CN111153441B - Preparation method of potassium cobaltate particles - Google Patents

Preparation method of potassium cobaltate particles Download PDF

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CN111153441B
CN111153441B CN202010016417.2A CN202010016417A CN111153441B CN 111153441 B CN111153441 B CN 111153441B CN 202010016417 A CN202010016417 A CN 202010016417A CN 111153441 B CN111153441 B CN 111153441B
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于琪瑶
王伟
胡俊
锁国权
方岱宁
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Beijing Institute of Technology BIT
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    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • 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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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract

The invention discloses a preparation method of potassium cobaltate particles, which comprises the steps of mixing a prepared cubic cobalt precursor with potassium carbonate and then calcining, or mixing prepared cobalt oxide particles with potassium carbonate and then calcining, and cooling to obtain the potassium cobaltate particles, particularly nano-scale potassium cobaltate particles.

Description

Preparation method of potassium cobaltate particles
Technical Field
The invention belongs to the technical field of functional nano materials, and particularly relates to a preparation method of potassium cobaltate particles.
Background
The 21 st century is the century of energy, which is the basis of the development of human society. The development of human society cannot leave energy sources, and the society developing at a high speed causes the over-quick consumption of lithium resources by people, so that the price rises; meanwhile, people put forward higher demands on energy density of batteries, so that future development of lithium ion batteries faces more challenges.
In order to solve the above problems, researchers have conducted many intensive studies around metal ion secondary batteries in recent years in order to meet market demands. On one hand, researchers continue to deeply excavate from the interior of the lithium ion battery system and research and develop a plurality of electrode materials with excellent performance; on the other hand, compared with metal lithium, sodium-potassium metal not only has abundant reserves, low price and environmental protection, but also has the energy storage mechanism of room-temperature sodium-ion batteries and potassium-ion batteries which is very similar to that of lithium-ion batteries, so the sodium-potassium metal is considered to be one of the ideal choices for the next generation of automobile power sources and large-scale power stations matching power sources instead of the lithium-ion batteries. However, sodium potassium ions have larger ionic radius and slower kinetic rate, and become main factors restricting the development of potassium storage materials, and the development of high-performance potassium-embedded cathode materials is the key to improve the specific energy of the potassium ion battery and promote the application of the potassium ion battery.
Potassium cobaltate (K)xCoO2) Is a transition metal oxide having a layered structure of which crystal structure has K+And CoO2Stacked alternately along the c-axis to form a layered structure with highly two-dimensional characteristics. Due to potassium cobaltate (K)xCoO2) The typical layered structure is beneficial to the transmission and stability of electrons, has the advantages of high use temperature, low resistivity, oxidation resistance, no pollution, long service life and the like, and also has the advantages of rich raw material resources, convenient preparation by directly sintering in oxygen during preparation, low cost and the like, thereby being attracted by people. Currently potassium cobaltate (K)xCoO2) The synthesis method mainly comprises the steps of mixing cobalt oxide and potassium hydroxide or carrying out high-temperature sintering after ball milling, and the potassium hydroxide is corrosive and harsh in synthesis conditions, so that the cobalt oxide and the potassium hydroxide cannot be directly mixed with powder in a grinding mode and the particle size and the morphology of the powder cannot be controlled.
So far, no method for synthesizing potassium cobaltate particles by adopting potassium carbonate has been reported. Therefore, the method has extremely important theoretical and practical significance for the development of potassium cobaltate materials by controlling and synthesizing potassium cobaltate particles with specific shapes. For literature research, no report is found on the synthesis of potassium cobaltate particles by high-temperature sintering of potassium carbonate.
The information disclosed in this background of the invention section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any way to imply that this information forms part of the prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
To this end, the present invention is intended to provide a process for producing potassium cobaltate particles, which process enables the production of potassium cobaltate particles (K) simply, efficiently and at low costxCoO2Particles), in particular nanoscale potassium cobaltate particles.
Firstly, the preparation method of the potassium cobaltate particles provided by the invention comprises the following steps:
step 1: dissolving 0.1 mmol-1.0 mmol of cobalt sulfate and 0.1 mmol-1.0 mmol of sodium citrate in 10 mL-50 mL of deionized water to form a solution A;
step 2: dissolving 0.1 mmol-1.0 mmol potassium hexacyanocobaltate in 10 mL-50 mL deionized water to form a solution B;
and step 3: mixing the solution A and the solution B for 10-30 min under magnetic stirring to form a mixed solution C;
and 4, step 4: aging the mixed solution C at room temperature for 1-72 h, collecting precipitates by centrifugation, washing with water and ethanol, and performing vacuum drying for at least 12h to obtain a cubic cobalt precursor;
and 5: weighing and mixing the cubic cobalt precursor and potassium carbonate according to the molar ratio of potassium to cobalt of 0.6-0.9, heating the mixture to 700-900 ℃ at a speed of 2-10 ℃/min in an oxygen atmosphere, calcining for 1-12 h,
step 6: and the calcination can promote the complete combustion and the full reaction of the mixture, and the mixture is cooled after the calcination to obtain the potassium cobaltate particles.
In addition, the invention provides another preparation method of potassium cobaltate particles, which comprises the following steps:
step 1: preparing cobalt oxide particles;
step 2: weighing and mixing the cobalt oxide particles and potassium carbonate according to the molar ratio of potassium to cobalt of 0.6-0.7, heating the mixture to 700-900 ℃ at a speed of 2-10 ℃/min in an oxygen atmosphere, and calcining for 1-12 h;
and step 3: and cooling after calcining to obtain the potassium cobaltate particles.
As described above, the present invention providesAt least two simple, high-efficiency and low-cost potassium cobaltate particle preparation methods are provided, and the potassium cobaltate particles (K) prepared by the methodxCoO2Particles), in particular nanoscale potassium cobaltate particles, having a specific structure and a small size, which greatly increase their potassium intercalation capacity, are preparedxCoO2Particles) can significantly improve the performance of the potassium ion battery when applied to the positive electrode material for the potassium ion battery.
Compared with the prior art, the invention has the following beneficial technical effects:
1) the method is simple to prepare, and the required potassium cobaltate particles can be directly prepared by high-temperature sintering.
2) The method has the advantages of simple raw materials, low cost, no toxicity, no corrosion and safety of potassium carbonate as a potassium source.
3) The size and the shape of the finished product prepared by the method can be regulated, and the potassium cobaltate particles with different sizes and different structures can be prepared by regulating the raw materials, the reaction temperature and the reaction time.
4) The method has the advantages of low process cost, controllable preparation process and good application prospect in the field of potassium ion batteries.
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The foregoing and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings. In the drawings, like reference numerals refer to the same or similar parts or elements throughout the several views unless otherwise specified. The figures are not necessarily to scale. It is appreciated that these drawings depict only some embodiments in accordance with the disclosure and are therefore intended to provide a further understanding of the invention, and are not to be considered limiting of its scope, as it is defined by the present application. Wherein:
FIG. 1 is an X-ray diffraction pattern of potassium cobaltate particles prepared by the preparation method provided by the invention;
FIG. 2 is a scanning electron microscope photograph of potassium cobaltate particles prepared by the preparation method provided by the present invention;
fig. 3 is a charge/discharge curve of the positive electrode material for a potassium ion battery based on the potassium cobaltate particles provided by the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and should not be taken to be limiting.
First, the present invention provides a method for preparing potassium cobaltate particles (K) simply and efficiently at low costxCoO2Granules), wherein:
example one
In a typical synthesis, 0.3mmol cobalt sulfate and 0.1mmol sodium citrate are dissolved in 20mL deionized water (DI) to form solution A; 0.2mmol of potassium hexacyanocobaltate (III) was dissolved in 20mL of deionized water to form solution B.
Then, mixing the solution A and the solution B for 10min under magnetic stirring to obtain a mixed solution C; and aging the mixed solution C at room temperature for 12h, collecting precipitates by centrifugation, washing with water and ethanol, and performing vacuum drying for at least 12h to obtain a cobalt cube precursor.
Weighing the cubic cobalt precursor and potassium carbonate according to the molar ratio of potassium to cobalt of 0.6, heating to 700 ℃ at 2 ℃/min in an oxygen atmosphere, calcining for 6h to promote complete combustion of the mixture and sufficient reaction of the mixture, and cooling after calcining to obtain the potassium cobaltate particles (K) to be prepared by the inventionxCoO2Particles).
Example two
In a typical synthesis, 0.3mmol cobalt sulfate and 0.5mmol sodium citrate are dissolved in 25mL deionized water (DI) to form solution A, and 0.2mmol potassium hexacyanocobaltate (III) is dissolved in 25mL deionized water to form solution B.
Then, mixing the solution A and the solution B for 20min under magnetic stirring to obtain a mixed solution C; and aging the mixed solution C at room temperature for 24h, collecting precipitates by centrifugation, washing with water and ethanol, and drying in vacuum for 12h to obtain a cobalt cube precursor.
Weighing the cubic cobalt precursor and potassium carbonate according to the molar ratio of potassium to cobalt of 0.7, heating to 750 ℃ at 2 ℃/min in an oxygen atmosphere, calcining for 8 hours to promote complete combustion of the mixture and sufficient reaction of the mixture, and cooling after calcination to obtain the potassium cobaltate particles (K) to be prepared by the inventionxCoO2Particles).
EXAMPLE III
In a typical synthesis, 0.6mmol cobalt sulfate and 1.0mmol sodium citrate are dissolved in 50mL deionized water (DI) to form solution A and 0.4mmol potassium hexacyanocobaltate (III) is dissolved in 50mL deionized water to form solution B.
Then, mixing the solution A and the solution B for 30min under magnetic stirring to obtain a mixed solution C; and aging the mixed solution C at room temperature for 24h, collecting precipitates by centrifugation, washing with water and ethanol, and drying in vacuum for 12h to obtain a cobalt cube precursor.
Weighing the cubic cobalt precursor and potassium carbonate according to the molar ratio of potassium to cobalt of 0.8, heating to 750 ℃ at 5 ℃/min in an oxygen atmosphere for calcining for 10h, wherein the calcining aims to promote complete combustion of the mixture and sufficient reaction of the mixture, and cooling after calcining to obtain the potassium cobaltate particles (K) to be prepared by the inventionxCoO2Particles).
Example four
In a typical synthesis, 0.3mmol cobalt sulfate and 0.5mmol sodium citrate are dissolved in 25mL deionized water (DI) to form solution A, and 0.2mmol potassium hexacyanocobaltate (III) is dissolved in 25mL deionized water to form solution B.
Then, mixing the solution A and the solution B for 20 minutes under magnetic stirring to obtain a mixed solution C; and aging the mixed solution C at room temperature for 24h, collecting precipitates by centrifugation, washing with water and ethanol, and drying in vacuum for 12h to obtain a cobalt cube precursor.
Weighing the cubic cobalt precursor and potassium carbonate according to the molar ratio of potassium to cobalt of 0.8, and carrying out oxygen atmosphere treatmentHeating to 800 ℃ at the speed of 5 ℃/min for calcining for 12h, wherein the calcining aims to promote the complete combustion of the mixture and the full reaction of the mixture, and cooling after calcining to obtain the potassium cobaltate particles (K) to be prepared by the inventionxCoO2Particles).
EXAMPLE five
In a typical synthesis, cobalt oxide particles are prepared, either as commercially available finished cobalt oxide particles or as currently prepared by any method.
Weighing the cobalt oxide particles and the potassium carbonate according to the molar ratio of potassium to cobalt of 0.6, grinding and uniformly mixing the powder, heating to 750 ℃ at 2 ℃/min in an oxygen atmosphere for calcining for 8h, wherein the calcining aims to promote complete combustion of the mixture and sufficient reaction of the mixture, and cooling after calcining to obtain the potassium cobaltate particles (K) to be prepared by the inventionxCoO2Particles).
EXAMPLE six
In a typical synthesis, cobalt oxide particles are prepared, either as commercially available finished cobalt oxide particles or as currently prepared by any method.
Weighing the cobalt oxide particles and the potassium carbonate according to the molar ratio of potassium to cobalt of 0.7, grinding and uniformly mixing the powder, heating to 850 ℃ at 2 ℃/min in an oxygen atmosphere for calcining for 10h, wherein the calcining aims to promote the complete combustion of the mixture and the sufficient reaction of the mixture, and cooling after calcining to obtain the potassium cobaltate particles (K) to be prepared by the inventionxCoO2Particles).
Preferably, in the preparation methods provided in the first to sixth embodiments of the present invention, the particle size of the cubic cobalt precursor prepared in the relevant step is 20nm to 1000 nm;
it should be noted that, in the preparation methods provided in the above-mentioned fifth and sixth embodiments of the present invention, the cobalt oxide particles used are not limited in shape and size, including but not limited to nano cobalt oxide materials.
Preferably, in order to further improve the preparation effect, in the preparation methods provided in the above-mentioned examples five and six of the present invention, the cobalt oxide particles may be ground to 200 mesh or less before being mixed with the potassium carbonate.
It should be noted that, based on the preparation methods provided in the first to sixth embodiments of the present invention, potassium cobaltate particles (K) can be directly prepared by high temperature sinteringxCoO2Particles), and potassium cobaltate nanoparticles (K) with different sizes and structures can be prepared by regulating and controlling raw materials, reaction temperature and reaction timexCoO2Particles), in particular nano-scale potassium cobaltate particles, can be prepared, the finally prepared nano-scale potassium cobaltate particles can have the particle size of 20nm to 1000nm, and the K value isxCoO2For particles, x is in the range of 0.5<x<0.9。
Wherein, fig. 1 shows an X-ray diffraction spectrum (also called XRD spectrum) of the potassium cobaltate particles prepared by the present invention, which shows the crystal structure of the potassium cobaltate particles; fig. 2 shows a Scanning Electron Microscope (SEM) photograph of the potassium cobaltate particles prepared by the present invention.
Further, the invention provides a positive electrode material for a potassium ion battery, which is manufactured based on the potassium cobaltate particles prepared by the preparation method. Fig. 3 shows a charge-discharge curve of the positive electrode material for a potassium ion battery based on the potassium cobaltate particles prepared by the present invention, specifically, a charge-discharge curve of the first cycle at a charge-discharge current density of 60mA/g, for displaying a voltage range, a specific capacity of the battery, and the like during charge and discharge of the battery.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.

Claims (2)

1. A preparation method of potassium cobaltate particles is characterized by comprising the following steps:
step 1: dissolving 0.1 mmol-1.0 mmol of cobalt sulfate and 0.1 mmol-1.0 mmol of sodium citrate in 10 mL-50 mL of deionized water to form a solution A;
step 2: dissolving 0.1 mmol-1.0 mmol potassium hexacyanocobaltate in 10 mL-50 mL deionized water to form a solution B;
and step 3: mixing the solution A and the solution B for 10-30 min under magnetic stirring to form a mixed solution C;
and 4, step 4: aging the mixed solution C at room temperature for 1-72 h, collecting precipitates by centrifugation, washing with water and ethanol, and performing vacuum drying for at least 12h to obtain a cubic cobalt precursor;
and 5: weighing and mixing the cubic cobalt precursor and potassium carbonate according to the molar ratio of potassium to cobalt of 0.6-0.9, heating the mixture to 700-900 ℃ at a speed of 2-10 ℃/min in an oxygen atmosphere, calcining for 1-12 h,
step 6: and the calcination can promote the complete combustion and the full reaction of the mixture, and the mixture is cooled after the calcination to obtain the potassium cobaltate particles.
2. The method according to claim 1, wherein the cubic cobalt precursor prepared in step 4 has a particle size of 20 to 1000 nm.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004107142A (en) * 2002-09-18 2004-04-08 Rikogaku Shinkokai WHISKER CRYSTAL OF LAYERED COBALT OXIDE NaxCoO2 HAVING THERMOELECTRIC CONVERSION CHARACTERISTIC AND METHOD OF PRODUCING THE SAME
CN109095514A (en) * 2018-09-11 2018-12-28 安徽工业大学 One kind preparing different-shape P2-Na with template0.7CoO2The method of material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004107142A (en) * 2002-09-18 2004-04-08 Rikogaku Shinkokai WHISKER CRYSTAL OF LAYERED COBALT OXIDE NaxCoO2 HAVING THERMOELECTRIC CONVERSION CHARACTERISTIC AND METHOD OF PRODUCING THE SAME
CN109095514A (en) * 2018-09-11 2018-12-28 安徽工业大学 One kind preparing different-shape P2-Na with template0.7CoO2The method of material

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"P2- and P3-KxCoO2 as an electrochemical potassium intercalation host ";Yuya Hironaka et al.;《Chem. Commun.》;20170307;第53卷;第3694页左栏第1段至右栏第1段，图1和图2 *
"Stoichiometric oxygen content in NaxCoO2";L. Viciu et al.;《PHYSICAL REVIEW B 》;20060629;第73卷;第212107-1页左栏第1段至第212107-2页左栏第1段 *
"THERMOELECTRIC PROPERTIES OF (Na,M)xCoO2 (M = Li, K, Cs) CERAMICS";N. S. Krasutskaya et al.;《Chemistry and Technology of Inorganic Materials and Substances》;20131231(第3期);第35页左栏第1段至第3段 *
Yuya Hironaka et al.."P2- and P3-KxCoO2 as an electrochemical potassium intercalation host ".《Chem. Commun.》.2017,第53卷第3693—3696页. *

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