CN110890541A - Preparation method of surface-modified lithium-rich manganese-based positive electrode material and lithium ion battery - Google Patents
Preparation method of surface-modified lithium-rich manganese-based positive electrode material and lithium ion battery Download PDFInfo
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- 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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Abstract
The invention relates to a preparation method of a surface modified lithium-rich manganese-based positive electrode material and a lithium ion battery, which comprises the following steps: step 1), uniformly mixing a raw material of a lithium-rich manganese-based positive electrode with a fast ion conductor coating solution, and carrying out solid-liquid separation to obtain a surface modified lithium-rich manganese-based positive electrode material precursor; the solute in the fast ion conductor coating liquid is selected from one or more of soluble hydrogen phosphate, pyrophosphate and metaaluminate, and the solvent is water; and 2), carrying out heat treatment on the surface modified lithium-rich manganese-based anode material precursor obtained in the step 1) to obtain the surface modified lithium-rich manganese-based anode material. The invention adopts a one-step process, achieves the dual effects of reducing the total alkali amount by coating and washing, has simple process flow and mild conditions, and is easy for batch amplification and industrial production. The total alkali amount on the surface of the modified material is obviously reduced, and the first coulombic efficiency and rate capability are greatly improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries; in particular to a preparation method of a surface modified lithium-rich manganese-based cathode material and a lithium ion battery.
Background
The endurance mileage is one of the restriction factors restricting the market popularization of the electric automobile, and the improvement of the energy density of the vehicle-mounted power battery also becomes a problem to be solved urgently in the industry. At present, the commercial lithium ion battery anode material mainly comprises a lithium cobaltate, lithium iron phosphate and a nickel-cobalt-manganese/aluminum ternary material, and the specific capacity of the current commercial high-nickel ternary material is not more than 210mAh/g, so that the improvement range of the energy density of the lithium ion battery is limited, and the requirement of an electric automobile on a power battery is difficult to meet.
Due to the advantages of high specific capacity (more than 250mAh/g), low cost and the like, a plurality of researchers think that the lithium-rich manganese-based positive electrode material is hopeful to become a preferred positive electrode material of a next-generation high-specific-energy battery. The molecular formula of the lithium-rich material can be written as xLi2MnO3·(1-x)LiMO2(M is usually a transition metal element such as Ni, Co, Mn, Cr, Fe, Ti, Mo or the like), and is Li having a monoclinic system and a layered structure2MnO3And hexagonal, layered structured LiMO2The formed solid solution-like structure. High voltage activation of Li is required for lithium-rich materials to exhibit high capacity2MnO3(> 4.5V), Li as Li during the first activation2The form of O is irreversibly removed, accompanied by oxygen release, resulting in low coulombic efficiency for the first time; the lithium-rich material has a low lithium ion diffusion coefficient, so that the rate performance is poor; transition metal ions of the lithium-rich manganese-based material migrate in the charge-discharge cycle process, and the layered structure is gradually changed into the spinel structure, so that the specific capacity and the discharge voltage are gradually attenuated. On the other hand, considering that high-temperature sintering is needed in the material preparation process, and part of lithium is volatilized in the sintering process, lithium sources with higher than stoichiometric ratio are generally added in the synthesis of the lithium-rich manganese-based material, which can lead to the synthesized lithium-rich manganese-based materialThe lithium-rich manganese-based material has high surface total alkali (residual lithium carbonate and lithium hydroxide), so that the pH value of the material is high, the problems that slurry is in a jelly state and is difficult to coat a pole piece and the like can occur in the preparation process of the battery, and the high-temperature cycle and storage performance of the battery can be influenced by the surface total alkali. These disadvantages severely restrict the commercial application of lithium-rich manganese-based positive electrode materials.
The surface coating can effectively improve the electrochemical performance of the material, and particularly, when the coating is a lithium fast ion conductor, the rate capability of the material can be greatly improved. Chen and team adopted Li3PO4The capacity retention rate of the coated lithium-rich material (J.Power Sources 341 (2017)) 147-155 is improved from the original 58% to 78% after 100 weeks of circulation, the 5C rate discharge specific capacity is obviously improved from 45mAh/g to 118mAh/g, but dopamine is polymerized on the surface of the lithium-rich material, then lithium phosphate is added, lithium phosphate cannot be formed in situ and additional lithium supplement is needed, and the problem of high total alkali amount on the surface of the lithium-rich manganese-based anode material cannot be solved although single coating modification can improve the electrochemical performance of the material.
In order to simplify the process, a multifunctional surface modification process needs to be developed, and the total alkali content of the material is reduced and the electrochemical performance is improved. Chinese patent CN104518214A discloses a preparation method of a lithium-rich solid solution cathode material, which comprises the steps of firstly reducing the total alkali content on the surface of the material through water washing treatment, and then carrying out surface modification and heat treatment on the treated intermediate product, thereby remarkably improving the cycle performance of the material. Chinese patent CN108878819A discloses a lithium ion battery anode material with a low lithium ion content on the surface and a preparation method thereof, wherein nano oxide and pure water are ultrasonically mixed, then the anode material is added, the material is obtained through filtering, drying and sintering, the residual alkali on the surface of the material is low, the cycling stability is good, the material is washed and coated in one step, but the coating uniformity is limited by the size of the nano oxide, the coating is oxide, the conductivity and lithium ion transmission performance of most oxides are poor, and the multiplying power performance of the material can be influenced after coating.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a preparation method of a surface modified lithium-rich manganese-based positive electrode material and a lithium ion battery.
One of the purposes of the invention is to provide a preparation method of a surface modified lithium-rich manganese-based positive electrode material, which comprises the following steps:
step 1), uniformly mixing a raw material of a lithium-rich manganese-based positive electrode with a fast ion conductor coating solution, and carrying out solid-liquid separation to obtain a surface modified lithium-rich manganese-based positive electrode material precursor; the solute in the fast ion conductor coating liquid is selected from one or more of soluble hydrogen phosphate, pyrophosphate and metaaluminate, and the solvent is water;
and 2), carrying out heat treatment on the surface modified lithium-rich manganese-based anode material precursor obtained in the step 1) to obtain the surface modified lithium-rich manganese-based anode material.
According to some preferred embodiments of the present invention, the solute is selected from one or more of diammonium hydrogen phosphate, sodium metaaluminate, potassium pyrophosphate and sodium pyrophosphate, and the solvent is deionized water; preferably, the solute is selected from sodium metaaluminate, potassium pyrophosphate and sodium pyrophosphate, more preferably potassium metaaluminate or sodium metaaluminate; the concentration of the fast ion conductor coating liquid is 0.01-1mol/L, preferably 0.05-0.5 mol/L.
According to some preferred embodiments of the present invention, the solute is present in a molar ratio of 1% to 10%, preferably 2% to 5%, based on the anion, to the starting material.
According to some preferred embodiments of the present invention, in step 1), the lithium-rich manganese-based positive electrode material has a general formula shown in formula (I):
xLi2MnO3·(1-x)LiMO2(I)
wherein x is more than or equal to 0.1 and less than or equal to 0.9, M is selected from one or more of Ni, Co, Mn, Cr, Fe, Ti, Mo, Ru, V, Nb, Zr and Sn, x is more than or equal to 0.2 and less than or equal to 0.5, and M at least comprises three elements of Ni, Co and Mn.
According to some preferred embodiments of the present invention, the total alkali content of the raw material of the lithium-rich manganese-based positive electrode material is not less than 0.5%, the total alkali content of the surface-modified lithium-rich manganese-based positive electrode material is less than 0.2%, and/or a fast ion conductor coating is grown in situ on the surface of the surface-modified lithium-rich manganese-based positive electrode material, wherein the fast ion conductor is one or more of lithium phosphate, lithium metaaluminate and lithium pyrophosphate. The lithium in the surface coating layer is derived from the residual lithium on the surface of the raw material, so the total alkali amount of the raw material is directly related to the amount of the added fast plasma coating liquid.
According to some preferred embodiments of the present invention, in step 2), the source of lithium in the coating formed on the surface of the modified lithium-rich manganese-based positive electrode material is lithium carbonate, lithium hydroxide and/or free lithium ions remaining on the surface of the raw material in step 1).
According to some preferred embodiments of the present invention, in step 1), after the uniform mixing, the liquid dissolved with the residual lithium is removed by a solid-liquid separation method, wherein the solid-liquid separation method is centrifugation or suction filtration, and is preferably suction filtration.
According to some preferred embodiments of the present invention, in step 2), the temperature of the heat treatment is 300-.
The invention also provides the surface modified lithium-rich manganese-based positive electrode material prepared by the method.
The invention further provides a lithium ion battery which comprises a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises the surface modified lithium-rich manganese-based positive electrode material.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, residual lithium on the surface of the lithium-rich manganese-based material is used as a lithium source, the lithium and polyanion contained in the fast ion conductor coating liquid form a coating layer, unreacted residual lithium is partially dissolved in an aqueous solution, and the total alkali amount on the surface of the material is obviously reduced.
(2) The method adopts an in-situ growth method to carry out fast plasma cladding on the raw material, the cladding uniformity is good, and the first coulombic efficiency and the rate capability of the material are greatly improved.
(3) The invention adopts a one-step process, achieves the dual effects of reducing the total alkali amount by coating and washing, has simple process flow and mild conditions, and is easy for batch amplification and industrial production.
Drawings
Fig. 1 is a first charge and discharge curve of the lithium-rich manganese-based positive electrode materials prepared in example 1 and comparative example 1 of the present invention.
Fig. 2 is a graph showing rate capability of the lithium-rich manganese-based positive electrode materials prepared in example 1 and comparative example 1 of the present invention.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The instruments and the like are conventional products which are purchased by normal distributors and are not indicated by manufacturers. The chemical raw materials used in the invention can be conveniently bought in domestic chemical product markets.
In the following examples, the lithium-rich manganese-based positive electrode material GM3 (raw material) was obtained from the institute of Power batteries of automobiles, national Union, and has a chemical formula of Li1.13Mn0.52Ni0.29Co0.06O2. The preparation method comprises the following steps: weighing lithium carbonate, manganese carbonate, nickel protoxide and cobaltosic oxide with corresponding mass according to the chemical formula proportion, adding a certain amount of water for ball milling, then carrying out spray drying on the ball milling slurry, and sintering the dried material in a muffle furnace to obtain the lithium-rich manganese-based GM3 material.
Example 1
Adding a certain amount of diammonium hydrogen phosphate into deionized water, stirring until the diammonium hydrogen phosphate is completely dissolved to form a solution with the concentration of 0.01mol/L, then adding a certain amount of GM3 raw material, continuously stirring (the molar ratio of the diammonium hydrogen phosphate to GM3 is 1:100, performing suction filtration to obtain an intermediate product, placing the intermediate product into a muffle furnace, heating to 550 ℃, preserving heat for 5 hours, and cooling to room temperature to obtain the surface-modified lithium-rich manganese-based positive electrode material.
Preparing a lithium ion battery: mixing the surface-modified lithium-rich manganese-based positive electrode material prepared in the example 1, acetylene black, polyvinylidene fluoride and N-methylpyrrolidone to form slurry, uniformly coating the slurry on the surface of an aluminum foil to obtain a positive electrode sheet, taking a lithium sheet as a negative electrode sheet, taking a 1mol/L Ethylene Carbonate (EC) and dimethyl carbonate (DMC) solution of lithium hexafluorophosphate (the volume ratio of EC to DMC is 1:1) as electrolyte, and assembling the electrolyte in a glove box to obtain the lithium ion battery.
The lithium ion battery of example 1 was subjected to a cycle performance test using an electrochemical tester at a test temperature of 25C at a current density of 0.1C (1C-200 mAg)-1) And testing the first charge-discharge performance of the battery within the charge-discharge voltage range of 4.8-2V. The rate performance of the cells was tested at 0.1C, 0.2C, 0.5C, 1C, 3C rates. The results are shown in Table 1.
Comparative example 1
And (3) assembling the button cell by using a lithium-rich manganese-based positive electrode material GM3 as a raw material to test the electrochemical performance. The method comprises the following specific steps: mixing GM3, acetylene black, polyvinylidene fluoride and N-methyl pyrrolidone to form slurry, and uniformly coating the slurry on the surface of an aluminum foil to obtain a positive pole piece; and then, assembling the lithium ion battery in a glove box by taking a lithium sheet as a negative electrode sheet and taking a 1mol/L Ethylene Carbonate (EC) and dimethyl carbonate (DMC) solution of lithium hexafluorophosphate (the volume ratio of EC to DMC is 1:1) as electrolyte to obtain the lithium ion battery.
Example 2
Adding a certain amount of diammonium hydrogen phosphate into deionized water, stirring until the diammonium hydrogen phosphate is completely dissolved to form a 0.05mol/L solution, then adding a certain amount of GM3 raw material, continuously stirring (the molar ratio of the diammonium hydrogen phosphate to GM3 is 3:100), carrying out suction filtration to obtain an intermediate product, putting the intermediate product into a muffle furnace, heating to 650 ℃, keeping the temperature for 2 hours, and cooling to room temperature to obtain the surface-modified lithium-rich manganese-based positive electrode material.
Lithium ion batteries were prepared and tested for performance as described in example 1, with the results shown in table 1.
Example 3
Adding a certain amount of potassium metaaluminate into deionized water, stirring and dissolving, preparing a solution with the concentration of 0.1mol/L, then adding a GM3 raw material, continuously stirring (the molar ratio of potassium metaaluminate to GM3 is 2:100 in terms of metaaluminate radical), carrying out suction filtration to obtain an intermediate product, putting the intermediate product into a muffle furnace, heating to 550 ℃, keeping the temperature for 5 hours, and cooling to room temperature to obtain the surface-modified lithium-rich manganese-based anode material.
Lithium ion batteries were prepared and tested for performance as described in example 1, with the results shown in table 1.
Example 4
Adding a certain amount of potassium pyrophosphate into deionized water, stirring until the potassium pyrophosphate is completely dissolved, preparing a solution with the concentration of 0.15mol/L, then adding a GM3 raw material, continuously stirring (the molar ratio of potassium pyrophosphate to GM3 is 5:100), carrying out suction filtration to obtain an intermediate product, putting the intermediate product into a muffle furnace, heating to 550 ℃, keeping the temperature for 5 hours, and cooling to room temperature to obtain the surface-modified lithium-rich manganese-based cathode material.
Lithium ion batteries were prepared and tested for performance as described in example 1, with the results shown in table 1.
Example 5
Adding a certain amount of sodium metaaluminate into deionized water, stirring and dissolving, preparing a solution with the concentration of 0.25mol/L, then adding a GM3 raw material, continuously stirring (the molar ratio of potassium metaaluminate to GM3 is 3:100 in terms of metaaluminate radical), carrying out suction filtration to obtain an intermediate product, putting the intermediate product into a muffle furnace, heating to 650 ℃, preserving heat for 4 hours, and cooling to room temperature to obtain the surface-modified lithium-rich manganese-based anode material.
Lithium ion batteries were prepared and tested for performance as described in example 1, with the results shown in table 1.
Example 6
Adding a certain amount of sodium pyrophosphate into deionized water, stirring and dissolving, preparing a solution with the concentration of 0.01mol/L, then adding a GM3 raw material, continuously stirring (the molar ratio of sodium pyrophosphate to GM3 is 1:100 in terms of pyrophosphate), carrying out suction filtration to obtain an intermediate product, putting the intermediate product into a muffle furnace, heating to 500 ℃, keeping the temperature for 2 hours, and cooling to room temperature to obtain the surface-modified lithium-rich manganese-based cathode material.
Lithium ion batteries were prepared and tested for performance as described in example 1, with the results shown in table 1.
Example 7
Adding a certain amount of sodium pyrophosphate into deionized water, stirring and dissolving, preparing a solution with the concentration of 0.01mol/L, then adding a GM3 raw material, continuously stirring (the molar ratio of sodium pyrophosphate to GM3 is 1:100 in terms of pyrophosphate), carrying out suction filtration to obtain an intermediate product, putting the intermediate product into a muffle furnace, heating to 300 ℃, preserving the temperature for 10 hours, and cooling to room temperature to obtain the surface-modified lithium-rich manganese-based cathode material.
Lithium ion batteries were prepared and tested for performance as described in example 1, with the results shown in table 1.
Example 8
Adding a certain amount of sodium metaaluminate into deionized water, stirring and dissolving, preparing a solution with the concentration of 1mol/L, then adding a GM3 raw material, continuously stirring (the molar ratio of potassium metaaluminate to GM3 is 8:100 in terms of metaaluminate radical), carrying out suction filtration to obtain an intermediate product, placing the intermediate product into a muffle furnace, heating to 800 ℃, keeping the temperature for 0.5h, and cooling to room temperature to obtain the surface-modified lithium-rich manganese-based anode material.
Lithium ion batteries were prepared and tested for performance as described in example 1, with the results shown in table 1.
TABLE 1 electrochemical Properties of comparative example 1 and examples 1 to 8
Table 2 total alkali amount of modified lithium-rich manganese-based positive electrode materials of examples 1 to 8 and comparative example 1
According to the test results, the first coulombic efficiency and the rate capability of the surface-modified lithium-rich manganese-based material prepared by the method are greatly improved, the first coulombic efficiency of the GM3 raw material is 70%, the first coulombic efficiency of the surface-modified material is more than 75%, and the highest coulombic efficiency can reach 81.4%; on the other hand, aiming at the defect of high total alkali quantity on the surface of the lithium-rich material, the total alkali quantity of the material before modification is 3892ppm, and the total alkali quantity of the sample after modification is greatly reduced and is only 466ppm at least; as shown in fig. 1 and fig. 2, the first charge-discharge curve and rate capability of the lithium-rich manganese-based positive electrode material prepared by the method disclosed by the invention realize excellent effects of improving electrochemical performance (first efficiency and rate capability) and reducing total alkali amount.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a surface modified lithium-rich manganese-based positive electrode material is characterized by comprising the following steps:
step 1), uniformly mixing a raw material of a lithium-rich manganese-based positive electrode with a fast ion conductor coating solution, and carrying out solid-liquid separation to obtain a surface modified lithium-rich manganese-based positive electrode material precursor; the solute in the fast ion conductor coating liquid is selected from one or more of soluble hydrogen phosphate, pyrophosphate and metaaluminate, and the solvent is water;
and 2), carrying out heat treatment on the surface modified lithium-rich manganese-based anode material precursor obtained in the step 1) to obtain the surface modified lithium-rich manganese-based anode material.
2. The method according to claim 1, wherein the solute is one or more selected from the group consisting of diamine hydrogen phosphate, sodium metaaluminate, potassium pyrophosphate and sodium pyrophosphate, and the solvent is deionized water; preferably, the solute is selected from sodium metaaluminate, potassium pyrophosphate and sodium pyrophosphate, more preferably potassium metaaluminate or sodium metaaluminate; the concentration of the fast ion conductor coating liquid is 0.01-1mol/L, preferably 0.05-0.5 mol/L.
3. A method according to claim 2, wherein the solute is present in a molar ratio, calculated as anions, of 1% to 10%, preferably 2% to 5%, of the starting material.
4. The method according to any one of claims 1 to 3, wherein in step 1), the lithium-rich manganese-based positive electrode material has a general formula shown in formula (I):
xLi2MnO3·(1-x)LiMO2(I)
wherein x is more than or equal to 0.1 and less than or equal to 0.9, M is selected from one or more of Ni, Co, Mn, Cr, Fe, Ti, Mo, Ru, V, Nb, Zr and Sn, x is more than or equal to 0.2 and less than or equal to 0.5, and M at least comprises three elements of Ni, Co and Mn.
5. The method according to any one of claims 1 to 4, wherein the total alkali content of the raw material of the lithium-rich manganese-based positive electrode material is not less than 0.5%, the total alkali content of the surface-modified lithium-rich manganese-based positive electrode material is less than 0.2%, and/or a fast ion conductor coating is grown in situ on the surface of the surface-modified lithium-rich manganese-based positive electrode material, and the fast ion conductor is one or more of lithium phosphate, lithium metaaluminate and lithium pyrophosphate.
6. The method according to any one of claims 1 to 5, wherein the source of lithium in the coating formed on the surface of the modified lithium-rich manganese-based positive electrode material in step 2) is lithium carbonate, lithium hydroxide and/or free lithium ions remaining on the surface of the raw material in step 1).
7. The method according to any one of claims 1 to 6, wherein in the step 1), the liquid dissolved with residual lithium is removed by a solid-liquid separation method after uniform mixing, wherein the solid-liquid separation method is centrifugation or suction filtration, and is preferably suction filtration.
8. The method as claimed in any one of claims 1 to 7, wherein the temperature of the heat treatment in step 2) is 300-800 ℃ and the treatment time is 0.5-10h, preferably the temperature of the heat treatment is 500-650 ℃ and the treatment time is 2-5 h.
9. A surface-modified lithium-rich manganese-based positive electrode material prepared by the method of any one of claims 1 to 8.
10. A lithium ion battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises the surface-modified lithium-rich manganese-based positive electrode material according to claim 9.
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