CN116230887A - Precursor of positive electrode material of sodium ion battery, positive electrode material with Cu concentration gradient, preparation method and sodium ion battery - Google Patents
Precursor of positive electrode material of sodium ion battery, positive electrode material with Cu concentration gradient, preparation method and sodium ion battery Download PDFInfo
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Abstract
The invention belongs to the field of secondary batteries, and particularly discloses a preparation method of a precursor material and a positive electrode material of a sodium ion battery with a Cu concentration gradient. Specifically, pH is regulated by coprecipitation method to obtain shell-core precursor material without Cu crystal nucleus and Cu shell layer, high-temperature diffusion of Cu element is carried out by sintering process, and sodium ion battery anode material with Cu concentration gradient from outer layer to center is obtained, and molecular formula is Na β Fe x Ni y Cu z Mn (1‑x‑y‑z) O 2 Wherein beta is more than or equal to 0.8 and less than or equal to 1.05,x is more than or equal to 0.3 and less than or equal to 0.6, and y+z is more than or equal to 0.1 and less than or equal to 0.3. The obtained Na with Cu concentration gradient β Fe x Ni y Cu z Mn (1‑x‑y‑z) O 2 The positive electrode material has high specific volume and cycle stability and can reduce the material cost.
Description
Technical Field
The invention belongs to the field of secondary batteries, in particular relates to an electrode material of a secondary battery, and more particularly relates to a positive electrode material of a sodium ion battery and a preparation method thereof.
Background
The development of green energy technology and low carbon economy has increased the demand for low cost commercial sodium ion batteries. Compared with a lithium ion battery, the sodium ion battery has the advantages that the sodium source material is rich in storage, sodium ions do not form alloy with aluminum, an aluminum foil can be used as a current collector for a negative electrode, the over-discharge characteristic and the like are avoided, and particularly, the low-cost advantage of the lithium ion battery is expected to replace the traditional lithium ion battery in large-scale energy storage.
The Fe-Ni-Mn-based ternary oxide is one of alternatives of the positive electrode material of the sodium ion battery, has a good smooth charge-discharge curve and a high reversible specific capacity, and has obvious advantages in the aspect of material availability compared with the Ni-Co-Mn ternary oxide.
The iron-nickel-manganese-based ternary anode material of the sodium ion battery obtained by the prior art has certain defects. One of the materials is that the Fe-Ni-Mn-based ternary material has certain phase change, and obvious capacity attenuation can occur under long-time charge-discharge cycle, so that the requirement of long service life of a large-scale energy storage market is not met. In order to improve the cycle performance of the iron-nickel-manganese-based ternary material, a plurality of methods for doping elements, namely homogeneously doping rare metal elements, are reported to improve the stability of the material structure. However, the increase in the content of the low-capacity component lowers the specific capacity, and the balance between electrochemical performance and cycle stability cannot be achieved.
Disclosure of Invention
The invention aims to provide a sodium ion battery precursor material based on Fe-Ni-Mn so as to improve the electrochemical performance and the cycling stability of a sodium ion battery obtained by the precursor material, and further provides a sodium ion battery anode material based on Fe-Ni-Mn and a preparation method.
The precursor of the positive electrode material of the sodium ion battery comprises Fe x Ni y Cu z Mn (1-x-y-z) (OH) 2 Wherein x, y, z have values greater than 0 and less than 1, the precursor comprising a crystal nucleus and a shell, wherein the shell comprises Cu. .
In a specific embodiment, cu is incorporated in an amount of between 0.05 and 0.15 times, preferably between 0.05 and 0.10 times the molar sum of Fe, ni and Mn in the shell.
In one embodiment, 1.ltoreq.y+z.ltoreq.0.3 in the formula.
One preparation method for obtaining the precursor comprises the following steps:
1) Respectively preparing an iron-nickel-manganese sulfate mixed solution A, a sodium hydroxide solution B, a complexing agent solution C and an iron-nickel-copper-manganese sulfate mixed solution D;
2) Respectively pumping the solution A, the solution B and the solution C into a reaction kettle at the same time, and obtaining iron-nickel-manganese hydroxide crystal nucleus through reaction;
3) Pumping the solution B, C, D into a reaction kettle respectively and simultaneously, and obtaining a shell-core type reactant through reaction;
4) And aging, filtering, washing and drying the obtained shell-core reactant to obtain the precursor.
In order to further obtain the positive electrode material of the sodium ion battery, a preparation method comprises the steps of mixing a sodium source substance and a precursor in proportion, and performing a two-stage calcination process in a high-temperature furnace to obtain Fe with Cu concentration gradient x Ni y Cu z Mn (1-x-y-z) O 2 A positive electrode material of a sodium ion battery.
Compared with the prior art, the invention has the following advantages:
the invention reduces the cost of raw materials through element substitution and doping, further reduces the manufacturing cost of the anode material, and is beneficial to commercial production;
the invention adopts the coprecipitation method to prepare the shell-core precursor material, can flexibly adjust the technological parameters, and obtain precursor materials and anode materials with loose texture, uniform particle size and higher tap density and different proportions and structures so as to be suitable for different application scene requirements;
the reaction time is adjusted to control the doping amount, the grain diameter and the grain diameter distribution of copper so as to improve the structural stability of the material, inhibit phase change and further improve the circulation stability of the material.
Drawings
FIG. 1 is a scanning electron micrograph of a precursor material of example 1;
fig. 2 is a discharge graph at 0.2C of the positive electrode material obtained in example 1.
Detailed Description
In the present specification, unless otherwise specified, when referring to particle size, it refers to median particle size.
In the invention, iron nickel manganese hydroxide is used as a crystal nucleus, iron nickel copper manganese hydroxide is used as a shell layer, a precursor material of the shell-core type sodium ion battery is prepared, and copper in the precursor of the shell-core type sodium ion battery is subjected to concentration diffusion at high temperature by a sintering process to obtain the positive electrode material of the sodium ion battery with Cu concentration gradient. The ternary positive electrode material based on iron-nickel-manganese has low material cost and higher specific volume. And a small amount of copper element is doped to replace part of nickel element, so that the cycle stability of the battery is improved well.
In a first aspect of the present invention, the positive electrode material precursor has Fe x Ni y Cu z Mn (1-x-y-z) (OH) 2 In an exemplary embodiment of the invention, the sum of the moles of nickel and copper is preferably between 0.1 and 0.3, if calculated as the sum of the moles of the four elements iron nickel copper manganese is 1. Wherein the proportion of copper to nickel is between 0.1 and 0.5, preferably between 0.2 and 0.4 on a molar basis. In the precursor, copper is present only in the shell.
In an exemplary embodiment of the invention, the precursor is obtained as co-precipitate. Firstly, preparing soluble salt of iron, nickel and manganese into a mixed solution A according to a proportion, then mixing the mixed solution A with a sodium hydroxide solution B and a complexing agent solution C, and carrying out coprecipitation reaction for a time required by the reaction to obtain crystal nucleus with a preset particle size.
Purified water can be firstly put into the reaction kettle, and the ammonia content can be regulated, so that the pH value can be kept in the range of 11.8-13.1. And then synchronously conveying the mixed solution A, the sodium hydroxide solution B and the complexing agent solution C into a reaction kettle under the stirring state, and maintaining the temperature of the reaction kettle between 40 and 70 ℃. As the reaction proceeds, the crystal nucleus size increases. Monitoring particle size by a particle size analyzer, adjusting pH value to be 9.1-12.0 after the particle size reaches a required value, respectively and simultaneously pumping the solution B, the solution C and the mixed solution D of the soluble salt of Fe-Ni-Cu-Mn into a reaction kettle, and performing coprecipitation reaction to obtain a shell-core type reactant with a certain particle size; after the reaction is finished, the obtained shell-core type reactant is aged, filtered, washed and dried to obtain a precursor Fe x Ni y Cu z Mn (1-x-y-z) (OH) 2 。
In the present invention, the soluble salts of iron, nickel, manganese, copper are divalent salts, and the reaction is usually carried out in an inert atmosphere in order to prevent oxidation of a part of iron, manganese, etc. The soluble salts may be sulphates, hydrochlorides, phosphates and the like.
In the invention, the concentration of the iron-nickel-manganese soluble salt mixed solution A and the iron-nickel-copper-manganese soluble salt mixed solution D can be 1.0-1.8mol/L, and the complexing agent can be trisodium citrate, ammonia water, EDTA or a mixture thereof.
In the present invention, the particle size of the precursor may be between 3 and 15. Mu.m, preferably 4 to 10. Mu.m. Among them, the diameter of the crystal nucleus is preferably 25 to 60% of the diameter of the precursor, more preferably 30 to 50%. In an exemplary embodiment of the present invention, the crystal nuclei have a particle size in the range of 4-5 μm and the precursor has a particle size of 7-8 μm.
In a second aspect of the invention, the precursor is sintered to obtain the positive electrode material of the sodium ion battery.
For this purpose, the Na source material and the precursor are uniformly mixed according to a certain proportion, and are placed in a high-temperature furnace, and the molecular formula Na with Cu concentration gradient is finally obtained through a two-stage calcination process β Fe x Ni y Cu z Mn (1-x-y-z) O 2 Sodium ion battery positive electrode material of (2). The sodium source material may be oxyhydrogenSodium sulfide, sodium carbonate, sodium oxalate, sodium citrate, etc. Here β has a value of 0.8-1.05:1. the first sintering temperature is 600-800 ℃, and the second sintering temperature is 900-1100 ℃.
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Precursor preparation
In a molar ratio of 5:2:3, preparing an iron-nickel-manganese sulfate mixed solution A, wherein the concentration of the mixed solution A is 1.5mol/L; preparing a sodium hydroxide solution B with the concentration of 6 mol/L; preparing an ammonia water solution C with the concentration of 6.65 mol/L; in a molar ratio of 5:1.5:0.5: and 3, preparing an iron-nickel-copper-manganese sulfate mixed solution D, wherein the concentration of the mixed solution D is 1.5mol/L.
Ammonia water with ammonia content of 5.8g/L is put into the reaction kettle, nitrogen protection is carried out, the pH value of about 12.5 and the temperature of 55 ℃ are maintained, and the mixed solution A, the sodium hydroxide solution B and the ammonia water solution are synchronously pumped into the reaction kettle. The iron nickel manganese hydroxide crystal nucleus with the grain diameter of 4.5 mu m is obtained through reaction and monitoring by a particle size analyzer.
Adjusting the pH value to be 11.8, synchronously pumping a sodium hydroxide solution B, an ammonia water solution C and a mixed solution D into a reaction kettle, and finally obtaining a shell-core type reactant with the particle size of 8 mu m through reaction and particle size meter monitoring; aging, filtering, washing and drying the obtained shell-core type reactant to obtain Fe 0.5 Ni 0.15 Cu 0.05 Mn 0.3 (OH) 2 A precursor. The scanning electron microscope photograph is shown in figure 1.
(2) NaFe with Cu concentration gradient 0.5 Ni 0.15 Cu 0.05 Mn 0.3 O 2 Preparation of sodium ion battery anode material
Sodium hydroxide powder and a precursor are mixed according to a mole ratio of 1.02:1, uniformly mixing, sintering at 680 ℃ for 10 hours in a high-temperature furnace, heating to 1000 ℃ in 1 hour, and sintering for 10 hours again to finally obtain the sodium ion battery anode material with Cu concentration gradient.
Example 2
(1) Precursor preparation
In a molar ratio of 5:2:3, preparing an iron-nickel-manganese sulfate mixed solution A, wherein the concentration of the mixed solution A is 1.5mol/L; preparing a sodium hydroxide solution B with the concentration of 6 mol/L; preparing an ammonia water solution C with the concentration of 6.65 mol/L; in a molar ratio of 5:1.2:0.8: and 3, preparing an iron-nickel-copper-manganese sulfate mixed solution D, wherein the concentration of the mixed solution D is 1.5mol/L.
Ammonia water with ammonia content of 5.8g/L is put into the reaction kettle, nitrogen protection is carried out, the pH value of about 12.5 and the temperature of 55 ℃ are maintained, and the mixed solution A, the sodium hydroxide solution B and the ammonia water solution are synchronously pumped into the reaction kettle. The iron nickel manganese hydroxide crystal nucleus with the grain diameter of 4.5 mu m is obtained through reaction and monitoring by a particle size analyzer.
Adjusting the pH value to be 11.8, synchronously pumping a sodium hydroxide solution B, an ammonia water solution C and a mixed solution D into a reaction kettle, and finally obtaining a shell-core type reactant with the particle size of 8 mu m through reaction and particle size meter monitoring; and aging, filtering, washing, drying and the like the obtained shell-core reactant to obtain a precursor. The scanning electron microscope results are substantially the same as those of fig. 1.
(2) NaFe with Cu concentration gradient 0.5 Ni 0.15 Cu 0.05 Mn 0.3 O 2 Preparation of sodium ion battery anode material
Sodium hydroxide and a precursor are mixed according to a mole ratio of 1.02:1, uniformly mixing, sintering at 680 ℃ for 10 hours in a high-temperature furnace, heating to 1000 ℃ in 1 hour, and sintering for 10 hours again to finally obtain the sodium ion battery anode material with Cu concentration gradient.
Comparative example 1
This example differs from example 1 in that: the preparation method of the undoped sodium ion battery anode material comprises the following steps:
(1) Precursor preparation
Molar ratio = 5:2:3, preparing an iron-nickel-manganese sulfate mixed solution A, wherein the concentration of the mixed solution A is 1.5mol/L; preparing a sodium hydroxide solution B with the concentration of 6 mol/L; preparing an ammonia water solution C with the concentration of 6.65mol/L for later use;
at the temperature of 55 ℃ of stirring and reaction, clean water is used as reaction base solution, and the reaction base solution is placed in a reaction kettle, and the ammonia content is adjusted to be 5.8g/L and the pH=12.5;
pumping the solution A, B, C into a reaction kettle respectively and simultaneously, and finally obtaining a reactant with the particle size of 8 mu m through reaction and monitoring by a particle size analyzer; the obtained reactant is aged, filtered, washed, dried and the like to obtain Fe0.5Ni0.2Mn0.3 (OH) 2 precursor.
(2) Preparation of NaFe0.5Ni0.2Mn0.3O2 sodium ion battery anode material
High-temperature sintering: the molar ratio of the sodium source and the precursor is 1.02:1, uniformly mixing, placing in a high-temperature furnace at 680 ℃ for 10 hours for primary sintering; secondary sintering at 1000 ℃ for 10 hours to finally obtain NaFe 0.5 Ni 0.2 Mn 0.3 O 2 A sodium ion battery positive electrode material;
comparative example 2
This example differs from example 1 in that: the preparation method of the homogeneous copper-doped sodium ion battery anode material comprises the following steps:
(1) Precursor preparation
Molar ratio = 5:1.5:0.5:3, preparing an iron-nickel-copper-manganese mixed sulfate solution A, wherein the concentration of the mixed sulfate solution A is 1.5mol/L; preparing a sodium hydroxide solution B with the concentration of 6 mol/L; preparing an ammonia water solution C with the concentration of 6.65 mol/L;
at the temperature of 55 ℃ of stirring and reaction, clean water is used as reaction base solution, and the reaction base solution is placed in a reaction kettle, and the ammonia content is adjusted to be 5.8g/L and the pH=12.5;
pumping the solution A, B, C into a reaction kettle respectively and simultaneously, and finally obtaining a reactant with the particle size of 8 mu m through reaction and monitoring by a particle size analyzer; aging, filtering, washing, drying and the like the obtained reactant to obtain Fe 0.5 Ni 0.15 Cu 0.05 Mn 0.3 (OH) 2 A precursor.
(2) Preparation of battery anode material
The molar ratio of the sodium source and the precursor is 1.02:1, uniformly mixing, placing in a high-temperature furnace at 680 ℃ for 10 hours for primary sintering; secondary sintering is carried out at 1000 ℃ for 10 hours, and finally the NaFe of the homogeneous phase copper doped anode material is obtained 0.5 Ni 0.15 Cu 0.05 Mn 0.3 O 2 A sodium ion battery positive electrode material;
the positive electrode materials of the sodium ion batteries of the examples and the comparative examples are subjected to crushing, sieving and demagnetizing, then the positive electrode plate is prepared, and the positive electrode plate is assembled into a sodium ion half battery for charge and discharge test at 0.2 ℃.
Table 1. Electrochemical performance evaluation results are as follows:
the test result shows that the shell layer of the precursor of the positive electrode material of the battery is doped with copper to partially replace nickel, so that the sintered positive electrode material particles have Cu concentration gradient which is gradually reduced from outside to inside, the discharge specific capacity and the cycle performance of the sodium ion battery are improved, and the advantage effect is achieved. A concentration gradient is shown. It is to be easily understood that the relative proportions of the respective elements of the electrode material of the present invention are not limited to the specific values in the examples and the ranges mentioned in the present specification.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (13)
1. A precursor of a positive electrode material of a sodium ion battery is characterized by comprising Fe x Ni y Cu z Mn (1 -x-y-z)(OH) 2 Wherein x, y, z have values greater than 0 and less than 1, the precursor comprising a crystal nucleus and a shell, wherein the shell comprises Cu.
2. The sodium ion battery cathode material precursor according to claim 1, wherein Cu is introduced in an amount of between 0.05-0.15 times, preferably 0.05-0.10 times the sum of the iron-nickel-manganese moles in the shell layer.
3. The sodium ion battery positive electrode material precursor according to claim 2, wherein 0.1.ltoreq.y+z.ltoreq.0.3.
4. The sodium ion battery positive electrode material precursor according to claim 1, having a particle size of between 3 and 15 μm, preferably between 4 and 10 μm, the crystal nuclei preferably having a diameter of between 25 and 60%, more preferably between 30 and 50% of the precursor diameter.
5. A positive electrode material of a sodium ion battery is characterized by having a molecular formula Na β Fe x Ni y Cu z Mn (1-x-y-z) O 2 Wherein beta is more than or equal to 0.8 and less than or equal to 1.05,0.3 and x is more than or equal to 0.6, the material is obtained by sintering the precursor according to any one of claims 1-4, wherein the concentration of Cu element gradually decreases from the outer layer to the central layer, and the Cu concentration gradient exists.
6. The method for preparing a precursor of a positive electrode material of a sodium ion battery according to any one of claims 1 to 4, comprising the steps of:
1) Respectively preparing an iron-nickel-manganese sulfate mixed solution A, a sodium hydroxide solution B, a complexing agent solution C and an iron-nickel-copper-manganese sulfate mixed solution D;
2) Respectively pumping the solution A, the solution B and the solution C into a reaction kettle at the same time, and obtaining iron-nickel-manganese hydroxide crystal nucleus through reaction;
3) Pumping the solution B, C, D into a reaction kettle respectively and simultaneously, and obtaining a shell-core type reactant through reaction;
4) And aging, filtering, washing and drying the obtained shell-core reactant to obtain the precursor.
7. The method for preparing a precursor according to claim 6, wherein the complexing agent is one or more of trisodium citrate, ammonia water, and EDTA.
8. The method for producing a precursor according to claim 6, wherein after the completion of step 2), the reaction solution is adjusted to ph=9.1 to 12.0.
9. The method for preparing a precursor according to claim 6, wherein the reaction temperature of steps 2) and 3) is 42 to 70 ℃.
10. The method for preparing a precursor according to claim 6, wherein the concentration of the mixed solution of iron nickel manganese sulfate A and the mixed solution of iron nickel copper manganese sulfate D is 1.0-1.8mol/L.
11. The preparation method as claimed in claim 6, wherein the crystal nuclei have a particle size of 4 to 5 μm and the precursor has a particle size of 7 to 8 μm at the end of the step 2).
12. The method for preparing a positive electrode material for a sodium ion battery according to claim 5, wherein a sodium source substance and the precursor are mixed in proportion, and the mixture is subjected to a two-stage calcination process in a high temperature furnace to finally obtain Fe with a Cu concentration gradient x Ni y Cu z Mn (1-x-y-z) O 2 The molar ratio of the sodium source substance to the precursor of the sodium ion battery positive electrode material is preferably 0.8-1.05:1,
preferably, the first sintering temperature is 600-800 ℃ and the second sintering temperature is 900-1100 ℃.
13. A sodium ion battery comprising the positive electrode material of claim 5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116581286A (en) * | 2023-07-11 | 2023-08-11 | 天津国安盟固利新材料科技股份有限公司 | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
| CN117059796A (en) * | 2023-10-13 | 2023-11-14 | 山西华钠铜能科技有限责任公司 | Sodium-electricity layered oxide positive electrode material, preparation method thereof, positive electrode plate, sodium-ion battery and electric equipment |
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2023
- 2023-02-15 CN CN202310121952.8A patent/CN116230887A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116581286A (en) * | 2023-07-11 | 2023-08-11 | 天津国安盟固利新材料科技股份有限公司 | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
| CN116581286B (en) * | 2023-07-11 | 2023-10-20 | 天津国安盟固利新材料科技股份有限公司 | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
| CN117059796A (en) * | 2023-10-13 | 2023-11-14 | 山西华钠铜能科技有限责任公司 | Sodium-electricity layered oxide positive electrode material, preparation method thereof, positive electrode plate, sodium-ion battery and electric equipment |
| CN117059796B (en) * | 2023-10-13 | 2024-01-23 | 山西华钠铜能科技有限责任公司 | Sodium-electricity layered oxide positive electrode material, preparation method thereof, positive electrode plate, sodium-ion battery and electric equipment |
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