CN113443652B - Preparation method and application of octahedral lithium manganate - Google Patents

Preparation method and application of octahedral lithium manganate Download PDF

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CN113443652B
CN113443652B CN202110506018.9A CN202110506018A CN113443652B CN 113443652 B CN113443652 B CN 113443652B CN 202110506018 A CN202110506018 A CN 202110506018A CN 113443652 B CN113443652 B CN 113443652B
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lithium manganate
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李忆非
赵佳琦
康晓红
谭兴华
褚卫国
王耀国
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Ningbo Fengcheng Advanced Energy Materials Research Institute Co ltd
National Center for Nanosccience and Technology China
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Abstract

The application discloses a preparation method and application of octahedral lithium manganate. The preparation method of the octahedral lithium manganate comprises the steps of drying a mixed solution containing lithium salt, manganese carbonate and an orientation agent to obtain mixed powder, calcining and cooling to obtain the octahedral lithium manganate. Through improving the preparation method of lithium manganate, the (111) crystal face of spinel lithium manganate is exposed to the maximum extent, and the spinel lithium manganate is used as a positive electrode material for a water-based battery, has excellent electrochemical performance, inhibits the dissolution of manganese in the circulation process, and improves the long-term circulation stability of the water-based battery. The preparation method has simple process and convenient operation, and is easy to realize large-scale production.

Description

Preparation method and application of octahedral lithium manganate
Technical Field
The application relates to a preparation method and application of octahedral lithium manganate, and belongs to the technical field of lithium ion batteries.
Background
At present, the lithium ion battery has entered into the aspects of people's life, but has many advantages, and the lithium ion battery also has non-negligible disadvantages, especially the organic electrolyte has inflammable, toxic and other unsafe factors. Therefore, in order to improve the safety performance of lithium ion batteries, aqueous lithium ion batteries employing an aqueous solution as an electrolyte have been attracting attention.
The spinel type lithium manganate structure belongs to a cubic crystal system, has a better three-dimensional tunnel structure, is favorable for reversible deintercalation of lithium ions in crystal lattices thereof, and does not cause structural collapse, so that the material has excellent rate performance and stability, and has a theoretical specific capacity of 148mAh/g. In addition, the lithium manganate has the advantages of rich resources, low cost, environmental friendliness and the like, and is the anode material with the most application potential at present. However, in the cycling process, the lithium manganate can generate Jahn-Teller effect, mn dissolution and other phenomena, so that the capacity is rapidly attenuated, and the cycling performance is deteriorated. In order to solve the problem of lithium manganate cycle stability, the modification method which is commonly adopted at present is ion doping or surface coating. For ion doping, the main doping elements are iron, aluminum, chromium, cobalt, fluorine and the like, and the surface coating is usually to coat a layer of Al on the surface of lithium manganate 2 O 3 、Co 3 O 4 Various oxides such as ZnO, etc., stabilize the structure of lithium manganate in the circulating process and inhibit the dissolution of manganese, thereby improving the circulating stability.
Disclosure of Invention
Aiming at the defects of the lithium manganate anode material in the circulation process, the invention provides a novel lithium manganate anode material synthesis method by improving the preparation method of lithium manganate. The method aims to synthesize the octahedral spinel lithium manganate, expose compact and stable (111) crystal faces to the greatest extent, inhibit the dissolution of manganese in the circulation process and improve the long-term circulation stability of the water-based battery.
According to a first aspect of the present application, a method of preparing octahedral lithium manganate is provided. The morphology of the lithium manganate is octahedral.
The preparation method of the octahedral lithium manganate comprises the steps of drying a mixed solution containing lithium salt, manganese carbonate and an orientation agent to obtain mixed powder, calcining and cooling to obtain the octahedral lithium manganate.
Optionally, the molar ratio of the lithium salt, the manganese carbonate and the orientation agent is 1-1.2:2-2.4:0.05-0.1.
Alternatively, the molar concentration of lithium salt in the mixed solution is 1 to 1.2mol/L.
Alternatively, the molar concentration of the lithium salt in the mixed solution is 1mol/L.
Optionally, the molar ratio of the lithium salt to manganese carbonate is 1.05:2.
Wherein the mole number of the lithium salt is calculated as the mole number of the lithium element contained therein.
Optionally, the orientation agent is at least one selected from sodium dodecyl sulfonate, polyvinylpyrrolidone, ammonium fluoride and ammonium chloride.
Alternatively, the lithium salt is selected from LiCl, liOH, li 2 CO 3 At least one of them.
Optionally, the conditions of the calcination are: in the oxygen-containing gas atmosphere, the temperature rising speed is 1-10 ℃/min, the temperature is 550-850 ℃ and the time is 4-12 h.
Alternatively, the firing temperature is independently selected from any value or range of values between any two of 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃.
Alternatively, the short time is independently selected from any value or range of values between any two of 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h.
Alternatively, the heating rate is independently selected from any value or range of values between any two of 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min.
Optionally, the calcination is performed under an oxygen-containing gas atmosphere.
Optionally, in the oxygen-containing gas, the volume fraction of oxygen is 20-100%.
Optionally, in the oxygen-containing gas, the volume fraction of oxygen is 80-100%.
Optionally, the oxygen-containing gas is air.
Optionally, the preparation method of the manganese carbonate comprises the following steps: mixing the solution A containing manganese salt and the solution B containing carbonate, reacting, and drying to obtain manganese carbonate;
in the solution A containing manganese salt, the manganese salt is selected from at least one of manganese chloride, manganese fluoride, manganese nitrate and manganese acetate;
in the solution B containing carbonate, the carbonate is at least one selected from sodium carbonate, potassium carbonate and ammonium carbonate.
Optionally, the molar ratio of the manganese salt to the carbonate is 1-1.1:1.2-1.32.
Optionally, in the solution A, the molar concentration of the manganese salt is 1-1.1mol/L.
Optionally, the molar concentration of carbonate in the solution B is 1-1.1mol/L.
Optionally, the molar concentration of carbonate in the solution B is 1.2-1.32mol/L.
Alternatively, the molar concentration of the manganese salt in the solution A is 1mol/L.
Alternatively, the molar concentration of carbonate in the solution B is 1mol/L.
Optionally, the molar ratio of manganese salt to carbonate is 1:1.2.
alternatively, the temperature of the reaction is 10 to 70 ℃.
Alternatively, the temperature of the reaction is independently selected from any value or range of values between any two of 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃,70 ℃.
Optionally, the B solution is pumped into the a solution.
Optionally, the pumping speed is 1-100 rpm.
Optionally, the drying conditions are: vacuum drying at 70deg.C for 12 hr.
As a preferred embodiment, the method for preparing manganese carbonate comprises:
preparing manganese salt into solution A, preparing carbonate into solution B, wherein the molar ratio of manganese salt to carbonate is 1:1.2, pumping B into solution A under continuous stirring, filtering after the reaction is completed, and drying to obtain manganese carbonate powder.
Specifically, at 10-70 ℃, pumping the carbonate B solution into the manganese salt A solution under continuous stirring at the pumping speed of 1-100rpm, filtering after the reaction is completed, and vacuum drying at 70 ℃ for 12 hours to obtain manganese carbonate precursor powder.
As a preferred embodiment, the method for preparing octahedral lithium manganate comprises:
(1) Preparing manganese salt into solution A, preparing carbonate into solution B, wherein the molar ratio of manganese salt to carbonate is 1:1.2, pumping B into solution A under continuous stirring, filtering after the reaction is completed, and drying to obtain manganese carbonate precursor powder;
(2) Weighing lithium salt and the manganese carbonate precursor powder according to a molar ratio of 1.05:2, introducing an orientation agent to prepare a solution C, stirring, evaporating and drying to obtain mixed powder;
(3) Calcining the mixed powder to obtain the octahedral lithium manganate.
According to a second aspect of the present application, there is provided an octahedral lithium manganate. The morphology of the lithium manganate is octahedral, the octahedral crystal form is perfect, the electrochemical performance is excellent, and the cycle stability is improved.
The octahedral lithium manganate prepared by the preparation method is of a pure-phase spinel structure.
Optionally, the octahedral lithium manganate has a particle size of 0.5-2 μm.
According to a third aspect of the present application there is provided the use of an octahedral lithium manganate as a positive electrode material. The octahedral lithium manganate positive electrode material has a pure-phase spinel structure, a compact and stable (111) crystal face is exposed to the greatest extent, dissolution of manganese in a circulation process is inhibited, and long-term circulation stability of a water-based battery is improved.
The octahedral lithium manganate prepared by the preparation method is applied as a positive electrode material.
According to a fourth aspect of the present application, there is provided the use of octahedral lithium manganate in an aqueous battery. The octahedral lithium manganate is used as a positive electrode material in an aqueous battery.
The octahedral lithium manganate prepared by the preparation method is applied to a water-based battery.
Optionally, the capacity retention rate of the water-based battery is greater than or equal to 95% after 500 cycles when the current density is 1000 mA/g.
Optionally, the octahedral lithium manganate positive electrode material is prepared by mixing 2.5M Li 2 SO 4 The specific capacity of the aqueous solution was 121mAh/g at a current density of 100 mA/g.
In this application, "room temperature" means 25.+ -. 5 ℃.
The beneficial effects that this application can produce include:
1) The preparation method of the octahedral lithium manganate provided by the application is simple in preparation process, convenient to operate and easy to realize large-scale production.
2) According to the preparation method of the octahedral lithium manganate, the prepared octahedral lithium manganate is of a pure-phase spinel structure, a compact and stable (111) crystal face is exposed to the greatest extent, the octahedral lithium manganate is used as a positive electrode material for a water-based battery, electrochemical performance is excellent, dissolution of manganese in a circulating process is inhibited, and long-term circulating stability of the water-based battery is improved.
Drawings
Fig. 1 is an X-ray powder diffraction pattern (XRD) of octahedral lithium manganate prepared in example 2.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of the octahedral lithium manganate prepared in example 4.
Fig. 3 is a first charge-discharge curve of the octahedral lithium manganate prepared in example 7 applied as a positive electrode material in a water-based battery at a current of 100 mA/g.
Fig. 4 is a charge-discharge cycle curve of the octahedral lithium manganate prepared in example 9 applied to a water-based battery as a positive electrode material under a current of 1000 mA/g.
Fig. 5 is a Scanning Electron Microscope (SEM) photograph of the lithium manganate prepared in comparative example 1.
Fig. 6 is a Scanning Electron Microscope (SEM) photograph of the lithium manganate prepared in comparative example 2.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all materials used in the examples of this application were purchased commercially, and unless otherwise indicated, all conventional methods were used for testing, and all manufacturer-recommended settings were used for instrument settings.
The analytical method in the examples of the present application is as follows:
the structural characteristics of the sample were analyzed by X-ray diffraction (XRD) test, the model of the analyzer was D/MAX-2500, japanese science, the test conditions were 10V, 300mA current, and the scanning speed was 5 degrees/min.
The topographical features of the samples were analyzed by Scanning Electron Microscope (SEM) testing, analytical instrument model number NanoSEM 430, FEI company, usa.
In the examples, the room temperature is in particular 25 ℃.
In the examples, rpm means revolutions per minute.
Example 1:
respectively weighing manganese chloride and potassium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of potassium carbonate is prepared into a 1mol/L potassium carbonate aqueous solution (marked as B solution), the B solution is pumped into the A solution at a speed of 1rpm under the continuous stirring of 10 ℃, and after the reaction is completed, the filtration is carried out, and the vacuum drying is carried out at 70 ℃ for 12 hours, so as to obtain manganese carbonate precursor powder;
the molar ratio of LiCl to manganese carbonate is 1:2. Adding 1mol of LiCl into an orientation agent polyvinylpyrrolidone (PVP) with the dosage of 0.05 mol, adding water to prepare a solution C, adding 1mol/L of LiCl into the solution C, adding manganese carbonate precursor powder (2 mol of manganese carbonate precursor), stirring, evaporating to dryness, and vacuum-drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 8 hours at 550 ℃ in an air atmosphere, wherein the heating speed is 1 DEG/min, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 2:
respectively weighing manganese chloride and potassium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of potassium carbonate is prepared into a 1mol/L potassium carbonate aqueous solution (marked as B solution), the B solution is pumped into the A solution at a speed of 1rpm under the continuous stirring of 10 ℃, and after the reaction is completed, the filtration is carried out, and the vacuum drying is carried out at 70 ℃ for 12 hours, so as to obtain manganese carbonate precursor powder;
the molar ratio of LiCl to manganese carbonate is 1.05:2. Adding 1.05 mol of LiCl into 0.05 mol of polyvinylpyrrolidone (PVP) serving as an orientation agent, adding water to prepare a solution C, adding 1mol/L of LiCl into the solution C, adding manganese carbonate precursor powder (2 mol of manganese carbonate precursor), stirring, evaporating to dryness, and vacuum-drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 8 hours at 550 ℃ in an air atmosphere, wherein the heating speed is 1 DEG/min, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 3:
respectively weighing manganese chloride and potassium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of potassium carbonate is prepared into a 1mol/L potassium carbonate aqueous solution (marked as B solution), the B solution is pumped into the A solution at a speed of 1rpm under the continuous stirring of 10 ℃, and after the reaction is completed, the filtration is carried out, and the vacuum drying is carried out at 70 ℃ for 12 hours, so as to obtain manganese carbonate precursor powder;
the molar ratio of LiCl to manganese carbonate is 1.2:2. Adding 1.2mol of LiCl into 0.05 mol of polyvinylpyrrolidone (PVP) serving as an orientation agent, adding water into the mixture to prepare a solution C, adding manganese carbonate precursor powder (2 mol of manganese carbonate precursor) into the solution C, stirring, evaporating to dryness, and vacuum-drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 8 hours at 550 ℃ in an air atmosphere, wherein the heating speed is 1 DEG/min, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 4:
respectively weighing manganese chloride and sodium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of sodium carbonate is prepared into a 1mol/L sodium carbonate aqueous solution (marked as B solution), B is pumped into A at a speed of 100rpm under continuous stirring at 10 ℃, filtering is carried out after the reaction is completed, and vacuum drying is carried out at 70 ℃ for 12 hours to obtain manganese carbonate precursor powder;
LiCl and manganese carbonate are weighed according to the mol ratio of 1.05:2.2. Adding 1.05 mol of LiCl into 1.05 mol of sodium dodecyl sulfonate serving as an orientation agent, adding water into the mixture to prepare a solution C, wherein the molar concentration of LiCl in the solution C is 1mol/L, adding manganese carbonate precursor powder (2.2 mol of manganese carbonate precursor powder), stirring, evaporating to dryness, and vacuum drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 8 hours at 850 ℃ in an air atmosphere, wherein the heating speed is 1 DEG/min, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 5:
respectively weighing manganese chloride and sodium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of sodium carbonate is prepared into a 1mol/L sodium carbonate aqueous solution (marked as B solution), B is pumped into A at a speed of 1rpm under continuous stirring at 70 ℃, filtering is carried out after the reaction is completed, and vacuum drying is carried out at 70 ℃ for 12 hours to obtain manganese carbonate precursor powder;
LiOH and manganese carbonate are weighed according to the mol ratio of 1.05:2. Adding 1.05 mol of LiCl into the solution, adding 0.05 mol of ammonium fluoride serving as an orientation agent, preparing a solution C, adding 1mol/L of LiCl into the solution C, adding 2mol of manganese carbonate precursor powder, stirring, evaporating to dryness, and vacuum-drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 12 hours at 750 ℃ in an air atmosphere, wherein the heating speed is 10 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 6:
respectively weighing manganese acetate and ammonium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese acetate is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of ammonium carbonate is prepared into a 1mol/L ammonium carbonate aqueous solution (marked as B solution), B is pumped into A at a speed of 100rpm under continuous stirring at 20 ℃, filtering is carried out after the reaction is completed, and vacuum drying is carried out at 70 ℃ for 12 hours to obtain manganese carbonate precursor powder;
Li 2 CO 3 weighing the mixture and manganese carbonate in a molar ratio of 1.05:2. Li (Li) 2 CO 3 The dosage is 0.525 mole, the orientation agent ammonium chloride is introduced, the dosage is 0.05 mole, and the solution C is prepared 2 CO 3 Is introduced at a molar concentration of 1mol/LManganese carbonate precursor powder (the dosage of the manganese carbonate precursor powder is 2 mol), stirring, evaporating to dryness, and vacuum drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder at 650 ℃ for 12 hours in an air atmosphere, wherein the temperature rising speed is 5 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 7:
respectively weighing manganese chloride and ammonium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of ammonium carbonate is prepared into a 1mol/L ammonium carbonate aqueous solution (marked as B solution), B is pumped into A at a speed of 50rpm under continuous stirring at 40 ℃, filtering is carried out after the reaction is completed, and the manganese carbonate precursor powder is obtained after vacuum drying at 70 ℃ for 12 hours;
LiOH and manganese carbonate are weighed according to the mol ratio of 1.1:2.4. Adding 1.1mol of LiOH, adding 0.1 mol of sodium dodecyl sulfonate serving as an orientation agent, adding water to prepare a solution C, adding 1mol/L of LiOH in the solution C, adding manganese carbonate precursor powder (2.4 mol of manganese carbonate precursor), stirring, evaporating to dryness, and vacuum-drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 4 hours at 650 ℃ in an air atmosphere, wherein the temperature rising speed is 3 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 8:
respectively weighing manganese nitrate and ammonium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese nitrate is prepared into a 1mol/L manganese nitrate aqueous solution (marked as A solution), 3.6 moles of ammonium carbonate is prepared into a 1mol/L ammonium carbonate aqueous solution (marked as B solution), B is pumped into A at a speed of 50rpm under continuous stirring at 70 ℃, filtering is carried out after the reaction is completed, and vacuum drying is carried out at 70 ℃ for 12 hours to obtain manganese carbonate precursor powder;
weighing LiOH and manganese carbonate according to a molar ratio of 1.05:2, wherein the dosage of LiOH is 1.05 mol, introducing an orientation agent ammonium fluoride, wherein the dosage is 0.1 mol, adding water to prepare a solution C, wherein the molar concentration of LiOH in the solution C is 1mol/L, introducing manganese carbonate precursor powder (the dosage of manganese carbonate precursor is 2 mol), stirring, evaporating to dryness, and vacuum drying at 70 ℃ for 12h to obtain mixed powder;
calcining the mixed powder for 4 hours at 800 ℃ in an air atmosphere, wherein the heating speed is 8 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 9:
respectively weighing manganese chloride and ammonium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese nitrate aqueous solution (marked as A solution), 3.6 moles of ammonium carbonate is prepared into a 1mol/L ammonium carbonate aqueous solution (marked as B solution), B is pumped into A at a speed of 50rpm under continuous stirring at 30 ℃, filtering is carried out after the reaction is completed, and the manganese carbonate precursor powder is obtained after vacuum drying at 70 ℃ for 12 hours;
Li 2 CO 3 weighing the mixture and manganese carbonate according to a molar ratio of 1.05:2, and carrying out Li 2 CO 3 Adding water to prepare solution C with the dosage of 0.525 mol, introducing an orientation agent of ammonium chloride with the dosage of 0.1 mol, and adding Li into the solution C 2 CO 3 Introducing manganese carbonate precursor powder (the dosage of the manganese carbonate precursor is 2 mol) into the mixture, stirring, evaporating to dryness, and vacuum-drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 8 hours at 800 ℃ in an air atmosphere, wherein the heating speed is 8 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 10:
respectively weighing manganese fluoride and potassium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese fluoride is prepared into a 1mol/L manganese fluoride aqueous solution (marked as A solution), 3.6 moles of potassium carbonate is prepared into a 1mol/L potassium carbonate aqueous solution (marked as B solution), B is pumped into A at a speed of 50rpm under continuous stirring at 70 ℃, filtering is carried out after the reaction is completed, and vacuum drying is carried out at 70 ℃ for 12 hours to obtain manganese carbonate precursor powder;
Li 2 CO 3 weighing the manganese carbonate according to the mol ratio of 1.05:2. Li (Li) 2 CO 3 In an amount of 0.525 mol, the orientation agent ammonium chloride and sodium dodecyl sulfonate were introduced in a total amount of 0.05 mol (wherein the amount of ammonium chloride was 0.03 mol, dodecaneSodium sulfonate 0.02 mol), adding water to prepare solution C, wherein Li is 2 CO 3 Introducing manganese carbonate precursor powder (the dosage of the manganese carbonate precursor is 2 mol) into the mixture, stirring, evaporating to dryness, and vacuum-drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 8 hours at 800 ℃ in an air atmosphere, wherein the heating speed is 8 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 11:
respectively weighing manganese chloride and potassium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of potassium carbonate is prepared into a 1mol/L potassium carbonate aqueous solution (marked as B solution), B is pumped into A at a speed of 50rpm under continuous stirring at 70 ℃, filtering is carried out after the reaction is completed, and vacuum drying is carried out at 70 ℃ for 12 hours to obtain manganese carbonate precursor powder;
Li 2 CO 3 weighing the mixture and manganese carbonate according to a molar ratio of 1.05:2, and carrying out Li 2 CO 3 The amount of the solution is 0.525 mol, the total amount of the added orientation agent ammonium fluoride and sodium dodecyl sulfonate is 0.05 mol (wherein the amount of the ammonium fluoride is 0.03 mol and the amount of the sodium dodecyl sulfonate is 0.02 mol), and the solution C is prepared by adding water 2 CO 3 Introducing manganese carbonate precursor powder (the dosage of the manganese carbonate precursor is 2 mol) into the mixture, stirring, evaporating to dryness, and vacuum-drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 8 hours at 750 ℃ in an air atmosphere, wherein the heating speed is 2 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 12:
respectively weighing manganese chloride and potassium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of potassium carbonate is prepared into a 1mol/L potassium carbonate aqueous solution (marked as B solution), B is pumped into A at a speed of 50rpm under continuous stirring at 70 ℃, filtering is carried out after the reaction is completed, and vacuum drying is carried out at 70 ℃ for 12 hours to obtain manganese carbonate precursor powder;
LiCl and manganese carbonate are weighed according to the mol ratio of 1.05:2. Adding 1.05 mol of LiCl into 1.1mol of ammonium chloride and PVP serving as orientation agents, preparing a solution C with the total amount of 0.1 mol of ammonium chloride and 0.05 mol of PVP, wherein the molar concentration of LiCl in the solution C is 1mol/L, adding manganese carbonate precursor powder (with 2mol of manganese carbonate precursor), stirring, evaporating to dryness, and vacuum drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 6 hours at 750 ℃ in an air atmosphere, wherein the heating speed is 8 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 13:
respectively weighing manganese chloride and potassium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of potassium carbonate is prepared into a 1mol/L potassium carbonate aqueous solution (marked as B solution), B is pumped into the A solution at a speed of 10rpm under continuous stirring at 30 ℃, filtering is carried out after the reaction is completed, and vacuum drying is carried out at 70 ℃ for 12 hours, so as to obtain manganese carbonate precursor powder;
LiCl and manganese carbonate are weighed according to the mol ratio of 1.05:2. Adding 1.05 mol of LiCl, introducing sodium dodecyl sulfonate and PVP serving as orientation agents, wherein the total dosage is 0.1 mol (wherein the dosage of sodium dodecyl sulfonate is 0.05 mol and the dosage of PVP is 0.05 mol), adding water to prepare a solution C, wherein the molar concentration of LiCl in the solution C is 1mol/L, introducing manganese carbonate precursor powder (the dosage of manganese carbonate precursor is 2 mol), stirring, evaporating to dryness, and vacuum drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder at 650 ℃ for 6 hours in an air atmosphere, wherein the temperature rising speed is 5 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 14:
respectively weighing manganese chloride and potassium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of potassium carbonate is prepared into a 1mol/L potassium carbonate aqueous solution (marked as B solution), B is pumped into the A solution at a speed of 10rpm under continuous stirring at 30 ℃, filtering is carried out after the reaction is completed, and vacuum drying is carried out at 70 ℃ for 12 hours, so as to obtain manganese carbonate precursor powder;
LiCl and Li 2 CO 3 The mixed lithium salt and manganese carbonate of the formula (I) are weighed according to the mol ratio of 1.05:2, the LiCl dosage is 0.525 mol and Li is as follows 2 CO 3 The amount of the catalyst was 0.2625 mol, and the amount of the orientation agent sodium dodecyl sulfate and ammonium chloride introduced was 0.05 mol (wherein the amount of sodium dodecyl sulfate was 0.02 mol, and the amount of ammonium chloride was 0.03 mol), to prepare a solution C in which LiCl and Li were contained 2 CO 3 The molar concentration of (2) was 1mol/L. Introducing manganese carbonate precursor powder (the dosage of the manganese carbonate precursor is 2 mol), stirring, evaporating to dryness, and vacuum drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 8 hours at 650 ℃ in an air atmosphere, wherein the temperature rising speed is 5 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 15:
respectively weighing manganese chloride and potassium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of potassium carbonate is prepared into a 1mol/L potassium carbonate aqueous solution (marked as B solution), the B solution is pumped into the A solution at a speed of 10rpm under continuous stirring at 30 ℃, filtering is carried out after the reaction is completed, and the manganese carbonate precursor powder is obtained by vacuum drying at 70 ℃ for 12 hours;
LiOH and Li 2 CO 3 The mixed lithium salt and manganese carbonate are weighed according to the mol ratio of 1.05:2, the LiOH consumption is 0.525 mol and Li is as follows 2 CO 3 The amount of the catalyst was 0.2625 mol, the orientation agent sodium dodecyl sulfate and ammonium chloride were introduced in an amount of 0.05 mol (wherein the amount of sodium dodecyl sulfate was 0.02 mol, and the amount of ammonium chloride was 0.03 mol), and water was added to prepare a solution C in which LiCl and Li were contained 2 CO 3 Introducing manganese carbonate precursor powder (the dosage of the manganese carbonate precursor is 2 mol) into the mixture, stirring, evaporating to dryness, and vacuum-drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 8 hours at 650 ℃ in an air atmosphere, wherein the temperature rising speed is 5 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 16:
respectively weighing manganese chloride and potassium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of potassium carbonate is prepared into a 1mol/L potassium carbonate aqueous solution (marked as B solution), the B solution is pumped into the A solution at a speed of 10rpm under continuous stirring at 50 ℃, filtering is carried out after the reaction is completed, and the manganese carbonate precursor powder is obtained by vacuum drying at 70 ℃ for 12 hours;
weighing mixed lithium salt of LiCl and LiOH and manganese carbonate according to the molar ratio of 1.05:2, wherein the use amount of LiOH is 0.525 mole and the use amount of LiOH is 0.525 mole, introducing orientation agents of sodium dodecyl sulfate and ammonium chloride, wherein the use amount of sodium dodecyl sulfate is 0.05 mole and the use amount of ammonium chloride is 0.05 mole, preparing a solution C, wherein the molar concentration of LiCl and LiOH in the solution C is 1 mole/L, introducing manganese carbonate precursor powder (the use amount of manganese carbonate precursor is 2 mole), stirring, evaporating to dryness, and vacuum drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 8 hours at 650 ℃ in an air atmosphere, wherein the temperature rising speed is 5 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 17:
respectively weighing manganese chloride and potassium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of potassium carbonate is prepared into a 1mol/L potassium carbonate aqueous solution (marked as B solution), the B solution is pumped into the A solution at a speed of 1rpm under continuous stirring at 60 ℃, filtering is carried out after the reaction is completed, and the manganese carbonate precursor powder is obtained by vacuum drying at 70 ℃ for 12 hours;
the molar ratio of LiCl to manganese carbonate is 1.05:2. Adding 1.05 mol of LiCl into 0.05 mol of polyvinylpyrrolidone (PVP) serving as an orientation agent, adding water to prepare a solution C, adding 1mol/L of LiCl into the solution C, adding manganese carbonate precursor powder (2 mol of manganese carbonate precursor), stirring, evaporating to dryness, and vacuum-drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 12 hours at 550 ℃ in an air atmosphere, wherein the heating speed is 1 DEG/min, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 18:
respectively weighing manganese acetate and ammonium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese acetate is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of ammonium carbonate is prepared into a 1mol/L ammonium carbonate aqueous solution (marked as B solution), B is pumped into A at a speed of 100rpm under continuous stirring at 20 ℃, filtering is carried out after the reaction is completed, and vacuum drying is carried out at 70 ℃ for 12 hours to obtain manganese carbonate precursor powder;
Li 2 CO 3 weighing the mixture and manganese carbonate in a molar ratio of 1.05:2. Li (Li) 2 CO 3 The dosage is 0.525 mole, the orientation agent ammonium chloride is introduced, the dosage is 0.05 mole, and the solution C is prepared 2 CO 3 Introducing manganese carbonate precursor powder (the dosage of the manganese carbonate precursor powder is 2 mol) into the mixture, stirring, evaporating the mixture to dryness, and carrying out vacuum drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder at 650 ℃ for 6 hours in an air atmosphere, wherein the temperature rising speed is 5 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 19:
respectively weighing manganese chloride and ammonium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese nitrate aqueous solution (marked as A solution), 3.6 moles of ammonium carbonate is prepared into a 1mol/L ammonium carbonate aqueous solution (marked as B solution), B is pumped into A at a speed of 50rpm under continuous stirring at 30 ℃, filtering is carried out after the reaction is completed, and the manganese carbonate precursor powder is obtained after vacuum drying at 70 ℃ for 12 hours;
Li 2 CO 3 weighing the mixture and manganese carbonate according to a molar ratio of 1.05:2, and carrying out Li 2 CO 3 Adding water to prepare solution C with the dosage of 0.525 mol, introducing an orientation agent of ammonium chloride with the dosage of 0.1 mol, and adding Li into the solution C 2 CO 3 The molar concentration of (1) mol/L, introducing manganese carbonate precursor powder (the dosage of the manganese carbonate precursor is 2 mol), stirring,evaporating to dryness, and vacuum drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 12 hours at 800 ℃ in an air atmosphere, wherein the heating speed is 8 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 20:
respectively weighing manganese chloride and potassium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of potassium carbonate is prepared into a 1mol/L potassium carbonate aqueous solution (marked as B solution), B is pumped into the A solution at a speed of 10rpm under continuous stirring at 30 ℃, filtering is carried out after the reaction is completed, and vacuum drying is carried out at 70 ℃ for 12 hours, so as to obtain manganese carbonate precursor powder;
LiCl and manganese carbonate are weighed according to the mol ratio of 1.05:2. Adding 1.05 mol of LiCl, introducing sodium dodecyl sulfonate and PVP serving as orientation agents, wherein the total dosage is 0.1 mol (wherein the dosage of sodium dodecyl sulfonate is 0.05 mol and the dosage of PVP is 0.05 mol), adding water to prepare a solution C, wherein the molar concentration of LiCl in the solution C is 1mol/L, introducing manganese carbonate precursor powder (the dosage of manganese carbonate precursor is 2 mol), stirring, evaporating to dryness, and vacuum drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder at 650 ℃ for 12 hours in an air atmosphere, wherein the temperature rising speed is 10 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 21:
respectively weighing manganese chloride and ammonium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese nitrate aqueous solution (marked as A solution), 3.6 moles of ammonium carbonate is prepared into a 1mol/L ammonium carbonate aqueous solution (marked as B solution), B is pumped into A at a speed of 50rpm under continuous stirring at 30 ℃, filtering is carried out after the reaction is completed, and the manganese carbonate precursor powder is obtained after vacuum drying at 70 ℃ for 12 hours;
Li 2 CO 3 weighing the mixture and manganese carbonate according to a molar ratio of 1.05:2, and carrying out Li 2 CO 3 Adding water to prepare solution C with the dosage of 0.525 mol, introducing an orientation agent of ammonium chloride with the dosage of 0.1 mol, and adding Li into the solution C 2 CO 3 Introducing manganese carbonate precursor powder (the dosage of the manganese carbonate precursor is 2 mol) into the mixture, stirring, evaporating to dryness, and vacuum-drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 12 hours at 800 ℃ in an oxygen atmosphere, wherein the temperature rising speed is 5 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 22:
respectively weighing manganese chloride and potassium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of potassium carbonate is prepared into a 1mol/L potassium carbonate aqueous solution (marked as B solution), the B solution is pumped into the A solution at a speed of 1rpm under continuous stirring at 60 ℃, filtering is carried out after the reaction is completed, and the manganese carbonate precursor powder is obtained by vacuum drying at 70 ℃ for 12 hours;
the molar ratio of LiCl to manganese carbonate is 1.05:2. Adding 1.05 mol of LiCl into 0.05 mol of polyvinylpyrrolidone (PVP) serving as an orientation agent, adding water to prepare a solution C, adding 1mol/L of LiCl into the solution C, adding manganese carbonate precursor powder (2 mol of manganese carbonate precursor), stirring, evaporating to dryness, and vacuum-drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 12 hours at 550 ℃ in an air atmosphere, wherein the heating speed is 1 DEG/min, and then cooling to room temperature along with a furnace to obtain the octahedral lithium manganate.
Example 23:
x-ray powder diffraction (XRD) analysis is carried out on the octahedral lithium manganate prepared in the above example, and the XRD test chart of the octahedral lithium manganate prepared in example 2 is shown in figure 1, so that the obtained octahedral lithium manganate has high crystallinity, does not contain any impurity phase, and has a pure-phase spinel structure.
Example 24:
scanning Electron Microscope (SEM) analysis is carried out on the octahedral lithium manganate prepared in the above example, and the SEM photograph of the octahedral lithium manganate prepared in example 4 is shown in FIG. 2, so that the obtained octahedral lithium manganate is a perfect octahedral crystal form and has a particle size of 0.5-2 μm.
Example 25:
the octahedral lithium manganate prepared in the above example is applied to a water-based battery as a positive electrode material.
Electrode preparation and battery assembly:
in the positive electrode sheet, an active material: acetylene black: the mass ratio of PTFE is 8:1:1, and the active material in the positive electrode is the octahedral lithium manganate prepared by the above example; in the negative electrode sheet, active material: acetylene black: the mass ratio of PTFE is 6:3:1, and polyimide is selected as an active material in the negative electrode. Wherein ethanol is used as a cosolvent in the preparation process of the pole piece. The current collector is a 200-mesh stainless steel net, and the electrolyte is 2.5M Li 2 SO 4 The solution, glass fiber membrane, served as separator. The mass ratio of the positive plate to the negative plate is 1:1.5. Battery performance was tested in CR2032 coin cells.
The octahedral lithium manganate prepared in example 7 is typically used as an active material in a positive electrode, and is assembled into a water-based battery according to the above method. The first charge-discharge curve of the material at 100mA/g current is shown in figure 3, and the discharge mass specific capacity is 121mAh g -1 。
An octahedral lithium manganate prepared in example 9 is typically used as an active material in a positive electrode, and is assembled into a water-based battery according to the above method. The charge-discharge cycle curve at 1000mA/g current is shown in FIG. 4, and the specific capacity of the initial discharge mass is 74mAh g -1 After 500 cycles, the mass specific capacity was 71mAh g -1 The capacity retention rate is as high as 95%.
It can be seen that the octahedral lithium manganate has good long-term cycling stability as a positive electrode material of the water-based battery.
Comparative example 1:
respectively weighing manganese acetate and ammonium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese acetate is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of ammonium carbonate is prepared into a 1mol/L ammonium carbonate aqueous solution (marked as B solution), B is pumped into A at a speed of 10rpm under continuous stirring at 20 ℃, filtering is carried out after the reaction is completed, and vacuum drying is carried out at 70 ℃ for 12 hours to obtain manganese carbonate precursor powder;
Li 2 CO 3 weighing the mixture and manganese carbonate in a molar ratio of 1.05:2. Li (Li) 2 CO 3 The dosage is 0.525 mol, and is prepared into solution C, wherein Li is as follows 2 CO 3 Introducing manganese carbonate precursor powder (the dosage of the manganese carbonate precursor powder is 2 mol) into the mixture, stirring, evaporating the mixture to dryness, and carrying out vacuum drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 8 hours at 650 ℃ in an air atmosphere, wherein the temperature rising speed is 5 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the non-octahedral lithium manganate. Fig. 5 is a Scanning Electron Microscope (SEM) analysis picture thereof, and it can be seen that the non-octahedral lithium manganate is obtained without introducing an alignment agent.
Comparative example 2:
respectively weighing manganese chloride and potassium carbonate according to a molar ratio of 1:1.2, wherein 3 moles of manganese chloride is prepared into a 1mol/L manganese chloride aqueous solution (marked as A solution), 3.6 moles of potassium carbonate is prepared into a 1mol/L potassium carbonate aqueous solution (marked as B solution), the B solution is pumped into the A solution at a speed of 1rpm under the continuous stirring of 10 ℃, and after the reaction is completed, the filtration is carried out, and the vacuum drying is carried out at 70 ℃ for 12 hours, so as to obtain manganese carbonate precursor powder;
the molar ratio of LiCl to manganese carbonate is 1.05:2. Adding 1.05 mol of LiCl into 0.05 mol of polyvinylpyrrolidone (PVP) serving as an orientation agent, adding water to prepare a solution C, adding 1mol/L of LiCl into the solution C, adding manganese carbonate precursor powder (2 mol of manganese carbonate precursor), stirring, evaporating to dryness, and vacuum-drying at 70 ℃ for 12 hours to obtain mixed powder;
calcining the mixed powder for 8 hours at 900 ℃ in an air atmosphere, wherein the heating speed is 10 ℃ per minute, and then cooling to room temperature along with a furnace to obtain the non-octahedral lithium manganate. Fig. 6 is a Scanning Electron Microscope (SEM) analysis picture thereof, and it can be seen that the firing temperature was too high, and non-octahedral lithium manganate was obtained.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (6)

1. The preparation method of the octahedral lithium manganate is characterized by drying a mixed solution containing lithium salt, manganese carbonate and an orientation agent to obtain mixed powder, calcining and cooling to obtain the octahedral lithium manganate;
the molar ratio of the lithium salt to the manganese carbonate to the orientation agent is 1-1.2:2-2.4:0.05-0.1;
the orientation agent is at least one selected from sodium dodecyl sulfonate, polyvinylpyrrolidone, ammonium fluoride and ammonium chloride;
the conditions of the calcination are as follows: in the atmosphere of oxygen-containing gas, the temperature rising speed is 1-10 ℃/min, the temperature is 550-850 ℃ and the time is 4-12 h;
the preparation method of the manganese carbonate comprises the following steps: mixing the solution A containing manganese salt and the solution B containing carbonate, reacting, and drying to obtain manganese carbonate;
in the solution A containing manganese salt, the manganese salt is selected from at least one of manganese chloride, manganese fluoride, manganese nitrate and manganese acetate;
in the solution B containing carbonate, the carbonate is at least one selected from sodium carbonate, potassium carbonate and ammonium carbonate.
2. The method of claim 1, wherein the lithium salt is selected from LiCl, liOH, li 2 CO 3 At least one of them.
3. The octahedral lithium manganate prepared by the preparation method according to any one of claims 1-2, wherein the octahedral lithium manganate has a pure-phase spinel structure;
the particle size of the octahedral lithium manganate is 0.5-2 mu m.
4. The use of the octahedral lithium manganate prepared by the preparation method of any one of claims 1-2 as a positive electrode material.
5. The use of the octahedral lithium manganate prepared by the preparation method of any one of claims 1-2 in an aqueous battery.
6. The use according to claim 5, wherein the capacity retention rate of the aqueous battery after 500 cycles is 95% or more at a current density of 1000 mA/g.
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