CN110697797B - Preparation method and application of hollow carbonate precursor - Google Patents
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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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Abstract
The invention discloses a preparation method of a hollow carbonate precursor, which comprises the following steps: 1) mixing a metal salt solution with a surfactant to obtain a solution A, wherein metal elements in the metal salt solution comprise nickel and manganese; 2) adding a precipitant into the solution A, and performing hydrothermal reaction at the temperature of 150-; 3) and after the hydrothermal reaction is finished, filtering, washing, filtering and drying the obtained solid precipitate to obtain the hollow carbonate precursor. According to the invention, the hollow carbonate precursor can be directly obtained by a hydrothermal method, the prepared precursor has uniform particle size, and the synthesized material has good consistency. The hollow carbonate precursor prepared by the preparation method can be used for further mixing lithium to prepare the lithium battery anode material, and has the advantages of excellent cycle stability and rate capability.
Description
Technical Field
The invention relates to the field of chemistry and chemical engineering, in particular to a method for preparing a hollow carbonate precursor and application thereof.
Background
The lithium ion battery anode material has higher energy density and better stability, and can be applied to new energy automobiles or 3C batteries. For the lithium battery positive electrode material, the particle size has a large influence on the electrochemical performance of the material. Generally speaking, the particle size is large, the corrosion degree of the material body by the electrolyte is low, and the cycle performance of the material is good. But the corresponding electrochemical polarization is also large, and the large-current charge and discharge performance of the material is poor. The particle size is small, the rate performance of the material is good, but the surface free energy of the small particles is higher, the side reaction with the electrolyte is easy to occur, and the cycle performance of the material is poor. How to control the particle size and balance the relationship between the particle size and the particle size has not been good.
The chemical migration of lithium ions in the solid crystal lattice is the speed control in the charge and discharge process, and the hollow structure can shorten the transmission path of the lithium ions in the material, effectively reduce the electrochemical polarization in the charge and discharge process and improve the electrochemical performance of the lithium ion anode material.
The patent CN105185979A discloses a preparation method of a hollow-structured lithium ion battery anode material, which comprises the steps of preparing more than one of nickel salt, cobalt salt and manganese salt into a metal salt solution by using a coprecipitation method, adding a complexing agent into a reaction kettle, carrying out coprecipitation by adopting a mode of controlling the reaction temperature, the reaction time and the reaction pH value in sections to obtain a precursor with a loose core and a compact shell, finally uniformly mixing the precursor and a lithium source according to the molar ratio of the total metal content in the precursor to the lithium element being 1 (0.9-2.2), and then assisting a section temperature control calcination process to obtain the hollow-structured lithium ion battery anode material. The hollow structure is mainly manufactured by utilizing the kirkendall effect in the temperature rising process, and the generation of complete crystal lattices is not facilitated due to the excessively high temperature rising speed.
Patent CN104953110A discloses a preparation method of a lithium-rich manganese-based cathode material with a hollow structure, which has electrochemical properties superior to those of conventional small-particle and large-particle size cathode materials, but the preparation process is complicated and has high requirements on equipment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a hollow-structure positive electrode material for a lithium ion battery.
The first purpose of the invention is to provide a method for preparing a hollow carbonate precursor, which is beneficial to preparing a lithium ion battery anode material with high energy density and long cycle life.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a hollow carbonate precursor comprises the following steps: mixing a solution containing metal ions such as nickel, cobalt, manganese and the like in a solution containing a surfactant, carrying out hydrothermal reaction for a certain time together with a reactant capable of generating carbonate through pyrolysis to generate a carbonate precursor with a hollow structure, wherein the structural schematic diagram is shown in figure 1. The specific operation steps are as follows:
1) mixing a metal salt solution with a surfactant to obtain a solution A, wherein metal elements in the metal salt solution comprise nickel and manganese;
2) adding a precipitant into the solution A, and then carrying out hydrothermal reaction at the temperature of 150 ℃ and 240 ℃, wherein the precipitant is one or the combination of two of urea and Hexamethylenetetramine (HMT);
3) and after the hydrothermal reaction is finished, filtering, washing, filtering and drying the obtained solid precipitate to obtain the hollow carbonate precursor.
In the above preparation method, preferably, in the step 1), the metal element in the metal salt solution includes M, where M represents one or more of cobalt, aluminum, titanium, chromium, vanadium, tin, zirconium, iron, boron, and a rare earth element; the metal salt is sulfate, chloride or acetate.
In the above preparation method, preferably, the surfactant is one or more of polyethylene glycol, sodium lactate and dimethylformamide.
In the preparation method, the time of the hydrothermal reaction is preferably 10-36 h.
In the above preparation method, preferably, the molar ratio of nickel to manganese in the metal salt solution is 1: (0.5-8).
In the preparation method, the temperature of the hydrothermal reaction is preferably 170-210 ℃ and the time is 18-35 h.
As a general inventive concept, the invention also provides an application of the hollow carbonate precursor in preparing the anode material of the lithium ion and sodium ion battery.
Compared with the prior art, the invention has the advantages that:
according to the invention, the hollow carbonate precursor can be directly obtained by a hydrothermal method, the prepared precursor has uniform particle size, and the synthesized material has good consistency. The hollow carbonate precursor prepared by the preparation method can be used for further mixing lithium to prepare the lithium battery anode material, and has the advantages of excellent cycle stability and rate capability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic structural view of a hollow carbonate precursor according to the present invention.
Fig. 2 is a scanning electron microscope image of the hollow carbonate precursor prepared in example 1 of the present invention.
Fig. 3 is a cycle performance diagram of the cathode material obtained in example 2 of the present invention and the cathode material prepared by the conventional method in a voltage range of 2.0 to 4.6V.
Fig. 4 is an XRD diffractogram of the positive electrode material obtained in example 2 of the present invention.
FIG. 5 is a scanning electron micrograph of a section of the precursor obtained in example 3 of the present invention.
FIG. 6 is a graph showing the distribution of the particle size of the precursor obtained in example 4 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a preparation method of a hollow carbonate precursor comprises the following steps:
weighing nickel chloride hexahydrate, cobalt chloride hexahydrate and manganese chloride tetrahydrate according to the molar ratio of 13:13:54, stirring, adding water for dissolution, adding sodium lactate as a surfactant with the volume of 1/2 to form a uniform solution, adding ammonium bicarbonate with the amount of 2.5 times of the total metal ions, heating to 180 ℃, and carrying out hydrothermal reaction for 25 hours; naturally cooling, filtering, washing with purified water and anhydrous ethanol for three times, and drying to obtain hollow Mn0.54Ni0.13Co0.13(CO3)0.8And (3) a carbonate precursor.
Fig. 2 is a scanning electron micrograph of the precursor obtained in this example.
And mixing the carbonate precursor and lithium carbonate according to the stoichiometric ratio Li/Mn of 2.22:1, and roasting at 900 ℃ for 16h to obtain the lithium-rich manganese-based cathode material. The button cell made of the obtained positive electrode material is tested for cycle performance at 1C within the voltage range of 2.0-4.6V, the first charge-discharge efficiency is 76%, the first discharge capacity is 230mAh/g, and the capacity retention rate after 100 cycles is 90.3%.
Example 2:
a preparation method of a hollow carbonate precursor comprises the following steps:
weighing nickel acetate and manganese acetate according to a molar ratio of 1:2, stirring, adding water for dissolving, adding a surfactant polyethylene glycol 600 with the volume of 1/4 of the solution to form a uniform solution, then adding urea with the amount of 3.5 times of the total metal ions, heating to 200 ℃, carrying out hydrothermal reaction for 18h, naturally cooling, filtering, washing with purified water and absolute ethyl alcohol for three times, and drying to obtain hollow Mn0.66Ni0.0.33CO3。
Mixing the carbonate precursor with lithium carbonate according to the stoichiometric ratio Li/Mn of 2.49:1, and roasting at 850 ℃ for 20h to obtain the lithium-rich manganese-based positive electrode material Li1.2Mn0.6Ni0.3CO3. Then, the product is processedCompared with a button cell prepared from a positive electrode material prepared by a traditional coprecipitation method, the button cell prepared from the lithium-rich manganese-based positive electrode material is tested for cycle performance within a voltage range of 2.0-4.6V and at 1C, as shown in figure 3, the hollow lithium-rich manganese-based positive electrode material synthesized by the method has more excellent electrochemical performance.
Fig. 4 is an XRD of the carbonate precursor synthesized in this example, which is almost identical to the conventional co-precipitated commercial precursor crystal form.
Example 3:
a preparation method of a hollow carbonate precursor comprises the following steps:
weighing nickel sulfate, cobalt sulfate and manganese sulfate according to a molar ratio of 1:1:1, stirring, adding water for dissolution, adding a surfactant dimethylformamide with a volume of 1/3 of the solution to form a uniform solution, adding hexamethylenetetramine with the amount of 1.5 times of the total metal ions, adding the hexamethylenetetramine to the uniform solution, carrying out hydrothermal reaction at 200 ℃ for 30 hours, naturally cooling, filtering, washing with purified water and absolute ethyl alcohol for three times, and drying to obtain hollow Mn0.33Ni0.33Co0.33CO3And (3) a carbonate precursor.
Fig. 5 is a scanning electron microscope image of the carbonate precursor prepared in this example. It can be seen from the figure that the obtained precursor has a distinct hollow structure, and the wall thickness is about 5 microns.
Mixing the carbonate precursor with sodium carbonate according to the stoichiometric ratio of Na/Mn to 2.22:1, and roasting at 900 ℃ for 16h to obtain NaMn0.33Ni0.33Co0.33O2. The button cell made of the obtained positive electrode material is tested for cycle performance at 1C within the voltage range of 1.5-4.0V, the first charge-discharge efficiency is 86%, the first discharge capacity is 110mAh/g, and the capacity retention rate after 100 weeks of cycle is 80.3%.
Example 4:
a preparation method of a hollow carbonate precursor comprises the following steps:
weighing nickel acetate, cobalt acetate and manganese acetate according to a molar ratio of 1:1:1, stirring, adding water for dissolution, adding a surfactant polyethylene glycol 200 with a volume of 1/3, adding hexamethylenetetramine with the amount of 2.0 times of the total metal ions when a uniform solution is formed, and heating to a temperature ofPerforming hydrothermal reaction at 210 ℃ for 20 hours, naturally cooling, filtering, washing with purified water and absolute ethyl alcohol for three times, and drying to obtain hollow Mn0.54Ni0.13Co0.13(CO3)0.8And (3) a carbonate precursor.
Fig. 6 is a distribution diagram of the particle size of the precursor obtained in the present example, and it can be seen from the figure that the particle size of the precursor obtained is relatively uniform.
Mixing the carbonate precursor with lithium hydroxide carbonate according to the ratio of Li/Mn to 2.22:1, and roasting at 900 ℃ for 20h to obtain LiMn0.33Ni0.33Co0.33O2And (3) a positive electrode material. The button cell made of the obtained positive electrode material is tested for cycle performance at 1C within the voltage range of 2.0-4.3V, the first charge-discharge efficiency is 96%, the first discharge capacity is 135mAh/g, and the capacity retention rate after 100 weeks of cycle is 97%.
Claims (6)
1. The preparation method of the hollow carbonate precursor is characterized by comprising the following steps of:
1) mixing a metal salt solution with a surfactant to obtain a solution A, wherein metal elements in the metal salt solution comprise nickel and manganese; the surfactant is one or more of polyethylene glycol, sodium lactate and dimethylformamide;
2) adding a precipitant into the solution A, and performing hydrothermal reaction at the temperature of 150-;
3) and after the hydrothermal reaction is finished, filtering, washing, filtering and drying the obtained solid precipitate to obtain the hollow carbonate precursor.
2. The preparation method according to claim 1, wherein in step 1), the metal element in the metal salt solution comprises M, wherein M represents one or more of cobalt, aluminum, titanium, chromium, vanadium, tin, zirconium, iron and rare earth elements.
3. The method according to claim 1, wherein the hydrothermal reaction is carried out for a period of time of 10 to 36 hours.
4. The method of claim 1, wherein the molar ratio of nickel to manganese in the metal salt solution is 1: (0.5-8).
5. The preparation method as claimed in claim 1, wherein the hydrothermal reaction is carried out at a temperature of 170 ℃ and a temperature of 210 ℃ for 18-35 h.
6. Use of the hollow carbonate precursor obtained by the preparation method according to any one of claims 1 to 5 in the preparation of a positive electrode material for a lithium-ion or sodium-ion battery.
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