CN115893526B - Nickel-iron-manganese layered hydroxide precursor for sodium ion battery, preparation method and application - Google Patents
Nickel-iron-manganese layered hydroxide precursor for sodium ion battery, preparation method and application Download PDFInfo
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- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000002243 precursor Substances 0.000 title claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 45
- 239000012266 salt solution Substances 0.000 claims abstract description 19
- 238000000975 co-precipitation Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000012716 precipitator Substances 0.000 claims abstract description 6
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 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
- 239000007774 positive electrode material Substances 0.000 claims description 10
- -1 ammonium ions Chemical class 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 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
- 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
- 230000008569 process Effects 0.000 abstract description 32
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 42
- 239000000047 product Substances 0.000 description 25
- 239000002585 base Substances 0.000 description 16
- 230000001276 controlling effect Effects 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 12
- 239000011572 manganese Substances 0.000 description 12
- 239000003513 alkali Substances 0.000 description 10
- 230000006911 nucleation Effects 0.000 description 10
- 238000010899 nucleation Methods 0.000 description 10
- 239000008188 pellet Substances 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004806 packaging method and process 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
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 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 description 3
- 239000012527 feed solution Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910000863 Ferronickel 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
- 239000012467 final product Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035772 mutation Effects 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
- 238000003483 aging Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 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
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 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
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
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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 thereof, 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 bottom solution which is prepared for coprecipitation reaction, controlling the reaction temperature and the rotating 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 precipitant 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 globules in the growth process, can smoothly grow to the target granularity, does not need to add a reducing agent, has good sphericity, is suitable for industrial mass production, and the sodium ion battery anode material prepared by the precursor has excellent 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 sodium ion batteries is the positive electrode material, and the cost thereof is one of the main factors determining the cost of sodium ion batteries. The layered transition metal oxide has the advantages of low cost, wide raw material sources, simple synthesis process, convenience for large-scale industrial production, high energy density, high voltage platform, excellent comprehensive performance and the like, and is the main flow research direction of the current sodium ion battery anode material.
Just like the nickel cobalt manganese layered hydroxide precursor for the lithium ion battery, the nickel iron manganese layered hydroxide precursor for the sodium ion battery is mainly industrially produced by adopting a liquid phase coprecipitation method at present. However, due to the specificity of iron ions, problems such as easy generation of pellets, difficult further growth of particles and the like in the growth process exist when preparing the nickel-iron-manganese hydroxide precursor by using a liquid phase coprecipitation method, and the larger the precursor particles are, the more serious the problems are, and the higher the iron content is, so that the problems are more obvious.
This is because Fe ions cannot complex with ammonia, but can only precipitate directly with OH -, the solubility product constants (K sp) of Ni 2+、Mn2+ are 10 -14.7 and 10 -10.4 respectively, and after complexing with ammonia water, K sp is 10 -9.11 and 10 -9.23 respectively, and in the case of Fe 3+, K sp is about 2.79 x 10 -39, precipitation is very easy to occur before Ni 2+、Mn2+, so that the pellets are spontaneously nucleated, and the grains are difficult to continue to grow; however, if Fe 2+ is used, the K sp is about 4.87×10 -17, and an inert gas protection and even a reducing agent must be used to prevent the precursor from being oxidized into Fe 3+ in the feed solution, so that the precursor is directly precipitated before Ni 2+、Mn2+, so that it is important to inhibit the oxidation of Fe 2+ in the feed solution and control the ordered precipitation of Fe ions, so that a large number of coprecipitation schemes related to large-particle, high-iron content nickel-iron-manganese layered hydroxide precursors for sodium ion batteries have not been reported.
In view of this, the present invention has been made.
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 producing 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 method for preparing a nickel-iron-manganese layered hydroxide precursor, 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 prepared with base solution for 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, the concentration of the complexing agent to be less than or equal to 6.0mol/L, controlling the reaction temperature and the rotating speed, and continuously introducing inert gas in the reaction process, and continuously reacting until the granularity of the product reaches the 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 pellets are easy to appear in the growth process, particles are difficult to continue to grow and the like exist in the preparation of the nickel-iron-manganese hydroxide precursor by using a liquid phase coprecipitation method, and the larger the precursor particles, the more serious the problems are, the higher the iron content is, and the more obvious the problems are.
In order to solve the problems that pellets are easy to be produced in the growth process and the particles are difficult to further grow in the process of preparing large-particle and high-iron content nickel-iron-manganese hydroxide precursors by a liquid phase coprecipitation method, the inventor discovers that:
The mixed metal salt solution consisting of nickel salt, ferrous salt and manganese salt is fed together, so that better dispersion uniformity of Ni 2+、Fe2+、Mn2 + in a feed liquid system is guaranteed, and the mixed metal salt solution can be integrally and jointly prepared by adding acid during preparation so as to inhibit oxidation of Fe 2+.
In order to better control the fluctuation of pH and NH 4 + in the reaction kettle and reduce the viscosity of the feed liquid in the reaction kettle, the inventor effectively dilutes the concentrations of the metal salt solution, the complexing agent solution and the precipitant solution, is favorable for improving the diffusivity of the solution system of Ni 2+、Fe2 +、Mn2+、OH-、NH4 + plasma in the reaction kettle, and prevents adverse factors such as pH mutation, slow ion diffusion and the like caused by overhigh local concentration, thereby generating pellets in the growth process.
Definition according to supersaturation (S): s= ([ M 2+][OH-]2)/Ksp,M(OH)2(Ksp,M(OH)2 is the solubility product of M (OH) 2, [ M 2+ ] and [ OH - ] are the concentration of free metal ions (Ni 2+、Fe2+、Mn2+) and hydroxide in the system), when oversaturation S is in the low range, the system grows mainly. In the growth process, the pH value, NH 4 + and other technological parameters are adjusted in a phased manner in time according to the actual growth condition of the particles, which is beneficial to controlling the free M 2+ and OH - concentration in the system so as to regulate and control the supersaturation degree of the system, prevent the generation of pellets in the growth process and keep the normal fluctuation of the particles.
The method provided by the invention has general applicability, can be expanded to the preparation of other large-particle and high-iron-content nickel-iron-manganese ternary precursors, is also suitable for the preparation of small-particle and medium-particle nickel-iron-manganese ternary precursors with different iron contents, and the sodium ion battery nickel-iron-manganese layered oxide positive electrode material prepared by using the method has excellent electrochemical performance.
In a preferred embodiment of the invention, when the target particle size of the product is less than or equal to 5.0 mu m, controlling the pH value in the reaction kettle to be a first pH value, and continuously reacting until the particle size D50 of the product reaches the target particle size of 1-5.0 mu m, wherein the concentration of ammonium ions (NH 4 +) is the first ammonium radical value.
For example, the temperature is controlled to be 60 ℃ and the rotating speed is controlled to be 500r/min, and the reaction is continued until the granularity D50 of the product reaches 1-5.0 mu m. Thus, small-particle (less than or equal to 5 um) nickel-iron-manganese precursor can be prepared.
In a preferred embodiment of the invention, when the target particle size of the product is more than 5.0 mu m, controlling the pH value in the reaction kettle to be a first pH value, and continuously reacting until the particle size D50 of the product reaches the first target particle size of 5.0 mu m, wherein the concentration of ammonium ions is the first ammonium radical value; 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, wherein the concentration of ammonium ions is xth ammonium radical value, x is more than or equal to 3, the first pH value is 12.50> the second pH value is > the xth pH value is >9.50,0.1mol/L < first ammonium radical value < second ammonium radical value < xth ammonium radical value <0.5mol/L, and continuously reacting until the granularity D50 of the product reaches the second target granularity of 5.0-20.0 mu m. Thus, a nickel-iron-manganese precursor with medium and large particles (> 5 um) can be prepared.
D50 refers to the particle size corresponding to a cumulative particle size distribution percentage of one sample reaching 50%.
In the growth process, the pH value, NH 4 + and other technological parameters are adjusted in a phased manner in time according to the actual growth condition of the particles, which is beneficial to controlling the free M 2+ and OH - concentration in the system so as to regulate and control the supersaturation degree of the system, prevent the generation of pellets in the growth process and keep the normal fluctuation of the particles. The large-particle high-iron content nickel-iron-manganese ternary precursor obtained by the process method basically has no small ball generation in the growth process, can smoothly grow to a target granularity of 5.0 mu m or more, has good sphericity, and is suitable for industrial mass production.
In an alternative embodiment, the target particle size D50 is 5-20 μm;
In an alternative embodiment, the target particle size D50 is 5-10 μm.
In a preferred embodiment of the present invention, the molar ratio of the nickel element, the iron element and the manganese element in the mixed metal salt solution may be any ratio, that is, the value of x in the chemical formula Ni xFeyMn1-x-y(OH)2 may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, etc., and the value of y may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, etc. For example, the molar ratio of nickel element, iron element and manganese element is 0.20:0.40:0.40, 0.28:0.36:0.36 or 0.10:0.30:0.60.
In an alternative embodiment, the inert gas is nitrogen. The inert gas may act to protect the Fe 2+ from oxidation to Fe 3+ in the feed solution, resulting in precipitation prior to Ni 2+、Mn2+, thereby producing pellets.
In an alternative embodiment, the product is subjected to ageing, centrifugation, drying, sieving and demagnetizing operations in sequence after the particle size of the product reaches the target particle size.
In a second aspect, the invention also provides a simple preparation method of the nickel-iron-manganese layered hydroxide precursor, and the prepared nickel-iron-manganese layered hydroxide precursor has a granularity D50 of 1-20 mu m.
In a third aspect, the invention also provides a preparation method of the nickel-iron-manganese layered oxide material, which comprises the following steps: and uniformly mixing the nickel-iron-manganese layered hydroxide precursor prepared by the preparation method of the nickel-iron-manganese layered hydroxide precursor with a sodium source, and calcining at a high temperature to obtain the nickel-iron-manganese layered oxide material Na (Ni xFeyMn1-x-y)O2, (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 present invention further provides a sodium ion battery, which includes the positive electrode sheet of the sodium ion battery.
The invention has the following beneficial effects:
The inventor feeds the mixed metal salt solution composed of nickel salt, ferrous salt and manganese salt together, which is beneficial to ensuring better dispersion uniformity of Ni 2+、Fe2+、Mn2+ in a feed liquid system, and the mixed metal salt solution can be integrally and jointly prepared by adding acid during preparation so as to inhibit Fe 2+ from being oxidized into Fe 3+; the concentration of the metal salt solution, the complexing agent solution and the precipitant solution is effectively diluted, so that the fluctuation of pH and NH 4 + in the reaction kettle is better controlled, the viscosity of feed liquid in the reaction kettle is reduced, the diffusivity of a solution system of Ni 2+、Fe2+、Mn2+、OH-、NH4 + plasma in the reaction kettle is improved, adverse factors such as pH mutation, slow ion diffusion and the like caused by overhigh local concentration are prevented, and then the pellets are generated in the growth process.
Therefore, the preparation method of the nickel-iron-manganese layered hydroxide precursor provided by the invention can ensure that the large-particle and high-iron-content nickel-iron-manganese layered hydroxide precursor basically has no small ball generation and normal fluctuation of the granularity in the growth process, can grow to the required target granularity faster, does not need to add a reducing agent, has better sphericity, and is suitable for industrial mass production. In addition, the method has general applicability, can be expanded to the preparation of other large-particle and high-iron-content nickel-iron-manganese ternary precursors, is also suitable for the preparation of small-particle and medium-particle nickel-iron-manganese precursors with different iron contents, and the sodium ion battery nickel-iron-manganese layered oxide positive electrode material prepared by using 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 that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the preparation of a nickel iron manganese layered hydroxide precursor;
FIG. 2 is an SEM image of Ni 0.20Fe0.40Mn0.40(OH)2 prepared according to example 1;
FIG. 3 is an SEM image of Ni 0.28Fe0.36Mn0.36(OH)2 prepared according to example 2;
FIG. 4 is an SEM image of Ni 0.10Fe0.30Mn0.60(OH)2 prepared according to example 3;
FIG. 5 is an SEM image of Ni 0.20Fe0.40Mn0.40(OH)2 of comparative example 1;
FIG. 6 is an SEM image of Ni 0.20Fe0.40Mn0.40(OH)2 prepared according to comparative example 2;
FIG. 7 is an SEM image of a positive electrode material corresponding to Ni 0.20Fe0.40Mn0.40(OH)2 prepared in example 1;
Fig. 8 is an electrochemical performance chart of a positive electrode material corresponding to Ni 0.20Fe0.40Mn0.40(OH)2 prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a preparation method of a nickel-iron-manganese layered hydroxide precursor (the preparation flow is shown by referring to fig. 1), which specifically comprises the following steps:
s1: adding pure water into a reaction kettle, heating to 50 ℃, introducing nitrogen at a flow rate of 30L/h, adding an ammonia water solution to prepare a base solution ammonium radical into 0.20mol/L, adding the prepared liquid-alkali solution to adjust the pH value of the base solution to 11.50, and uniformly mixing at a rotating speed of 500r/min by stirring paddles in the reaction kettle to prepare 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-alkali solution and 5.0mol/L of ammonia water solution into a reaction kettle, controlling the molar ratio of nickel-iron-manganese to be 20:40:40, and reacting for 0.5 hour under the conditions that the pH value of the reaction kettle is kept to 11.50 and the ammonium radical is kept to 0.20mol/L, thereby completing the nucleation task.
S3: after the nucleation task is completed, the process is changed into a growth process, 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 grain diameter of the product reaches 5.0 mu m.
S4: after 5.0 μm, the growth process is further regulated, 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 μm.
S5: the slurry is pumped into an aging tank through a discharge port, and the obtained product is subjected to aging, centrifugation, drying, screening, demagnetizing and packaging to obtain a nickel-iron-manganese ternary precursor, wherein a scanning electron microscope diagram of the nickel-iron-manganese ternary 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 by referring to fig. 1), which specifically comprises the following steps:
s1: adding pure water into a reaction kettle, heating to 50 ℃, introducing nitrogen at a flow rate of 30L/h, adding an ammonia water solution to prepare a base solution ammonium radical into 0.20mol/L, adding the prepared liquid-alkali solution to adjust the pH value of the base solution to 11.50, and uniformly mixing at a rotating speed of 500r/min by stirring paddles in the reaction kettle to prepare 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-alkali solution and 5.0mol/L of ammonia water solution into a reaction kettle, controlling the molar ratio of nickel-iron-manganese to be 28:36:36, and reacting for 0.5 hour under the conditions that the pH value of the reaction kettle is kept to 11.50 and the ammonium radical is kept to 0.20mol/L, thereby completing the nucleation task.
S3: after the nucleation task is completed, the process is changed into a growth process, 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 grain diameter of the product reaches 5.0 mu m.
S4: after 5.0 μm, the growth process is further regulated, 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 μm.
S5: the slurry is pumped into an aging tank through a discharge port, and the obtained product is subjected to aging, centrifugation, drying, screening, demagnetizing and packaging to obtain a nickel-iron-manganese ternary precursor, wherein a scanning electron microscope diagram of the nickel-iron-manganese ternary precursor is shown in figure 3.
Example 3
The embodiment provides a preparation method of a nickel-iron-manganese layered hydroxide precursor (the preparation flow is shown by referring to fig. 1), which specifically comprises the following steps:
s1: adding pure water into a reaction kettle, heating to 50 ℃, introducing nitrogen at a flow rate of 30L/h, adding an ammonia water solution to prepare a base solution ammonium radical into 0.20mol/L, adding the prepared liquid-alkali solution to adjust the pH value of the base solution to 11.50, and uniformly mixing at a rotating speed of 500r/min by stirring paddles in the reaction kettle to prepare 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-alkali solution and 5.0mol/L of ammonia water solution into a reaction kettle, controlling the molar ratio of nickel-iron-manganese to be 10:30:60, and reacting for 0.5 hour under the conditions that the pH value of the reaction kettle is kept at 11.50 and the ammonium radical is kept at 0.20mol/L, thereby completing the nucleation task.
S3: after the nucleation task is completed, the process is changed into a growth process, 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 grain diameter of the product reaches 5.0 mu m.
S4: after 5.0 μm, the growth process is further regulated, 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 μm.
S5: the slurry is pumped into an aging tank through a discharge port, and the obtained product is subjected to aging, centrifugation, drying, screening, demagnetizing and packaging to obtain a nickel-iron-manganese ternary precursor, wherein a scanning electron microscope diagram of the nickel-iron-manganese ternary precursor is shown in figure 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 ℃, adding an ammonia water solution to prepare the ammonium radical of the base solution into 0.20mol/L, adding the prepared aqueous alkali solution to adjust the pH value of the base solution to 11.50, and uniformly mixing the stirring blades in the reaction kettle at the rotating speed of 500r/min to prepare the base solution for the coprecipitation reaction.
S2: 1.3mol/L of nickel-manganese mixed salt solution, 1.4mol/L of FeSO 4 solution, 11.0mol/L of aqueous alkali solution and 8.0mol/L of aqueous ammonia solution are pumped into a reaction kettle at the same time, the molar ratio of nickel to iron to manganese is controlled to be 20:40:40, and coprecipitation reaction is carried out for 0.5 hour under the conditions that the pH value of the reaction kettle is kept to 11.50 and the ammonium radical is kept to be 0.20mol/L, so that the nucleation task is completed.
S3: after the nucleation task is completed, the process is changed into a growth process, 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 grain diameter of the product reaches 10.0 mu m.
S4: the slurry is pumped into an aging tank through a discharge port, and the obtained product is subjected to aging, centrifugation, drying, screening, demagnetizing and packaging to obtain a nickel-iron-manganese ternary precursor, wherein a scanning electron microscope diagram of the nickel-iron-manganese ternary precursor is shown in figure 5.
Comparing fig. 2,3 and 4, it can be seen that, when ferrite is added alone, the concentration of precipitant (sodium hydroxide) exceeds 8M, the concentration of complexing agent exceeds 6M, and step S4 is omitted to adjust the process, the prepared ferronickel manganese (NFM) ternary precursor with large particle size (10 μm) and high iron content (40 mol%) is produced in a large amount during the growth process, primary particles are seriously "pulverized", the granularity of the final product is only about 7 μm, and the final product cannot grow to the target granularity of 10 μm.
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 ℃, adding an ammonia water solution to prepare the ammonium radical of the base solution into 0.20mol/L, adding the prepared aqueous alkali solution to adjust the pH value of the base solution to 11.50, and uniformly mixing the stirring blades in the reaction kettle at the rotating speed of 500r/min to prepare the base solution for the coprecipitation reaction.
S2: 2.0mol/L of nickel-iron-manganese mixed salt solution, 8.0mol/L of aqueous alkali and 6.0mol/L of aqueous ammonia solution are pumped into a reaction kettle at the same time, the molar ratio of nickel-iron-manganese is controlled to be 20:40:40, and the reaction is carried out for 0.5 hour under the conditions that the pH value of the reaction kettle is kept to 11.50 and the ammonium radical is kept to 0.20mol/L, so that the nucleation task is completed.
S3: after the nucleation task is completed, the process is changed into a growth process, 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 grain diameter of the product reaches 10.0 mu m.
S4: the slurry is pumped into an aging tank through a discharge port, and the obtained product is subjected to aging, centrifugation, drying, screening, demagnetizing and packaging to obtain a nickel-iron-manganese ternary precursor, wherein a scanning electron microscope diagram of the nickel-iron-manganese ternary precursor is shown in figure 6.
Comparing fig. 2, 3 and 4, it can be seen that the absence of step S4 to adjust the process step results in the production of large particles (10 μm) and high iron content (40 mol%) ferronickel manganese (NFM) ternary precursor with partial globules generated during the growth process, but the primary particles have no "pulverization" phenomenon, and the particles can finally grow to the target particle size of 10 μm.
Experimental example 1
The inventors prepared the nickel-iron-manganese layered hydroxide precursor prepared in example 1 as a positive electrode material, and specifically prepared the same as the following, the nickel-iron-manganese ternary precursor obtained in example 1 was completely and uniformly mixed with sodium hydroxide in a mortar, and calcined at 880 ℃ for 12 hours to obtain a sodium ion battery positive electrode material Na (Ni 0.20Fe0.40Mn0.40)O2, as shown in fig. 7, and the prepared positive electrode material was subjected to electrochemical performance test at 2.0-4.05V and 0.2C, and as a result, the discharge specific capacity was 114.6mAh/g, as can be seen from fig. 8, the positive electrode material prepared based on the nickel-iron-manganese layered hydroxide precursor of the present invention was excellent in electrochemical performance.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the nickel-iron-manganese layered hydroxide precursor for the sodium ion battery is characterized by comprising the following steps of:
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 prepared with base solution for 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, the concentration of the complexing agent to be less than or equal to 6.0mol/L, controlling the reaction temperature and the rotating speed, and continuously introducing inert gas in the reaction process, and continuously reacting until the granularity of a product reaches the target granularity; when the target granularity of the product is more than 5.0 mu m, controlling the pH value in the reaction kettle to be a first pH value, and continuously reacting until the granularity D50 of the product reaches the first target granularity of 5.0 mu m, wherein the concentration of ammonium ions is a first ammonium radical value; 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, wherein the concentration of ammonium ions is xth ammonium radical value, x is more than or equal to 3, the first pH value is 12.50> the second pH value is > the xth pH value is more than 9.50,0.1mol/L < first ammonium radical value < second ammonium radical value < xth ammonium radical value <0.5mol/L, and continuously reacting until the granularity D50 of the product reaches a second target granularity, and the second target granularity is less than or equal to 20.0 mu m; the complexing agent is ammonia water.
2. The method for preparing a nickel-iron-manganese layered hydroxide precursor according to claim 1, wherein the precipitant is sodium hydroxide or potassium hydroxide, the temperature is 40-60 ℃, the rotation speed is 250-500r/min, and the inert gas is nitrogen or argon.
3. The method for preparing a nickel iron manganese layered hydroxide precursor according to claim 2, wherein the inert gas is nitrogen and the precipitant is sodium hydroxide.
4. The method for preparing a nickel iron manganese layered hydroxide precursor according to claim 1, wherein the mixed metal salt solution has the following chemical formula: ni xFeyMn1-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, and y has a value of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9.
5. The method for preparing a nickel-iron-manganese layered hydroxide precursor according to claim 1, wherein 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.
6. A nickel iron manganese layered hydroxide precursor prepared by the method of any of claims 1-5, wherein the particle size D50 of the precursor reaches a second target particle size of 5.0 μm < the second target particle size is less than or equal to 20.0 μm.
7. The preparation method of the nickel-iron-manganese layered oxide material is characterized by comprising the following steps of: the nickel-iron-manganese layered hydroxide precursor prepared by the preparation method of any one of claims 1-5 is uniformly mixed with a sodium source and then calcined at a high temperature to obtain a nickel-iron-manganese layered oxide material Na (Ni xFeyMn1-x-y)O2, 0< x <1,0< y < 1).
8. An electrode material for a sodium ion battery, the electrode material comprising: the positive electrode material of sodium ion battery prepared by the preparation method of the nickel-iron-manganese layered oxide material of claim 7.
9. A sodium ion battery comprising the electrode material of the sodium ion battery of claim 8.
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