CN114524467B - Preparation method of high-purity micron-sized spherical sodium-electricity material - Google Patents

Preparation method of high-purity micron-sized spherical sodium-electricity material Download PDF

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CN114524467B
CN114524467B CN202210186555.4A CN202210186555A CN114524467B CN 114524467 B CN114524467 B CN 114524467B CN 202210186555 A CN202210186555 A CN 202210186555A CN 114524467 B CN114524467 B CN 114524467B
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许新安
曾林超
朱建辉
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Xu Xinan
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    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • 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
    • H01M4/52—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
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    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
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Abstract

The invention relates to the field of battery preparation, in particular to a preparation method of a high-purity micron-sized spherical sodium-electricity material, which is suitable for synthesizing high-purity micron-sized spherical Na 0.7 CoO 2 On the basis of particles, the preparation method reduces the process flow and the production cost, and does not generate harmful gas, and the preparation method sequentially comprises the following steps of: analytically pure Co (OH) 2 Mixing NaOH and stirring, dissolving in deionized water, heating, stirring (400-600 rpm), heating in a muffle furnace, ball milling, taking out, pressing into blocks, heating at 550-850 deg.C for 2-6 h to obtain black powder, adding into 1M HCl solution, stirring for 20 min, separating liquid from solid, washing with deionized water for 3-6 times, vacuum drying to obtain high purity spherical Na 0.7 CoO 2 And (3) powder.

Description

Preparation method of high-purity micron-sized spherical sodium-electricity material
Technical Field
The invention relates to the field of battery preparation, in particular to a preparation method of a high-purity micron-sized spherical sodium-electricity material.
Background
Sodium ion batteries have become potential energy storage objects by virtue of the characteristics of high theoretical capacity, low manufacturing cost, rich sodium ore resources and the like. With the development of society, the demand of energy is increasing, and research related to the positive electrode material of sodium ion batteries is increasing. Can be selected as a sodium-electricity positive electrode material, and needs to have higher potential and stability. The material that is more widely used at present is sodium vanadium phosphate (Na 3 V 2 (PO 4 ) 3 ) The material has the advantages of higher theoretical capacity and better application effect under room temperature conditions, but the material has the defects of complex preparation process, high control difficulty and the like, and the raw material has high cost, and also contains elements such as vanadium, phosphorus and the like which are harmful to human bodies, so the material has certain limitation in the aspect of large-scale application.
Na 0.7 CoO 2 The material has two structures, namely a layered structure and a spherical structure, is used as a positive electrode material of the sodium ion battery, has the potential as high as 3.8V, is a novel sodium ion battery material with potential at present, has the greatest advantages of stable cycle performance, can work for a long time in room temperature environment, has no toxicity and pollution, has the advantages of good electrochemical reversibility, low raw material cost, low preparation process cost, high stability of a synthesized product, high purity and the like compared with sodium ion batteries, and is more suitable for large-scale application in sodium ion batteries. Compared with flaky Na 0.7 CoO 2 (phase change is easy to occur in the process of sodium ion deintercalation to cause poor circulation stability), spherical Na 0.7 CoO 2 Also has outstanding electrochemical performance and better stability, which indicates Na 0.7 CoO 2 Is an important development direction of sodium-electricity positive electrode materials.
At present, na is prepared 0.7 CoO 2 The sodium-electricity material comprises the following steps: the cobalt precursor is firstly burned to Co 3 O 4 Adding Na 2 CO 3 Firing under air atmosphere at proper temperature to obtain Na 0.7 CoO 2 . The method has the defects of powder pollution, higher treatment temperature, long treatment time, larger difference in product composition, particle distribution and the like, low purity and the like.
The Chinese patent publication No. CN109095514A, the invention patent with publication date of 2018, 12 and 28 discloses a method for preparing P2-Na with different morphologies by using a template method 0.7 CoO 2 The material is prepared with basic cobalt carbonate in different forms as material and through forming cobaltosic oxide template and subsequent reaction with Na 2 CO 3 Solid phase sintering to prepare P2-Na 0.7 CoO 2 Can obtain Na with different shapes (granular, rod-like and flake-like) 0.7 CoO 2 A powder material. Although the invention does not produce toxic and harmful gases during the whole preparation process, it still has the following drawbacks:
firstly, a template method is adopted, cobalt-containing solution is required to be converted into multi-morphology basic cobalt carbonate, intermediate control links with higher difficulty coefficient exist, the process links are more, the morphology control difficulty is higher, and the phase is easy to be impure;
secondly, the control difficulty is higher when the multi-morphology basic cobalt carbonate is synthesized, the production cost is increased, certain pressure limitation is also needed in certain operations, and the production cost is increased again;
again, the invention produces Na by atmospheric calcination 0.7 CoO 2 Cannot be applied to high-purity micron-sized granular Na 0.7 CoO 2 Is prepared by the following steps.
Disclosure of Invention
In order to overcome the defects, the invention provides a preparation method of a high-purity micron-sized spherical sodium-electricity material, and in order to achieve the purposes, the invention can be realized by the following technical scheme:
the preparation method of the high-purity micron-sized spherical sodium-electricity material comprises the following steps:
s1, preparing a mixed solution: analytically pure Co (OH) 2 Mixing NaOH and deionized water, stirring to obtain mixed solution, and adding Na ＋ With Co 2＋ Is Na in the ratio of ＋ ：Co 2＋ ＝0.7：1；
S2, obtaining a precursor: continuously heating the mixed solution to 80 ℃, stirring, continuously stirring and continuously heating when the pink color of the mixed solution gradually fades and the brown color reacts to enable the mixed solution to continuously react, after the brown color is kept unchanged, filtering and drying the brown precursor, and then heating the precursor in a muffle furnace at 400-600 ℃ for 120-180 min to obtain black micron-sized granular cobaltosic oxide after the heating is finished;
s3, preparing a sodium electric material: mixing the above powder with sodium carbonate, ball milling for 2-h, taking out, pressing into blocks, feeding into muffle furnace, heating for 2-6 h at 550-850deg.C to obtain black powder, adding the black powder into 1M HCl solution, stirring for 20 min, liquid-solid separating, washing with deionized water for 3-6 times, and vacuum drying to obtain high purity spherical Na 0.7 CoO 2 Powder, high purity phase Na obtained 0.7 CoO 2 The particle size was 20. Mu.m.
Preferably, the mass ratio of the cobaltosic oxide powder to the sodium carbonate in the S3 is 0.175: 0.175 g:0.36: 0.36 g.
Preferably, the mass of the NaOH in S1 is equal to or greater than 4.0. 4.0 g.
Preferably, co (OH) in S1 2 The ratio of NaOH to deionized water is 0.2 g:4.0 g:100 ml.
Preferably, the speed of stirring in S2 is 400-600 rpm.
Preferably, the precursor heating temperature in S3 is 700 ℃ and the heating time is 120 min.
The electrochemical performance characterization method of the sodium electric material prepared by the preparation method of the high-purity micron-sized spherical sodium electric material comprises the following steps:
1) Stirring to obtain the high-purity spherical Na with the mass ratio of 8:1:1 0.7 CoO 2 Uniformly dispersing powder, carbon black and polyvinylidene fluoride in a methyl pyrrolidone solvent to prepare Na 0.7 CoO 2 Positive electrode slurry;
2) Coating one side of the aluminum foil with 100 μm Na by doctor blade coating method 0.7 CoO 2 The positive electrode slurry is dried at 80 ℃ to obtain Na 0.7 CoO 2 An electrode film;
3) Na is prepared from 0.7 CoO 2 Cutting the electrode film into electrode plates with the diameter of 14 and cm, and assembling the electrode plates with a metal sodium plate to form a button type sodium ion battery;
4) And performing cyclic voltammetry test and charge-discharge test on the assembled button sodium ion battery, wherein the charge-discharge voltage interval is 2.0-3.8V.
Advantageous effects
1. The preparation method of the high-purity micron-sized spherical sodium electric material adopts a hydrothermal reaction in the process of obtaining a precursor to obtain a crystalline brown precursor, so that a final product is conveniently prepared later, and the whole production process only needs three process steps of preparing mixed liquid, obtaining the precursor and preparing the sodium electric material, and compared with the prior art, the process steps are greatly reduced; in addition, the hydrothermal reaction is carried out by dissolving the solid raw materials in the solution, so that the dispersion degree is good, the solid raw materials do not need to be ground and mixed for a long time, and the high mixing uniformity can be ensured by only stirring and dissolving, so that the defect that the solid raw materials in the traditional method need to be ground and mixed for a long time is effectively avoided. Therefore, the invention has less process links, and the solid raw materials do not need to be ground and mixed for a long time.
2. The precursor in the preparation method of the high-purity micron-sized spherical sodium-electricity material is heated only in an atmospheric environment and only needs to be fully oxidized, so that a protective atmosphere is not needed, but the heating temperature is not higher than 400-600 ℃ and the time is less than 120-180 min. Therefore, the invention has lower production cost.
3. The final product of the preparation method of the high-purity micron-sized spherical sodium-electricity material is granular Na 0.7 CoO 2 The particle size is about 20 mu m, belongs to micron level, has good uniformity of product composition and particle distribution and obvious spherical structure, and is favorable for preparing the bulk sodium-electricity material with high crystal orientation and high performance. Therefore, the invention not only can prepare the granular Na with micron level 0.7 CoO 2 And the sintering of the high-quality powder material is facilitated, the process is simple, the operation is safe, and no harmful gas is generated.
Drawings
FIG. 1 is a powder SEM characterization result diagram of the product of the present invention;
FIG. 2 is a powder XRD characterization result diagram of the product of the invention;
FIG. 3 is a flow chart of the present invention;
FIG. 4 is a cyclic voltammogram (sweep rate 0.2 mV s) of the product of the present invention as a positive electrode material for sodium ion batteries -1 ）；
FIG. 5 shows the cycle performance of the product of the invention as a positive electrode material for sodium ion batteries (current magnitude 0.4C, 1C =125 mA g -1 ）。
Detailed Description
The invention will be further illustrated with reference to specific examples. The following examples are only illustrative of the present invention and are not intended to limit the scope of the invention.
Referring to FIGS. 1-5, a micron-sized granular Na 0.7 CoO 2 The preparation method sequentially comprises a preparation process of mixed liquid, a precursor obtaining process and a preparation process of the sodium electric material, wherein the preparation process of the sodium electric material comprises the operation steps of heating the precursor to prepare the sodium electric material;
1) Preparing a mixed solution: analysis of pure Co (OH) 2 Mixing NaOH and deionized water, and stirring to obtain mixed solution; said Co (OH) 2 The ratio of NaOH to deionized water is 0.2 g:4.0 g:100 ml;
2) Precursor obtaining: the above mixture was continuously heated (80 ℃) and stirred (400-600 rpm), when the mixture was heated and gradually faded from pink, the brown color appeared to react, and continuously stirred and continuously heated to continuously react the mixture, and when the brown color remained unchanged, the reaction was ended. And (3) heating the crystalline brown precursor in a muffle furnace at 400-600 ℃ for 120-180 min to obtain black micron-sized granular cobaltosic oxide.
3) Preparation of sodium-electricity material: grinding the prepared micron-sized granular cobaltosic oxide powder (0.175-g) and sodium carbonate (0.36-g) into 2-h by ball milling, taking out and pressing into blocks, feeding into a muffle furnace, heating at 550-850 ℃ for 2-6 h to obtain black powder, adding the black powder into 1M HCl, stirring for 20 min, performing liquid-solid separation, washing with deionized water for 3-6 times, and vacuum drying to obtain high-purity spherical Na 0.7 CoO 2 And (3) powder.
The preparation of the sodium electric material comprises the following steps: the micron-sized granular Na 0.7 CoO 2 Is a high purity phase with a particle size of about 20 μm.
The principle of the invention is explained as follows:
1. preparing a mixed solution:
Co(OH) 2 the ratio of NaOH to deionized water is 0.2 g:4.0 g:100 The reason for ml is that: ensure the obtained Na 0.7 CoO 2 Na: co=0.7: 1, naOH accelerates ionization during heating, if Co (OH) 2 Too high a ratio to NaOH results in Co (OH) in the product 2 Residual, which ultimately results in CoOOH products of low purity, can have an impact on the final product composition. Deionized water is a basic condition in experiments, impurity ions in tap water can adversely affect the final products of the experiments, the sample cannot be dissolved due to too small consumption, excessive heat is generated, and the reaction cannot be carried out or the reaction time is too long due to too low concentration.
Co(OH) 2 The reason why the stirring speeds of NaOH and deionized water are all more than 400 rpm is that: too low a stirring speed may cause incomplete reaction of the raw materials and sedimentation and aggregation of solid particles together, and thus, the stirring speed may achieve an optimal synthesis effect only not lower than 400 rpm, and lower than this may cause incomplete purity of the reaction to be lowered.
2. Precursor obtaining:
precursor: the precursor is the reactant of the invention-Co (OH) 2 And NaOH, by hydrothermal reaction and calcination, to distinguish the end product Na 0.7 CoO 2 And is therefore referred to as a precursor. The precursor is heated only in the atmospheric environment, and only the material is fully oxidized, so that protective atmosphere is not needed, and the whole preparation process can be ensured not to generate toxic and harmful gas; in addition, the self-characteristics of the precursor determine that the heating temperature required for decomposition is low, so that the heating time is short. Therefore, the precursor is heated without atmosphere protection, and the heating temperature and time are low, so that the energy consumption is low.
Hydrothermal reaction: the invention generates a precursor through hydrothermal reaction and heating, and the whole process starts from the process of reacting mixed liquor and generating brown precipitate to the process of ending the process of completely brown state. The hydrothermal method adopted by the invention is that the solid raw materials are dissolved in the solution, so that the dispersity is good, the solid raw materials do not need to be ground and mixed for a long time, and high mixing uniformity can be ensured only by stirring and dissolving, and the traditional method is that the solid raw materials are directly heated for reaction, so that the uniformity can be ensured only by grinding and mixing for a long time.
Stirring: when the hydrothermal reaction starts, stirring is continued because when brown precipitate appears, the pink solution fades, and if stirring is stopped, solid particles precipitate and agglomerate to affect Co (OH) 2 To CoOOH.
3. Preparation of sodium-electricity material:
the heating temperature is 550-850 ℃, and the heating time is 120-180 min: the temperature and time directly influence the occurrence degree of the chemical reaction, and when the temperature and time are lower than the ranges, the reaction cannot completely occur, the product contains impurities, and when the temperature and time are higher than the ranges, na is generated 0.7 CoO 2 And (5) decomposing.
Ball milling: solid Co obtained by heating CoOOH solid 3 O 4 With Na and Na 2 CO 3 Ball milling 2 h is carried out because the solid is uniformly mixed with the solid, and good interface contact is beneficial to subsequent solid-solid phase reaction, prevents segregation from occurring, and influences Na 0.7 CoO 2 Quality is improved.
And (3) briquetting: co is to be 3 O 4 With Na and Na 2 CO 3 After ball milling, the mixture is pressed into blocks, and the reason is that the dense blocks are favorable for heat transfer, so that the reaction is complete.
Acid washing: the unreacted alkaline substance Na in the mixed powder after the heating reaction 2 CO 3 The reason for this is that the product purity is improved by means of a simple acid-base neutralization reaction.
4. Product-micron-sized granular Na 0.7 CoO 2 ：
The micron-sized granular Na prepared by the invention 0.7 CoO 2 The particle diameter is 20 mu m, and compared with pure particle diameter, the particle diameter has good uniformity, obvious spherical structure, high stability of synthesized products and stable high-temperature performance, and is favorable for sintering high-crystallization-orientation and high-performance block sodium electricityMaterials, but Na prepared by the prior art 0.7 CoO 2 There are problems such as uneven particle size and segregation of components.
Example 1:
referring to fig. 3, a preparation method of a high-purity micron-sized spherical sodium-electric material sequentially comprises the following processes;
preparing a mixed solution: analysis of pure Co (OH) 2 Mixing NaOH and deionized water, and stirring to obtain mixed solution; said Co (OH) 2 The ratio of NaOH to deionized water is 0.2 g:4.0 g:100 ml;
precursor obtaining: the mixture was heated continuously (80 ℃) and stirred (400-600 rpm) and when the mixture was heated and the pink gradually removed, the brown color appeared to react and started, stirring was continued and heating was continued to keep the mixture continuously reacting and when the brown color remained unchanged, the reaction ended. And (3) heating the brown precursor in a muffle furnace at 700 ℃ for 120 min to obtain black micron-sized granular cobaltosic oxide.
Preparation of sodium-electricity material: mixing the above powder (0.175-g) with sodium carbonate (0.36-g), ball milling 2-h, taking out, pressing into blocks, feeding into muffle furnace, heating at 550-850deg.C for 2-6-h to obtain black powder, adding the black powder into 1M HCl solution, stirring for 20 min, separating liquid from solid, washing with deionized water for 3-6 times, and vacuum drying to obtain high purity spherical Na 0.7 CoO 2 And (3) powder. As can be seen from FIG. 1, the product is in the form of particles, the particle size of 20 μm can be measured according to the scale of the picture, the size completely meets the micrometer definition, and as can be seen from FIG. 2, the composition of the product phase and the standard Na 0.7 CoO 2 The samples were consistent and proved to be in a highly pure phase morphology.
Characterization of electrochemical properties of sodium-electric materials: stirring to obtain the high-purity spherical Na with the mass ratio of 8:1:1 0.7 CoO 2 Uniformly dispersing powder, carbon black and polyvinylidene fluoride in a methyl pyrrolidone solvent to prepare Na 0.7 CoO 2 And (3) positive electrode sizing agent. Coating one side of the aluminum foil with 100 μm Na by doctor blade coating method 0.7 CoO 2 The positive electrode slurry is dried at 80 ℃ to obtain Na 0.7 CoO 2 An electrode film. Na is mixed with 0.7 CoO 2 The electrode film is cut into electrode plates with the diameter of 14 and cm, and the electrode plates and the metal sodium plates are assembled into the button type sodium ion battery. The assembled button sodium ion battery is subjected to cyclic voltammetry test and charge and discharge test, the charge and discharge voltage interval is 2.0-3.8V, as shown in figure 4, the cyclic voltammetry graph (the sweeping speed is 0.2 mV s) when the product of the invention is used as the positive electrode material of the sodium ion battery -1 ) As shown in FIG. 5, the product of the invention has the cycle performance (current magnitude of 0.4C, 1C =125 mA g) when used as a positive electrode material of a sodium ion battery -1 ) The invention prepares the micron-sized granular Na 0.7 CoO 2 The performance meets the requirements.
Example 2:
the basic content is the same as in example 1, except that the sodium-electric material is produced in the following way: the heating temperature is 700 ℃, and the heating time is 150 min.
Example 3:
the basic content is the same as in example 1, except that the sodium-electric material is produced in the following way: the heating temperature is 850 ℃, and the heating time is 180 min.

Claims (2)

1. The preparation method of the high-purity micron-sized spherical sodium-electricity material is characterized by comprising the following steps of:
s1, preparing a mixed solution: analytically pure Co (OH) 2 Mixing NaOH and deionized water, stirring to obtain mixed solution, and adding Na ＋ With Co 2＋ Is Na in the ratio of ＋ ：Co 2＋ ＝0.7：1；
S2, obtaining a precursor: continuously heating the mixed solution to 80 ℃, stirring, continuously stirring and continuously heating when the pink color of the mixed solution gradually fades and the brown color reacts to enable the mixed solution to continuously react, after the brown color is kept unchanged, filtering and drying the brown precursor, and then heating the precursor in a muffle furnace at 400-600 ℃ for 120-180 min to obtain black micron-sized granular cobaltosic oxide after the heating is finished;
s3, preparing a sodium electric material: mixing the above powder with sodium carbonate, ball milling for 2-h, taking out, pressing into blocks, feeding into muffle furnace, heating for 2-6 h at 550-850deg.C to obtain black powder, adding the black powder into 1M HCl solution, stirring for 20 min, liquid-solid separating, washing with deionized water for 3-6 times, and vacuum drying to obtain high purity spherical Na 0.7 CoO 2 Powder, high purity phase Na obtained 0.7 CoO 2 The grain diameter is 20 mu m;
s3, the mass ratio of the cobaltosic oxide powder to the sodium carbonate is 0.175: 0.175 g:0.36 g;
the mass of the NaOH in the S1 is more than or equal to 4.0 g;
co (OH) in S1 2 The ratio of NaOH to deionized water is 0.2 g:4.0 g:100 ml;
the stirring speed in the step S2 is 400-600 rpm;
and S3, heating the precursor at 700 ℃ for 120 min.
2. The method for characterizing the electrochemical performance of a sodium-electric material prepared by the preparation method of a high-purity micron-sized spherical sodium-electric material according to claim 1, which is characterized by comprising the following steps:
1) Stirring to obtain the high-purity spherical Na with the mass ratio of 8:1:1 0.7 CoO 2 Uniformly dispersing powder, carbon black and polyvinylidene fluoride in a methyl pyrrolidone solvent to prepare Na 0.7 CoO 2 Positive electrode slurry;
2) Coating one side of the aluminum foil with 100 μm Na by doctor blade coating method 0.7 CoO 2 The positive electrode slurry is dried at 80 ℃ to obtain Na 0.7 CoO 2 An electrode film;
3) Na is prepared from 0.7 CoO 2 Cutting the electrode film into electrode plates with the diameter of 14 and cm, and assembling the electrode plates with a metal sodium plate to form a button type sodium ion battery;
4) And performing cyclic voltammetry test and charge-discharge test on the assembled button sodium ion battery, wherein the charge-discharge voltage interval is 2.0-3.8V.
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Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
多种形貌特征Co3O4纳米材料的可控合成及性能研究;黄志芳;《中国博士学位论文全文数据库 工程科技I辑》;B014-16 *
纳米原料制备Na_(0.7)CoO_2多晶;杨有利, 张鹏翔, 林成天, 张辉, 周小方, 段云彪;云南大学学报(自然科学版)(02);146-148 *

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