery |
| CN116443955B (en) * | 2023-06-14 | 2023-09-26 | 宜宾光原锂电材料有限公司 | Nickel-iron-copper-manganese precursor, preparation method thereof, positive electrode material and battery |
| CN117105285A (en) * | 2023-08-25 | 2023-11-24 | 河北省科学院能源研究所 | Doped sodium ion battery positive electrode material precursor and preparation method thereof |
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