CN116759525A - Sodium ion battery positive electrode material precursor, preparation method thereof, sodium ion battery positive electrode material, sodium ion battery and electric equipment - Google Patents
Sodium ion battery positive electrode material precursor, preparation method thereof, sodium ion battery positive electrode material, sodium ion battery and electric equipment Download PDFInfo
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- CN116759525A CN116759525A CN202310954659.XA CN202310954659A CN116759525A CN 116759525 A CN116759525 A CN 116759525A CN 202310954659 A CN202310954659 A CN 202310954659A CN 116759525 A CN116759525 A CN 116759525A
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- ion battery
- sodium ion
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- positive electrode
- electrode material
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- 239000002243 precursor Substances 0.000 title claims abstract description 125
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 105
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011164 primary particle Substances 0.000 claims abstract description 40
- 239000011163 secondary particle Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 238000003756 stirring Methods 0.000 claims description 50
- 229910052751 metal Inorganic materials 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 34
- 239000011148 porous material Substances 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 24
- 239000010405 anode material Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 17
- 238000000975 co-precipitation Methods 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 239000011259 mixed solution Substances 0.000 description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 238000001000 micrograph Methods 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 238000001354 calcination Methods 0.000 description 9
- 238000007873 sieving Methods 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 238000000635 electron micrograph Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000012066 reaction slurry Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 3
- 238000001493 electron microscopy Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NTUKYEWPMLPVHZ-UHFFFAOYSA-N [Mn].[Ni].[Fe].[Mg] Chemical compound [Mn].[Ni].[Fe].[Mg] NTUKYEWPMLPVHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000005389 magnetism Effects 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a sodium ion battery positive electrode material precursor, a preparation method thereof, a sodium ion battery positive electrode material, a sodium ion battery and electric equipment. The precursor of the positive electrode material of the sodium ion battery comprises a plurality of secondary particles, and the growth direction consistency coefficient U of the secondary particles is as follows: u is more than or equal to 75 percent, and U= (360-alpha)/360 is 100 percent; wherein alpha is the sum of the angles of all central angles which do not meet the specified conditions; the central angle is the central angle of the vertex with the center of the section of the secondary particle in the section of the secondary particle; the specified conditions are as follows: in the section, the primary particles are intercalated and grown along the diameter direction of the section on the outer layer of the sector area corresponding to the central angle. The precursor of the positive electrode material of the sodium ion battery provided by the application has good uniformity of the growth direction of primary particles, and is beneficial to diffusion of sodium ions and improvement of material capacity and rate capability.
Description
Technical Field
The application relates to the field of sodium ion batteries, in particular to a precursor of a positive electrode material of a sodium ion battery, a preparation method of the precursor, the positive electrode material of the sodium ion battery, the sodium ion battery and electric equipment.
Background
The problems of lithium resource deficiency and high cost restrict the application of the lithium ion battery in the field of large-scale energy storage. The sodium ion battery and the lithium ion battery have the same working principle and similar battery parts, have good industrial foundation and obvious cost advantage, and have wide application space in the fields of novel energy storage and low-speed transportation. Currently, the positive electrode material is a decisive factor for restricting the performance of sodium ion batteries. The layered transition metal oxide in the sodium ion battery anode material is a sodium ion battery anode material with higher capacity, better stability and simple manufacturing method, but commercialization of the material is still hindered by the problems of low energy density, relatively poorer cycle life, poorer multiplying power performance and the like.
For the layered oxide cathode material, the physical and chemical indexes and morphological structural characteristics of the precursor directly influence the performance of the cathode material. Therefore, for the positive electrode material of the sodium ion battery, the precursor of the positive electrode material is often required to have proper physical and chemical indexes and morphological structural characteristics so as to improve the deintercalation rate of sodium ions in the positive electrode material, shorten the transmission path of the sodium ions and ensure the multiplying power performance and capacity of the sodium ion battery.
Disclosure of Invention
The application aims to provide a sodium ion battery positive electrode material precursor, a preparation method thereof, a sodium ion battery positive electrode material, a sodium ion battery and an electric device, so as to solve the problems.
In order to achieve the above purpose, the application adopts the following technical scheme:
a sodium ion battery positive electrode material precursor comprising a plurality of secondary particles; the growth direction uniformity coefficient U of the primary particles constituting the secondary particles satisfies: u is more than or equal to 75 percent, and U= (360-alpha)/360 is 100 percent;
wherein alpha is the sum of the angles of all central angles which do not meet the specified conditions; the central angle is the central angle of the vertex with the center of the section of the secondary particle in the section of the secondary particle; the specified conditions are as follows: in the section, the primary particles are intercalated and grown along the diameter direction of the section on the outer layer of the sector area corresponding to the central angle.
Preferably, the sodium ion battery positive electrode material precursor satisfies one or more of the following conditions:
A. the growth direction consistency coefficient U of the primary particles meets the following conditions: u is more than or equal to 85 percent;
B. the primary particles are flake-shaped, and the average thickness of the primary particles is 0.05-0.14 mu m;
C. the secondary particles have an average pore diameter of 13-15.5nm and an average pore volume of 0.042-0.065cm 3 /g。
Preferably, the sodium ion battery positive electrode material precursor satisfies one or more of the following conditions:
D. the particle diameter D50 of the precursor is 9.5-18 mu m;
E. the tap density TD of the precursor is not less than 1.8g/cm 3 ；
F. The specific surface area BET of the precursor is 12-22m 2 /g；
G. The particle size distribution Span of the precursor is 0.3-0.6;
H. the half-width FWHM (100) of the precursor is 0.38-0.58 degrees;
preferably, the chemical formula of the precursor of the positive electrode material of the sodium ion battery is Ni x Mn y Fe 1-x-y-z Me z (OH) 2 Wherein x is more than or equal to 0.15 and less than or equal to 0.4,0.2, y is more than or equal to 0.5, and z is more than or equal to 0 and less than or equal to 0.04; me is selected from one or more of Zn, ti, mg, al, zr, ca.
The application also provides a preparation method of the precursor of the positive electrode material of the sodium ion battery, which comprises the following steps:
mixing materials including complexing agent, precipitator and water to obtain base solution;
the target mixed metal salt solution, the precipitator and the complexing agent are added into the base solution in parallel, under the inert gas atmosphere, the pH value of a reaction system, the reaction stirring rate and the flow rate of the target mixed metal salt solution are controlled, and coprecipitation reaction is carried out to obtain the precursor of the anode material of the sodium ion battery;
mother liquor is continuously discharged during the process of carrying out the coprecipitation reaction.
Preferably, the preparation method of the sodium ion battery positive electrode material precursor meets one or more of the following conditions:
a. the pH value of the reaction system is 10-11;
b. in the process of carrying out the coprecipitation reaction, the stirring speed is reduced by 10-100 r/min/time every 4-8h until the stirring speed is reduced to the lowest stirring speed; preferably, the minimum stirring rate setting principle is as follows: when D50 is less than or equal to 11 mu m, the minimum stirring speed is 120r/min; when D50 is more than or equal to 11 mu m and less than or equal to 13 mu m, the minimum stirring speed is 110r/min; when D50 is more than or equal to 13 mu m and less than or equal to 15 mu m, the minimum stirring speed is 100r/min; when D50 is more than or equal to 15 mu m and less than or equal to 18 mu m, the minimum stirring speed is 90r/min;
c. in the process of performing the coprecipitation reaction, increasing the flow rate of the target mixed metal salt solution every time the particle diameter D50 of the particles obtained by the reaction is increased by 2-4 mu m, wherein the increasing amplitude of the flow rate of the target mixed metal salt solution is 1.5-3 times of that of the previous flow rate until the flow rate is increased to the maximum flow rate; the maximum flow rate is not higher than 8%/h of the available volume of the reaction vessel.
Preferably, the preparation method of the sodium ion battery positive electrode material precursor meets one or more of the following conditions:
d. the target mixed metal salt solution comprises nickel salt, manganese salt, ferrous salt and Me salt; me is selected from one or more of Zn, ti, mg, al, zr, ca;
e. after the coprecipitation reaction is finished, the method further comprises the following steps: and (3) carrying out solid-liquid separation to obtain a solid, and then carrying out alkali washing, water washing and drying to obtain the precursor of the sodium ion battery anode material.
The application also provides a sodium ion battery anode material, and the raw materials of the sodium ion battery anode material comprise the sodium ion battery anode material precursor.
The application also provides a preparation method of the sodium ion battery anode material, which comprises the following steps:
and mixing the sodium ion battery anode material precursor with a sodium source, and calcining to obtain the sodium ion battery anode material.
Preferably, the preparation method of the sodium ion battery positive electrode material meets one or more of the following conditions:
f. heating to 780-880 ℃ at a heating rate of 2-4 ℃/min, and calcining for 10-20h;
g. the ratio of the sum of the molar amounts of all metal elements in the sodium ion battery positive electrode material precursor to the molar amount of sodium in the sodium source is 1: (1.02-1.07).
The application also provides a sodium ion battery, and the raw materials of the sodium ion battery comprise the sodium ion battery anode material.
The application also provides an electric device comprising the sodium ion battery.
Compared with the prior art, the application has the beneficial effects that:
the precursor of the positive electrode material of the sodium ion battery provided by the application comprises a plurality of secondary particles, wherein the primary particles forming the secondary particles are intercalated and grown along the diameter direction of the secondary particles, and the uniformity of the growth direction is high, so that the transfer and deintercalation of sodium ions are facilitated, and the rate capability of the sodium ion battery prepared by the corresponding positive electrode material is improved.
The sodium ion battery anode material, the sodium ion battery and the electric equipment provided by the application have excellent electrical performance.
According to the preparation method of the sodium ion battery positive electrode material precursor, the pH value of a reaction system, the stirring speed and the flow rate of a target mixed metal salt solution are controlled under the condition of inert gas atmosphere by a coprecipitation process, so that the sodium ion battery positive electrode material precursor with good primary particle growth direction consistency is obtained.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, 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 application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a scanning electron microscope image of a nickel-iron-manganese precursor of example 1;
FIG. 2 is a partial surface electron micrograph of a nickel iron manganese precursor of example 1;
FIG. 3 is a cross-sectional electron microscope of the nickel-iron-manganese precursor of example 1;
FIG. 4 is a scanning electron microscope image of the nickel-iron-manganese precursor of example 2;
FIG. 5 is a cross-sectional electron microscopy of the nickel-iron-manganese precursor of example 2;
FIG. 6 is a scanning electron microscope image of the nickel-iron-manganese-magnesium precursor of example 3;
FIG. 7 is a cross-sectional electron microscope of the nickel-iron-manganese-magnesium precursor of example 3;
FIG. 8 is a scanning electron microscope image of a nickel-iron-manganese precursor of comparative example 1;
FIG. 9 is a partial surface electron micrograph of a nickel iron manganese precursor of comparative example 1;
FIG. 10 is a cross-sectional electron microscopy of the precursor of comparative example 1;
FIG. 11 is a scanning electron microscope image of a comparative example 2 nickel iron manganese precursor;
FIG. 12 is a cross-sectional electron microscopy of the precursor of comparative example 2.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
"at least one" means one or more, and "a plurality" means two or more.
A sodium ion battery positive electrode material precursor comprising a plurality of secondary particles, the growth direction uniformity coefficient U of primary particles constituting the secondary particles satisfying: u is more than or equal to 75 percent, and U= (360-alpha)/360 is 100 percent;
wherein alpha is the sum of the angles of all central angles which do not meet the specified conditions; the central angle is the central angle of the vertex with the center of the section of the secondary particle in the section of the secondary particle; the specified conditions are as follows: in the section, the primary particles are intercalated and grown along the diameter direction of the section on the outer layer of the sector area corresponding to the central angle.
It should be understood that, in the present application, the secondary particles of the precursor of the positive electrode material are spherical or spheroid, and the cross section refers to a plane cut through the center of the secondary particles in the diameter direction (when there is a deviation in actual test, the plane cut through the portion of the secondary particles near the center of the sphere may also be a cross section); the uniformity coefficient U of the growth direction of the primary particles is more than or equal to 75 percent, and the quantity of the secondary particles in the precursor is more than or equal to 60 percent.
In an alternative embodiment, the sodium ion battery positive electrode material precursor satisfies one or more of the following conditions:
A. the growth direction consistency coefficient U of the primary particles meets the following conditions: u is more than or equal to 85 percent;
B. the primary particles are flake-shaped, and the thickness of the primary particles is 0.05-0.14 mu m;
the primary particles are in a flake shape, so that the specific surface area of the precursor can be increased, and the contact area of the corresponding positive electrode material and electrolyte is increased, thereby improving the charge-discharge capacity and the rate capability of the corresponding sodium ion battery; alternatively, the thickness of the primary particles may be any value between 0.05 μm, 0.06 μm, 0.07 μm, 0.08 μm, 0.09 μm, 0.10 μm, 0.11 μm, 0.12 μm, 0.13 μm, 0.14 μm, or 0.05-0.14 μm;
C. the secondary particles have an average pore diameter of 13-15.5nm and an average pore volume of 0.042-0.065cm 3 /g。
The porous and evenly distributed pores provide permeation paths for the electrolyte, greatly improve the permeation efficiency of the electrolyte, facilitate the electrolyte to quickly permeate into the internal structure of the material, and improve the capacity and rate capability of the battery; the volume change generated in the process of sodium ion intercalation and deintercalation in the charge and discharge process can be relieved, and the service life of the battery is prolonged.
The secondary particles were found to have relatively uniform pores in the radial direction, with average pore diameters and average Kong Rongdou in the respective ranges (0-9 μm, 0-13.7 μm, 0-13.9 μm, 0-18 μm) being within the above-mentioned ranges.
Alternatively, the secondary particles may have an average pore size of any of 13nm, 13.5nm, 14nm, 14.5nm, 15nm, 15.5nm, or 13-15.5nm, and an average pore volume of 0.042cm 3 /g、0.045cm 3 /g、0.050cm 3 /g、0.055cm 3 /g、0.060cm 3 /g、0.065cm 3 /g or 0.042-0.065cm 3 Any value between/g.
In an alternative embodiment, the sodium ion battery positive electrode material precursor satisfies one or more of the following conditions:
D. the particle diameter D50 of the precursor is 9.5-18 mu m;
the whole precursor secondary particles are sphere-like or spherical, and the precursor has larger particle diameter, so that the tap density of the corresponding positive electrode material is increased, and the energy density of the battery is improved.
Alternatively, the particle size D50 of the precursor may be any value between 9.5 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, or 9.5-18 μm;
E. the tap density TD of the precursor is not less than 1.8g/cm 3 ；
Optionally, the precursor has a tap density TD of 1.8-2.2g/cm 3 Or 1.8-2.5g/cm 3 ；
Alternatively, the precursor may have a tap density TD of 1.8g/cm 3 、1.9g/cm 3 、2.0g/cm 3 、2.1g/cm 3 、2.2g/cm 3 、2.3g/cm 3 、2.4g/cm 3 、2.5g/cm 3 、2.6g/cm 3 、2.7g/cm 3 、2.8g/cm 3 、2.9g/cm 3 、3.0g/cm 3 Or not less than 1.8g/cm 3 Any one of the values of (2);
the precursor has high tap density, and can improve the volume energy density of the material, so that the corresponding battery has high discharge capacity and high charge-discharge efficiency;
F. the specific surface area BET of the precursor is 12-22m 2 /g；
Alternatively, the precursor may have a specific surface area BET of 12m 2 /g、13m 2 /g、14m 2 /g、15m 2 /g、16m 2 /g、17m 2 /g、18m 2 /g、19m 2 /g、20m 2 /g、21m 2 /g、22m 2 /g or 12-22m 2 Any value between/g;
G. the particle size distribution Span of the precursor is 0.3-0.6;
the Span value of the precursor is smaller, which indicates that the secondary particles of the precursor are uniform in size, and the precursor can be more densely filled when used for the positive electrode, so that the discharge capacity of the battery can be improved.
Alternatively, the particle size distribution Span of the precursor may be any value between 0.3, 0.4, 0.5, 0.6, or 0.3-0.6;
H. the half-width FWHM (100) of the precursor is 0.38-0.58 degrees;
the half-peak width of the precursor is narrower, the precursor crystallization is higher, and the corresponding cycle performance can be improved.
Alternatively, the full width at half maximum FWHM (100) of the precursor may be any value between 0.38 °, 0.40 °, 0.45 °, 0.50 °, 0.55 °, 0.58 °, or 0.38-0.58 °;
in an alternative embodiment, the sodium ion battery positive electrode material precursor has the chemical formula Ni x Mn y Fe 1-x-y-z Me z (OH) 2 Wherein x is more than or equal to 0.15 and less than or equal to 0.4,0.2, y is more than or equal to 0.5, and z is more than or equal to 0 and less than or equal to 0.04; me is selected from one or more of Zn, ti, mg, al, zr, ca.
Alternatively, x may be any value between 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, or 0.15-0.4, y may be any value between 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.04, 0.0.0.0.04, 0.48, 0.0.0.0.04, 0.0.0.0.0.02, or any value between 0.0.0.0.0.0.0.0.0.0.03-50.
The application also provides a preparation method of the precursor of the positive electrode material of the sodium ion battery, which comprises the following steps:
mixing materials including complexing agent, precipitator and water to obtain base solution;
adding a target mixed metal salt solution, the precipitator and the complexing agent into the base solution, and controlling the pH value of a reaction system, the reaction stirring rate and the flow rate of the target mixed metal salt solution under the inert gas atmosphere to perform coprecipitation reaction to obtain a precursor of the anode material of the sodium ion battery;
mother liquor is continuously discharged during the process of carrying out the coprecipitation reaction.
In an alternative embodiment, the method for preparing a precursor of a positive electrode material of a sodium ion battery satisfies one or more of the following conditions:
a. the pH value of the reaction system is 10-11;
alternatively, the pH of the reaction system may be any value between 10, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11, or 10-11;
b. in the process of carrying out the coprecipitation reaction, the stirring speed is reduced by 10-100 r/min/time every 4-8h until the stirring speed is reduced to the lowest stirring speed; preferably, the minimum stirring rate setting principle is as follows: when D50 is less than or equal to 11 mu m, the minimum stirring speed is 120r/min; when D50 is more than or equal to 11 mu m and less than or equal to 13 mu m, the minimum stirring speed is 110r/min; when D50 is more than or equal to 13 mu m and less than or equal to 15 mu m, the minimum stirring speed is 100r/min; when D50 is more than or equal to 15 mu m and less than or equal to 18 mu m, the minimum stirring speed is 90r/min;
alternatively, the time interval may be any value between 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or 4-8 hours, and the reduced stirring rate may be any value between 10 r/min/time, 20 r/min/time, 30 r/min/time, 40 r/min/time, 50 r/min/time, 60 r/min/time, 70 r/min/time, 80 r/min/time, 90 r/min/time, 100 r/min/time, or 10-100 r/min/time;
c. in the process of performing the coprecipitation reaction, increasing the flow rate of the target mixed metal salt solution every time the particle diameter D50 of the particles obtained by the reaction is increased by 2-4 mu m, wherein the increasing amplitude of the flow rate of the target mixed metal salt solution is 1.5-3 times of that of the previous flow rate until the flow rate is increased to the maximum flow rate; the maximum flow rate is not higher than 8%/h of the available volume of the reaction vessel.
In an alternative embodiment, the method for preparing a precursor of a positive electrode material of a sodium ion battery satisfies one or more of the following conditions:
d. the target mixed metal salt solution comprises nickel salt, manganese salt, ferrous salt and Me salt; me is selected from one or more of Zn, ti, mg, al, zr, ca;
e. after the coprecipitation reaction is finished, the method further comprises the following steps: and (3) carrying out solid-liquid separation to obtain a solid, and then carrying out alkali washing, water washing and drying to obtain the precursor of the sodium ion battery anode material.
The application also provides a sodium ion battery anode material, and the raw materials of the sodium ion battery anode material comprise the sodium ion battery anode material precursor.
The application also provides a preparation method of the sodium ion battery anode material, which comprises the following steps:
and mixing the sodium ion battery anode material precursor with a sodium source, and calcining to obtain the sodium ion battery anode material.
In an alternative embodiment, the method of preparing a sodium ion battery positive electrode material satisfies one or more of the following conditions:
f. heating to 780-880 ℃ at a heating rate of 2-4 ℃/min, and calcining for 10-20h;
alternatively, the temperature rise rate may be any value between 2 ℃/min, 3 ℃/min, 4 ℃/min or 2-4 ℃/min, the end point temperature may be any value between 780 ℃, 790 ℃, 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃ or 780-880 ℃, and the calcination time may be any value between 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h or 10-20h;
g. the ratio of the sum of the molar amounts of all metal elements in the sodium ion battery positive electrode material precursor to the molar amount of sodium in the sodium source is 1: (1.02-1.07).
Alternatively, the ratio of the sum of the molar amounts of all metal elements in the sodium-ion battery cathode material precursor to the molar amount of sodium in the sodium source may be 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07 or 1: any value between (1.02-1.07).
The application also provides a sodium ion battery, and the raw materials of the sodium ion battery comprise the sodium ion battery anode material.
The application also provides an electric device comprising the sodium ion battery.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. 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.
Example 1
The embodiment provides a precursor of a positive electrode material of a sodium ion battery, and the preparation method comprises the following steps:
nickel, manganese and ferrous sulfate crystals (molar ratio 1:1:1) are prepared into a uniform metal salt mixed solution with the concentration of 2 mol/L; mixing 10mol/L sodium hydroxide solution and 8mol/L ammonia water to prepare a base solution with pH of 11 and ammonia concentration of 4 g/L; adding the base solution into a reaction kettle with a stirring device, setting the reaction temperature to be 45 ℃ at a stirring rate of 320r/min, and slowly mixing according to a volume ratio of 1:8:20, ammonia water, sodium hydroxide solution and metal salt mixed solution are added in parallel flow, the adding speed of the metal salt mixed solution is 2 percent/h of the available volume of the reaction kettle, the pH value of the reaction system is controlled to be about 10.6, and the ammonia concentration is about 4 g/L; reducing the stirring rotating speed of the reaction system by 20r/min every 5h, and maintaining the stirring rotating speed unchanged when the rotating speed is reduced to 100r/min; when the flow rate of the metal salt mixed solution is increased to 8 percent/h of the available volume of the reaction kettle, the flow is not increased until the particle size of the reaction slurry reaches 13.7 mu m, and the feeding is stopped.
Centrifugally washing the precipitate, performing alkali washing with 0.5mol/L sodium hydroxide solution, performing water washing with 70 ℃ deionized water, dispersing, putting into a blast oven, drying and dehydrating at 120 ℃ for 12 hours, taking out, sealing and storing;
and crushing the obtained dried material in grinding equipment, and performing treatment such as sieving, demagnetizing and the like to obtain the nickel-iron-manganese ternary precursor. The molecular formula of the obtained precursor of the positive electrode material of the sodium ion battery is Ni 0.33 Mn 0.33 Fe 0.34 (OH) 2 。
Fig. 1 is an electron microscope image of the precursor prepared in this example 1, in which the primary particles on the outer layer of the secondary particles of the precursor are thin plates with relatively uniform sizes and have relatively good uniformity in growth direction. To more intuitively represent the size of the primary particles, fig. 2 is an exemplary partial surface electron microscope image of the precursor prepared in this example 1, and 5 primary particles having a representative size are selected from fig. 2 to measure, and the average thickness of 5 primary particles is calculated to be 0.06 μm. Fig. 3 is a cross-sectional electron microscope image of the precursor prepared in this example 1 (the angle in the figure is the degree of the central angle which does not meet the specified condition; the specified condition is that, in the cross-section, primary particles are intercalated and grown along the diameter direction of the cross-section in the outer layer of the sector area corresponding to the central angle), the whole primary particles of the cross-section can be seen to grow along the radial direction, the formed cross-section is crown-shaped, the structure of uniform pore distribution is provided, and the edge primary particles are intercalated and grown mainly along the diameter direction, so that the primary particle growth direction consistency coefficient u= (360-20)/360 x 100% = 94.4%) is calculated. The pore volume was measured to be 0.0526cm when the precursor was as long as 9.0. Mu.m 3 Per g, average pore diameter of 14.3nm, pore volume of 0.0499cm when precursor length is 13.7 μm 3 Per g, average pore diameter 13.7nm, measured difference from 9.0 μmThe pores are small, the pore distribution is uniform, the pore size is consistent, and the result is consistent with that of a section electron microscope.
Mixing the obtained precursors according to the element molar ratio (Ni+Mn+Fe) Na=1:1.05, heating to 830 ℃ in a muffle furnace at a heating rate of 3 ℃/min, calcining for 15 hours, cooling, crushing and sieving to prepare a positive pole piece, assembling the positive pole piece, a diaphragm, a sodium perchlorate electrolyte and a sodium piece negative pole to form a power-buckling battery, and testing the battery performance between 2 and 4.2V, wherein the current of 0.1 ℃ is 15mA/g.
Example 2
The embodiment provides a precursor of a positive electrode material of a sodium ion battery, which comprises the following specific steps:
nickel, manganese and ferrous sulfate crystals (molar ratio 28:36:36) are prepared into a uniform metal salt mixed solution with the concentration of 2 mol/L; mixing 10mol/L sodium hydroxide solution and 8mol/L ammonia water to prepare a base solution with pH of 11 and ammonia concentration of 4 g/L; adding the base solution into a reaction kettle with a stirring device, setting the reaction temperature to be 50 ℃ at a stirring rate of 320r/min, and slowly mixing according to a volume ratio of 1:8:20, ammonia water, sodium hydroxide solution and metal salt mixed solution are added in parallel flow, the adding speed of the metal salt mixed solution is 2 percent/h of the available volume of the reaction kettle, the pH value of the reaction system is controlled to be about 10.5, and the ammonia concentration is about 4 g/L; reducing the stirring rotating speed of the reaction system by 20r/min every 5h, and maintaining the stirring rotating speed unchanged when the rotating speed is reduced to 100r/min; when the flow rate of the metal salt mixed solution is increased to 8 percent/h of the available volume of the reaction kettle, the flow is not increased until the particle size of the reaction slurry reaches 13.9 mu m, and the feeding is stopped.
Centrifugally washing the precipitate, performing alkali washing with 0.5mol/L sodium hydroxide solution, performing water washing with 70 ℃ deionized water, dispersing, putting into a blast oven, drying and dehydrating at 120 ℃ for 12 hours, taking out, sealing and storing;
and crushing the obtained dried material in grinding equipment, and performing treatment such as sieving, demagnetizing and the like to obtain the nickel-iron-manganese ternary precursor. The molecular formula of the obtained precursor of the positive electrode material of the sodium ion battery is Ni 0.28 Mn 0.36 Fe 0.36 (OH) 2 . Fig. 4 and 5 are a surface electron microscope image and a cross-sectional electron microscope image (the degrees of the central angles of which angles do not meet the prescribed conditions are shown in fig. 5) of the precursor prepared in example 2, and it can be seen that example 2 has a similar morphology as example 1.
Mixing the obtained precursors according to the element molar ratio (Ni+Mn+Fe) Na=1:1.05, heating to 830 ℃ in a muffle furnace at a heating rate of 3 ℃/min for calcining for 15 hours, cooling, crushing and sieving, assembling the obtained product into a battery, and testing the battery performance between 2 and 4.2V.
Example 3
The embodiment provides a precursor of a positive electrode material of a sodium ion battery, which comprises the following specific steps:
nickel, manganese, ferrous and magnesium sulfate crystals (molar ratio 32:32:32:4) are prepared into a uniform metal salt mixed solution with the concentration of 2 mol/L; mixing 10mol/L sodium hydroxide solution and 8mol/L ammonia water to prepare a base solution with pH of 11 and ammonia concentration of 4 g/L; adding the base solution into a reaction kettle with a stirring device, setting the reaction temperature to 55 ℃ at a stirring rate of 360r/min, and then slowly mixing the base solution with the stirring device according to a volume ratio of 1:8:20, ammonia water, sodium hydroxide solution and metal salt mixed solution are added in parallel flow, the adding speed of the metal salt mixed solution is 2 percent/h of the available volume of the reaction kettle, the pH value of the reaction system is controlled to be about 10.4, and the ammonia concentration is controlled to be about 4 g/L; reducing the stirring rotating speed of the reaction system by 30r/min every 5h, and maintaining the stirring rotating speed unchanged when the rotating speed is reduced to 100r/min; when the flow rate of the metal salt mixed solution is increased to 8 percent/h of the available volume of the reaction kettle, the flow is not increased until the particle size of the reaction slurry reaches 12 mu m, and the feeding is stopped.
Centrifugally washing the precipitate, performing alkali washing with 0.5mol/L sodium hydroxide solution, performing water washing with 70 ℃ deionized water, dispersing, putting into a blast oven, drying and dehydrating at 120 ℃ for 12 hours, taking out, sealing and storing;
pulverizing the obtained dried material in pulverizing equipment, sieving, and removing magnetism to obtain the final productTo a nickel-iron-manganese ternary precursor. The molecular formula of the obtained precursor of the positive electrode material of the sodium ion battery is Ni 0.32 Mn 0.32 Fe 0.32 Mg 0.04 (OH) 2 . Fig. 6 and 7 are a surface electron microscope image and a cross-sectional electron microscope image (fig. 7 shows the degrees of the central angle of which the angle does not meet the prescribed condition) of the precursor prepared in example 3, and it can be seen that example 3 has a similar morphology as example 1.
Mixing the obtained precursors according to the element molar ratio (Ni+Mn+Fe+Mg): na=1:1.05, heating to 830 ℃ in a muffle furnace at a heating rate of 3 ℃/min for calcining for 15 hours, cooling, crushing and sieving, assembling the obtained product into a battery, and testing the battery performance between 2 and 4.2V.
Comparative example 1
This comparative example provides a precursor of a positive electrode material for a sodium ion battery, which has coarser primary particles and fewer internal voids than in example 1, and is prepared by the following steps:
nickel, manganese and ferrous sulfate crystals (molar ratio 1:1:1) are prepared into a uniform metal salt mixed solution with the concentration of 2 mol/L; mixing 10mol/L sodium hydroxide solution and 8mol/L ammonia water to prepare a base solution with pH of 11 and ammonia concentration of 4 g/L; adding the base solution into a reaction kettle with a stirring device, setting the reaction temperature to be 50 ℃ at a stirring rate of 400r/min, and slowly mixing according to a volume ratio of 1:8:20, ammonia water, sodium hydroxide solution and metal salt mixed solution are added in parallel flow, the adding speed of the metal salt mixed solution is 1 percent/h of the available volume of the reaction kettle, the pH value of the reaction system is controlled to be about 10.3, and the ammonia concentration is controlled to be about 4.5 g/L; reducing the stirring rotating speed of the reaction system by 20r/min every 4h, and maintaining the stirring rotating speed unchanged after the rotating speed is reduced to 120r/min; when the precursor grows to 2.5 mu m, the flow rate of the metal salt mixed solution is increased to 2 times that before, and after the flow rate of the metal salt mixed solution is increased to 6 percent/h of the available volume of the reaction kettle, the flow is not increased until the particle size of the reaction slurry reaches 10 mu m, and the feeding is stopped.
Centrifugally washing the precipitate, performing alkali washing with 0.5mol/L sodium hydroxide solution, performing water washing with 70 ℃ deionized water, dispersing, putting into a blast oven, drying and dehydrating at 120 ℃ for 12 hours, taking out, sealing and storing;
and crushing the obtained dried material in grinding equipment, and performing treatment such as sieving, demagnetizing and the like to obtain the nickel-iron-manganese ternary precursor. The molecular formula of the obtained precursor of the positive electrode material of the sodium ion battery is Ni 0.33 Mn 0.33 Fe 0.34 (OH) 2 . FIG. 8 is an electron micrograph of the precursor prepared in comparative example 1, in which the outer primary particles are thicker than in example 1, and FIG. 9 is a partial surface electron micrograph of the precursor of comparative example 1, in which 5 primary particles having a representative size are selected from FIG. 9 to measure, and the average value of the thicknesses of the 5 primary particles is calculated to obtain an average thickness of 0.12. Mu.m; FIG. 10 is a cross-sectional electron micrograph of comparative example 1 (FIG. 10 shows the degree of central angle of an angle not meeting the prescribed condition), and it can be seen that the inside is denser than example 1 and the pore distribution is not uniform as in example 1, and the average pore volume is 0.0348cm 3 /g。
Mixing the obtained precursors according to the element molar ratio (Ni+Mn+Fe) Na=1:1.05, heating to 830 ℃ in a muffle furnace at a heating rate of 3 ℃/min for calcining for 15 hours, cooling, crushing and sieving, assembling the obtained product into a battery, and testing the battery performance between 2 and 4.2V.
Comparative example 2
This comparative example provides a precursor of a positive electrode material for a sodium ion battery, which has poorer uniformity of primary particle growth direction than in example 1, and is prepared by the following steps:
nickel, manganese and ferrous sulfate crystals (molar ratio 1:1:1) are prepared into a uniform metal salt mixed solution with the concentration of 2 mol/L; mixing 10mol/L sodium hydroxide solution and 8mol/L ammonia water to prepare a base solution with pH of 11 and ammonia concentration of 4 g/L; adding the base solution into a reaction kettle with a stirring device, setting the reaction temperature to 40 ℃ at a stirring rate of 320r/min, and slowly mixing according to a volume ratio of 1:8:20, ammonia water, sodium hydroxide solution and metal salt mixed solution are added in parallel flow, the adding speed of the metal salt mixed solution is 2 percent/h of the available volume of the reaction kettle, the pH value of the reaction system is controlled to be about 10.6, and the ammonia concentration is about 4 g/L; reducing the stirring rotating speed of the reaction system by 20r/min every 5h, and maintaining the stirring rotating speed unchanged when the rotating speed is reduced to 100r/min; when the flow rate of the metal salt mixed solution is increased to 10 percent/h of the available volume of the reaction kettle, the flow is not increased until the particle size of the reaction slurry reaches 14 mu m, and the feeding is stopped.
Centrifugally washing the precipitate, performing alkali washing with 0.5mol/L sodium hydroxide solution, performing water washing with 70 ℃ deionized water, dispersing, putting into a blast oven, drying and dehydrating at 120 ℃ for 12 hours, taking out, sealing and storing;
and crushing the obtained dried material in grinding equipment, and performing treatment such as sieving, demagnetizing and the like to obtain the nickel-iron-manganese ternary precursor. The molecular formula of the obtained precursor of the positive electrode material of the sodium ion battery is Ni 0.33 Mn 0.33 Fe 0.34 (OH) 2 . FIG. 11 is an electron micrograph of the precursor prepared in comparative example 2, which had poor uniformity of primary particle growth direction and more tiling debris. Fig. 12 is a cross-sectional electron microscopic view of comparative example 2 (fig. 12 shows the degrees of the central angle of which the angle does not meet the prescribed condition), from which the primary particle growth direction uniformity coefficient U is calculated to be only 61.1%.
The results of physical and chemical property tests of example 1, example 2, example 3 and comparative example 1, comparative example 2 are shown in Table 1.
TABLE 1 physicochemical Property test results
Note that: the pore volume and the average pore diameter are measured by a full-automatic specific surface area and pore diameter distribution tester, and the measured values of different particle sizes are sampling tests in the reaction process.
The results of the electrical property tests of example 1, example 2, example 3 and comparative example 1, comparative example 2 are shown in table 2.
TABLE 2 results of electrical property tests
As can be seen from examples 1, 2 and 3, ni is based on the special structure and morphology of the present application 0.33 Mn 0.33 Fe 0.34 (OH) 2 、Ni 0.28 Mn 0.36 Fe 0.36 (OH) 2 、Ni 0.32 Mn 0.32 Fe 0.32 Mg 0.04 (OH) 2 NaNi synthesized by precursor 0.33 Mn 0.33 Fe 0.34 O 2 、NaNi 0.28 Mn 0.36 Fe 0.36 O 2 With Ni 0.32 Mn 0.32 Fe 0.32 Mg 0.04 O 2 The sodium ion battery corresponding to the positive electrode active material can simultaneously give consideration to better first discharge specific capacity, first coulombic efficiency, capacity retention rate and multiplying power performance, and the positive electrode material doped with a small amount of Mg has optimal first coulombic efficiency, capacity retention rate and multiplying power performance. Comparative example 1 has no special structure and morphology of the present application, has coarser primary particles and fewer pores, and has less uniformity of pore distribution and uniformity of primary particle growth direction than that of example 1, and has a capacity retention rate, a first discharge specific capacity and rate capability which are significantly inferior to those of example 1, although the first coulombic efficiency is close to that of example 1; comparative example 2 has poor uniformity of primary particle growth direction, a wider half-width than example 1, and the first coulombic efficiency, capacity retention and rate performance are inferior to those of example 1, although the first discharge specific capacity is close to that of example 1.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. The precursor of the positive electrode material of the sodium ion battery is characterized by comprising a plurality of secondary particles, wherein the growth direction consistency coefficient U of primary particles forming the secondary particles meets the following conditions: u is more than or equal to 75 percent, and U= (360-alpha)/360 is 100 percent;
wherein alpha is the sum of the angles of all central angles which do not meet the specified conditions; the central angle is the central angle of the vertex with the center of the section of the secondary particle in the section of the secondary particle; the specified conditions are as follows: in the section, the primary particles are intercalated and grown along the diameter direction of the section on the outer layer of the sector area corresponding to the central angle.
2. The sodium ion battery cathode material precursor of claim 1, wherein one or more of the following conditions are satisfied:
A. the growth direction consistency coefficient U of the primary particles meets the following conditions: u is more than or equal to 85 percent;
B. the primary particles are flake-shaped, and the average thickness of the primary particles is 0.05-0.14 mu m;
C. the secondary particles have an average pore diameter of 13-15.5nm and an average pore volume of 0.042-0.065cm 3 /g。
3. The sodium ion battery cathode material precursor of claim 1, wherein one or more of the following conditions are satisfied:
D. the particle diameter D50 of the precursor is 9.5-18 mu m;
E. the tap density TD of the precursor is not less than 1.8g/cm 3 ；
F. The specific surface area BET of the precursor is 12-22m 2 /g；
G. The particle size distribution Span of the precursor is 0.3-0.6;
H. the half-width FWHM (100) of the precursor is 0.38-0.58 degrees.
4. A sodium ion battery positive electrode material precursor according to any one of claims 1-3, wherein the sodium ion battery positive electrode material precursor has a chemical formula of Ni x Mn y Fe 1-x-y-z Me z (OH) 2 Wherein x is more than or equal to 0.15 and less than or equal to 0.4,0.2, y is more than or equal to 0.5, and z is more than or equal to 0 and less than or equal to 0.04; me is selected from one or more of Zn, ti, mg, al, zr, ca.
5. The preparation method of the precursor of the positive electrode material of the sodium ion battery is characterized by comprising the following steps:
mixing materials including complexing agent, precipitator and water to obtain base solution;
the target mixed metal salt solution, the precipitator and the complexing agent are added into the base solution in parallel, under the inert gas atmosphere, the pH value of a reaction system, the reaction stirring rate and the flow rate of the target mixed metal salt solution are controlled, and coprecipitation reaction is carried out to obtain the precursor of the anode material of the sodium ion battery;
mother liquor is continuously discharged during the process of carrying out the coprecipitation reaction.
6. The method of preparing a precursor of a positive electrode material for a sodium ion battery according to claim 5, wherein one or more of the following conditions are satisfied:
a. the pH value of the reaction system is 10-11;
b. in the process of carrying out the coprecipitation reaction, the stirring speed is reduced by 10-100 r/min/time every 4-8h until the stirring speed is reduced to the lowest stirring speed; preferably, the minimum stirring rate setting principle is as follows: when D50 is less than or equal to 11 mu m, the minimum stirring speed is 120r/min; when D50 is more than or equal to 11 mu m and less than or equal to 13 mu m, the minimum stirring speed is 110r/min; when D50 is more than or equal to 13 mu m and less than or equal to 15 mu m, the minimum stirring speed is 100r/min; when D50 is more than or equal to 15 mu m and less than or equal to 18 mu m, the minimum stirring speed is 90r/min;
c. in the process of performing the coprecipitation reaction, increasing the flow rate of the target mixed metal salt solution every time the particle diameter D50 of the particles obtained by the reaction is increased by 2-4 mu m, wherein the increasing amplitude of the flow rate of the target mixed metal salt solution is 1.5-3 times of that of the previous flow rate until the flow rate is increased to the maximum flow rate; the maximum flow rate is not higher than 8%/h of the available volume of the reaction vessel.
7. The method for producing a sodium ion battery positive electrode material precursor according to claim 5 or 6, wherein one or more of the following conditions are satisfied:
d. the target mixed metal salt solution comprises nickel salt, manganese salt, ferrous salt and Me salt; me is selected from one or more of Zn, ti, mg, al, zr, ca;
e. after the coprecipitation reaction is finished, the method further comprises the following steps: and (3) carrying out solid-liquid separation to obtain a solid, and then carrying out alkali washing, water washing and drying to obtain the precursor of the sodium ion battery anode material.
8. A positive electrode material for a sodium ion battery, wherein the raw materials comprise the precursor of the positive electrode material for a sodium ion battery according to any one of claims 1 to 4.
9. A sodium ion battery, characterized in that the raw material comprises the sodium ion battery positive electrode material according to claim 8.
10. An electrical device comprising the sodium ion battery of claim 9.
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