CN114665086A - Lithium-rich manganese-based positive electrode material and preparation method thereof - Google Patents
Lithium-rich manganese-based positive electrode material and preparation method thereof Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 98
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 83
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 81
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 73
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 64
- 239000002243 precursor Substances 0.000 claims abstract description 31
- -1 lithium salt compound Chemical class 0.000 claims abstract description 27
- 238000004729 solvothermal method Methods 0.000 claims abstract description 18
- 239000011777 magnesium Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229940069446 magnesium acetate Drugs 0.000 claims abstract description 13
- 235000011285 magnesium acetate Nutrition 0.000 claims abstract description 13
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- 238000002156 mixing Methods 0.000 claims abstract description 12
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 11
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 11
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
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- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 27
- 230000004048 modification Effects 0.000 abstract description 21
- 238000012986 modification Methods 0.000 abstract description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 abstract description 6
- 230000005012 migration Effects 0.000 abstract description 6
- 238000013508 migration Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
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- 229910021645 metal ion Inorganic materials 0.000 description 6
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- 238000005245 sintering Methods 0.000 description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910013191 LiMO2 Inorganic materials 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
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- 230000006866 deterioration Effects 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
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- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910006235 Li1+xM1-xO2 Inorganic materials 0.000 description 1
- 229910006255 Li1+xM1−xO2 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 description 1
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- 229910052596 spinel Inorganic materials 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium-rich manganese-based positive electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: adding nickel acetate, cobalt acetate and manganese acetate and a predetermined amount of precipitator into a solvent for solvothermal reaction to prepare a precursor material; presintering the precursor material, and cooling to obtain a presintering product; and uniformly mixing a lithium salt compound, a magnesium salt compound and the pre-sintered product, and then calcining to obtain the lithium-rich manganese-based positive electrode material. According to the preparation method provided by the invention, the lithium-rich manganese-based precursor material with a complete spherical structure and good dispersibility is synthesized by adopting a solvothermal method, and the magnesium acetate is used as a magnesium source for doping modification, so that the stability of the material is improved, and meanwhile, the material generates a porous structure, and the porous structure can shorten the migration path of lithium ions and provide more channels for the transmission of the lithium ions, thereby being beneficial to improving the electrochemical performance of the material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery electrode materials, and particularly relates to a lithium-rich manganese-based positive electrode material and a preparation method thereof.
Background
The lithium ion battery has the advantages of high voltage, high specific energy, long cycle life, good safety performance, wide working temperature range, environmental friendliness and the like, and is widely applied to portable devices such as mobile phones, notebooks and the like, medical equipment, electric tools and the like. In recent years, the application range of lithium ion batteries is also expanded to new fields of energy traffic (electric vehicles, hybrid electric vehicles and the like), smart power grids, novel energy storage (solar energy, wind energy) and the like, and the application of the lithium ion batteries puts higher requirements on the performance of lithium ion battery materials. The lithium ion battery comprises important components such as anode and cathode materials, electrolyte, a diaphragm and the like, wherein the anode material is used as a key factor influencing the electrochemical performance, safety, cost and the like of the whole battery, and the development of the lithium ion battery is widely concerned by the scientific community. The currently commonly used lithium ion battery anode material mainly comprises LiCoO with a laminated structure2，LiMnO2，LiNiO2，LiNixCoyMn1-x-yO2LiMn of spinel structure2O4And LiFePO of olivine structure4And the like. Unfortunately, almost all of the cathode materials reach the usable specific capacity (120-200 mAh.g)–1) And therefore, the development of a high specific capacity positive electrode material is imminent. Lithium-rich manganese-based positive electrode material xLi2MnO3·(1-x)LiMO2(M-Ni, Co, Mn), or may be represented by Li1+xM1-xO2(M ═ Ni, Co, Mn), has attracted much attention from researchers because of its property of exhibiting high capacity at high voltage. However, a great deal of research shows that the first excessive delithiation of the material during the charge and discharge process at high voltage damages the surface lattice structure of the material, so thatBut affects electrochemical properties such as poor cycle stability and rate capability. Therefore, the lithium-rich manganese-based material xLi is improved2MnO3·(1-x)LiMO2Structural stability of (M ═ Ni, Co, Mn), and improvement of electrochemical performance thereof are key problems to be solved at present. The currently common methods for improving the structural stability of the lithium-rich manganese-based cathode material mainly comprise doping, coating, combination of two methods and the like, but the modification methods do not achieve the expected modification effect, for example, although the coating layer can protect the cathode material particles from being corroded by electrolyte, the coating layer does not contribute to the inherent structural stability of the material; the doping can have the condition of uneven doping, segregation often exists, elements can be gathered to the surface, a pore channel structure can not be generated, and the migration of lithium ions is not contributed. In a plurality of lithium-rich manganese-based positive electrode materials xLi2MnO3·(1-x)LiMO2Among the synthesis methods of precursors of (M ═ Ni, Co, Mn), the coprecipitation method using ammonia water as a pH adjuster and a chelating agent for transition metals and water as a solvent is one of the methods generally used in the field of material synthesis at present. In addition, the material synthesized by the method has serious agglomeration, poor dispersibility, low first coulombic efficiency, incomplete spherical structure and obstruction to Li+The poor structural stability of the material results in the deterioration of electrochemical properties such as capacity, cycling stability and the like, and the exertion of the electrochemical properties of the material is influenced.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a lithium-rich manganese-based positive electrode material and a preparation method thereof, and aims to solve the environmental problems generated in the synthesis process of the conventional lithium-rich manganese-based positive electrode material synthesis method and the problems of incomplete spherical structure, poor dispersibility, poor structural stability, poor electrochemical performance and the like of the synthesized lithium-rich manganese-based positive electrode material.
In order to achieve the above object, one aspect of the present invention provides a method for preparing a lithium-rich manganese-based positive electrode material, which comprises:
s110, adding acetate of nickel, acetate of cobalt and acetate of manganese into a solvent together with a predetermined amount of precipitator to perform solvothermal reaction to prepare a precursor material;
s120, pre-burning the precursor material, and cooling to obtain a pre-burned product;
and S130, uniformly mixing a lithium salt compound, a magnesium salt compound and the pre-sintered product, and then calcining to obtain the lithium-rich manganese-based positive electrode material.
Preferably, the step S110 specifically includes:
dissolving nickel acetate, cobalt acetate and manganese acetate into a solvent according to a preset molar ratio, and stirring until the nickel acetate, the cobalt acetate and the manganese acetate are completely dissolved to obtain a first mixed solution;
adding a predetermined amount of a precipitant to the first mixed solution and dissolving and mixing to obtain a second mixed solution;
and placing the second mixed solution into a reaction kettle for solvothermal reaction, and cooling after the reaction is finished to obtain the precursor material.
Further preferably, the predetermined molar ratio is Mn according to the molecular formula of the precursor material0.54Ni0.13Co0.13(CO3)0.8The requirements of (2) are set.
Further preferably, the precipitating agent is urea.
Further preferably, the reaction temperature of the solvothermal reaction is 160-180 ℃, and the reaction time is 10-24 h.
Preferably, in the step S120, the pre-sintering temperature is 450 ℃ to 550 ℃, and the pre-sintering time is 6 hours to 10 hours.
Preferably, the step S130 specifically includes:
uniformly mixing a lithium salt compound, a magnesium salt compound and the pre-sintered product according to a preset reaction ratio to obtain a mixed material;
heating the mixed material to a preset temperature in an air atmosphere, and calcining to obtain the porous lithium-rich manganese-based positive electrode material;
further preferably, the predetermined temperature is 850-950 ℃, and the calcination time is 10-12 h.
Further preferably, the lithium salt compound is lithium carbonate, and the magnesium salt compound is magnesium acetate.
Further preferably, the molecular formula of the lithium-rich manganese-based cathode material is Li1.2[Mn0.54Ni0.13Co0.13]1- xMgxO2Wherein x is 0.01 to 0.05; the predetermined reaction proportion is that the molecular formula of the lithium-rich manganese-based positive electrode material is Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2The requirements of (2) are set.
Another aspect of the invention provides a lithium-rich manganese-based positive electrode material prepared by the preparation method.
Has the advantages that: according to the lithium-rich manganese-based positive electrode material and the preparation method thereof provided by the embodiment of the invention, the precursor material of the lithium-rich manganese-based positive electrode material with a complete spherical structure and good dispersibility is synthesized by using the solvent with dispersibility and adopting a solvothermal method, so that the problem of agglomeration in the synthesis process is favorably solved; in addition, the lithium-rich manganese-based positive electrode material is doped and modified by taking magnesium acetate as a magnesium source, so that the stability of the material is improved, and meanwhile, the lithium-rich manganese-based positive electrode material generates a porous structure, the porous structure is favorable for the diffusion of lithium ions, the migration path of the lithium ions can be shortened, more channels are provided for the transmission of the lithium ions, and the electrochemical performance of the material is favorably improved; in addition, no harmful substance is generated in the preparation process, so that the environmental pollution and the harm to human health are avoided.
Drawings
The above and other aspects, features and advantages of embodiments of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
fig. 1 is a flow chart of a method for preparing a lithium-rich manganese-based positive electrode material according to an embodiment of the present invention;
FIG. 2 is a scanned view of a precursor material provided in example 1 of the present invention;
fig. 3 is a scanning cross-sectional view of a lithium-rich manganese-based positive electrode material subjected to doping modification according to example 3 of the present invention;
fig. 4 is a cycle performance diagram of the lithium-rich manganese-based positive electrode material obtained by adding magnesium acetate with different contents for doping modification according to embodiments 2 to 4 of the present invention;
FIG. 5 is a cross-sectional view of a lithium-rich manganese-based positive electrode material provided in comparative example 1 of the present invention without doping modification;
fig. 6(a) is a scanned graph of a lithium-rich manganese-based positive electrode material provided in comparative example 1 of the present invention without doping modification;
fig. 6(b) is a scanned graph of the lithium-rich manganese-based positive electrode material subjected to doping modification provided in example 3 of the present invention.
Detailed Description
Hereinafter, specific embodiments of the present invention will be described in detail with reference to the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated.
As used herein, the term "include" and its variants mean open-ended terms in the sense of "including, but not limited to. The terms "based on," based on, "and the like mean" based at least in part on, "" based at least in part on. The terms "one embodiment" and "an embodiment" mean "at least one embodiment". The term "another embodiment" means "at least one other embodiment". The terms "first," "second," and the like may refer to different or the same object. Other definitions, whether explicit or implicit, may be included below. The definition of a term is consistent throughout the specification unless the context clearly dictates otherwise.
As described in the background art, the existing method for synthesizing the lithium-rich manganese-based positive electrode material mainly adopts a coprecipitation method, which easily causes environmental pollution in the synthesis process, and in addition, the material synthesized by the method has serious agglomeration, poor dispersibility, incomplete spherical structure, obstruction to lithium ion transmission and poor structural stability, thereby causing deterioration of electrochemical properties such as capacity, cycling stability and the like, and affecting the exertion of the electrochemical properties of the material. Therefore, in order to solve many technical problems of the lithium-rich manganese-based cathode material in the prior art, embodiments of the present invention provide a lithium-rich manganese-based cathode material and a preparation method thereof.
A lithium-rich manganese-based positive electrode material and a method for preparing the same according to an embodiment of the present invention will be described in detail below with reference to the accompanying drawings, and fig. 1 is a flowchart of a method for preparing a lithium-rich manganese-based positive electrode material according to an embodiment of the present invention.
Referring to fig. 1, in step S110, nickel acetate, cobalt acetate, and manganese acetate are added to a solvent together with a predetermined amount of a precipitant to perform a solvothermal reaction, thereby preparing a precursor material.
Preferably, the step S110 specifically includes:
dissolving nickel acetate, cobalt acetate and manganese acetate into a solvent according to a preset molar ratio, and stirring until the nickel acetate, the cobalt acetate and the manganese acetate are completely dissolved to obtain a first mixed solution;
adding a predetermined amount of a precipitant to the first mixed solution and dissolving and mixing to obtain a second mixed solution;
and placing the second mixed solution in a reaction kettle with a polytetrafluoroethylene inner container for solvothermal reaction, and cooling after the reaction is finished to obtain the precursor material.
Further preferably, the predetermined molar ratio is Mn according to the molecular formula of the precursor material0.54Ni0.13Co0.13(CO3)0.8Setting requirements of (1); that is, the molar ratio of the nickel acetate, the cobalt acetate, and the manganese acetate is 0.13: 0.13: 0.54.
further preferably, the solvent includes water, ethylene glycol and ethanol, and the solvent should have dispersibility to function to disperse and dissolve the nickel acetate, cobalt acetate and manganese acetate, and not introduce other impurity ions; further, the solvent is added in an amount capable of making the total concentration of the nickel metal ion, cobalt metal ion and manganese metal ion in the first mixed solution 0.5 mol/L.
Further preferably, the precipitant is urea, and the amount of the substance added to the precipitant is equal to the sum of the amounts of the substances of the nickel metal ion, the cobalt metal ion, and the manganese metal ion in the first mixed solution.
Further preferably, the reaction temperature of the solvothermal reaction is 160-180 ℃, and the reaction time is 10-24 h.
The precipitant has both N element and C element, and can complex three elements of nickel, cobalt and manganese together for coprecipitation under high-temperature and high-pressure reaction conditions in the process of carrying out solvothermal reaction, so as to form the precursor material.
According to the invention, the solvent with dispersibility is used, and the precursor material of the lithium-rich manganese-based anode material is synthesized by adopting a solvothermal method, so that the obtained precursor material has a complete spherical structure and good dispersibility, and the problem of agglomeration of the lithium-rich manganese-based anode material in the synthesis process is favorably solved.
In step S120, the precursor material is pre-baked, and is cooled to obtain a pre-baked product.
Preferably, the pre-sintering temperature is 450-550 ℃, and the pre-sintering time is 6-10 h.
In step S130, a lithium salt compound and a magnesium salt compound are uniformly mixed with the pre-fired product and then calcined to obtain the lithium-rich manganese-based positive electrode material.
Preferably, the step S130 specifically includes:
uniformly mixing a lithium salt compound, a magnesium salt compound and the pre-sintered product according to a preset reaction ratio to obtain a mixed material;
and heating the mixed material to a preset temperature in an air atmosphere, and calcining to obtain the porous lithium-rich manganese-based positive electrode material.
Further preferably, the predetermined temperature is 850-950 ℃, and the calcination time is 10-12 h.
Further preferably, the lithium salt compound is lithium carbonate, and the magnesium salt compound is magnesium acetate.
Preferably, the molecular formula of the lithium-rich manganese-based cathode material is Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2Wherein x is 0.01 to 0.05; the predetermined reaction proportion is that the molecular formula of the lithium-rich manganese-based positive electrode material is Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2The requirements of (2) are set.
Further preferably, x has a value of 0.01, or 0.03, or 0.05.
Wherein, the lithium carbonate should be added in an excess of 5 mol% because of volatilization of lithium ions during high-temperature calcination, resulting in loss of lithium ions.
According to the invention, magnesium acetate is used as a magnesium source, the lithium-rich manganese-based positive electrode material is doped and modified in the preparation process, and the magnesium acetate contains more C, H elements, so that carbon dioxide, water vapor and the like can be released in the high-temperature calcination process in the air atmosphere after being mixed with the presintered precursor material and a lithium carbonate compound, so that the lithium-rich manganese-based material generates a porous structure, the porous structure is favorable for diffusion of lithium ions, the migration path of the lithium ions is shortened, more channels are provided for transmission of the lithium ions, and the porous structure is more obvious along with increase of the magnesium doping amount, and in addition, the structural stability of the material can be improved by doping the magnesium ions, thereby improving the electrochemical performance of the material.
The embodiment of the invention also provides the lithium-rich manganese-based cathode material prepared by the preparation method. The lithium-rich manganese-based positive electrode material is doped and modified by using magnesium ions, so that the structural stability of the material is improved, and meanwhile, a porous structure is generated, the porous structure shortens the migration path of the lithium ions, and provides more channels for the transmission of the lithium ions, thereby improving the electrochemical performance of the material.
The above-described lithium-rich manganese-based positive electrode material and the method for preparing the same will be described below with reference to specific examples, and it will be understood by those skilled in the art that the following examples are only specific examples of the above-described lithium-rich manganese-based positive electrode material and the method for preparing the same of the present invention, and are not intended to limit the entirety thereof.
Example 1: preparation of precursor Material
Nickel acetate, cobalt acetate and manganese acetate were mixed in a ratio of 0.13: 0.13: dissolving the mixture in an ethylene glycol solvent according to a molar ratio of 0.54, and stirring the mixture until the mixture is completely dissolved to obtain a first mixed solution; adding a precipitator urea into the first mixed solution, dissolving and mixing to obtain a second mixed solution; pouring the second mixed solution into a reaction kettle with a polytetrafluoroethylene inner container, carrying out solvothermal reaction at 160 ℃ for 24 hours, cooling after the reaction is finished, and then washing and drying to obtain the precursor material, wherein the molecular formula of the precursor material is Mn0.54Ni0.13Co0.13(CO3)0.8。
Fig. 2 is a scanned graph of the precursor material prepared in example 1 of the present invention, and as shown in fig. 2, the precursor material prepared by the solvothermal method has a complete spherical structure and good dispersibility.
Examples 2 to 4: preparation of lithium-rich manganese-based positive electrode material modified by doping magnesium ions
Pre-burning the precursor material prepared in the embodiment 1 at 500 ℃ for 6h to obtain a pre-burned product;
uniformly mixing a lithium salt compound, a magnesium salt compound and the pre-sintered product according to a preset reaction ratio to obtain a mixed material; the predetermined reaction proportion is that the molecular formula of the lithium-rich manganese-based positive electrode material is Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2The requirement of (1), wherein the lithium carbonate should be added in an amount of 5% by mole in excess;
and heating the mixed material to 900 ℃ in an air atmosphere, and calcining for 12h to obtain the magnesium ion doped and modified lithium-rich manganese-based positive electrode material.
Examples 2 to 4 are different from the above-described lithium-rich manganese-based positive electrode material Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2Wherein x has values of 0.01, 0.03 and 0.05, respectively, and the rest are the same.
FIG. 3 shows example 3 of the present invention (Li-rich manganese-based positive electrode material)1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2The value of x is 0.03), and as shown in fig. 3, the lithium-rich manganese-based positive electrode material subjected to doping modification is in a porous structure, and the porous structure is favorable for diffusion of lithium ions, shortens the diffusion path of the lithium ions, and is further favorable for improving the electrochemical performance of the material.
FIG. 4 is a cycle performance diagram of the lithium-rich manganese-based positive electrode material obtained by doping modification of magnesium acetate with different contents in examples 2 to 4 of the present invention, as shown in FIG. 4, when the lithium-rich manganese-based positive electrode material Li1.2[Mn0.54Ni0.13Co0.13]1- xMgxO2When the value of x in the lithium-rich manganese-based positive electrode material is 0.03, the cycle performance of the lithium-rich manganese-based positive electrode material is optimal, and the capacity retention rate is 94.04% after 300 cycles.
Comparative example 1: preparation of lithium-rich manganese-based cathode material without doping modification
Pre-burning the precursor material prepared in the embodiment 1 at 500 ℃ for 6h to obtain a pre-burned product;
uniformly mixing the pre-sintering product with 5% molar excess of a lithium carbonate compound to obtain a mixed material;
and heating the mixed material to 900 ℃ in an air atmosphere, and calcining for 12h to obtain the lithium-rich manganese-based cathode material which is not subjected to doping modification.
Wherein, the comparative example 1 is different from the examples 2 to 4 only in that no magnesium acetate is added in the preparation process.
Fig. 5 is a scanning cross-sectional view of the lithium-rich manganese-based positive electrode material which is not subjected to doping modification and is prepared in comparative example 1 of the present invention, as shown in fig. 5, the lithium-rich manganese-based positive electrode material which is not subjected to doping modification has no porous structure, but the elements are uniformly distributed, which further indicates that the lithium-rich manganese-based positive electrode material with good dispersibility is favorably prepared by using the solvothermal method, and the reason why the lithium-rich manganese-based positive electrode material generates the porous structure is that magnesium acetate is added for doping modification.
FIG. 6(a) is a scanned graph of a lithium-rich manganese-based positive electrode material prepared in comparative example 1 according to the present invention without doping modification; FIG. 6(b) shows example 3 (Li-rich manganese-based positive electrode material) of the present invention1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2The value of x in the process is 0.03) and scanning the prepared lithium-rich manganese-based cathode material subjected to doping modification. As can be seen from fig. 6, the spherical structure of the obtained lithium-rich manganese-based positive electrode material remained intact regardless of whether magnesium acetate was added for doping modification, and the spherical particle size was about 4 μm.
In summary, according to the lithium-rich manganese-based positive electrode material and the preparation method thereof provided by the embodiment of the invention, the solvent with dispersibility is used, and the solvothermal method is adopted to synthesize the precursor material of the lithium-rich manganese-based positive electrode material, so that the obtained precursor material has a complete spherical structure and good dispersibility, and the problem of agglomeration of the lithium-rich manganese-based positive electrode material in the synthesis process is favorably solved; in addition, the preparation method also takes magnesium acetate as a magnesium source, and the lithium-rich manganese-based positive electrode material is doped and modified in the preparation process, so that the structural stability of the material is improved, and simultaneously a porous structure is generated, the porous structure is favorable for the diffusion of lithium ions, the migration path of the lithium ions is shortened, more channels are provided for the transmission of the lithium ions, and the porous structure is more obvious along with the increase of the magnesium doping amount, so that the electrochemical performance of the material is improved; in addition, no harmful substance is generated in the preparation process, so that the environmental pollution and the harm to human health are avoided.
The foregoing description has described certain embodiments of this invention. Other embodiments are within the scope of the following claims.
The terms "exemplary," "example," and the like, as used throughout this specification, mean "serving as an example, instance, or illustration," and do not mean "preferred" or "advantageous" over other embodiments. The detailed description includes specific details for the purpose of providing an understanding of the described technology. However, the techniques may be practiced without these specific details. In some instances, well-known structures and devices are shown in block diagram form in order to avoid obscuring the concepts of the described embodiments.
Alternative embodiments of the present invention are described in detail with reference to the drawings, however, the embodiments of the present invention are not limited to the specific details in the above embodiments, and within the technical idea of the embodiments of the present invention, many simple modifications may be made to the technical solution of the embodiments of the present invention, and these simple modifications all belong to the protection scope of the embodiments of the present invention.
The previous description of the disclosure is provided to enable any person skilled in the art to make or use the disclosure. Various modifications to the disclosure will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other variations without departing from the scope of the disclosure. Thus, the description is not intended to be limited to the examples and designs described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a lithium-rich manganese-based positive electrode material is characterized by comprising the following steps:
s110, adding acetate of nickel, acetate of cobalt and acetate of manganese into a solvent together with a predetermined amount of precipitator to perform solvothermal reaction to prepare a precursor material;
s120, pre-burning the precursor material, and cooling to obtain a pre-burned product;
and S130, uniformly mixing a lithium salt compound, a magnesium salt compound and the pre-sintered product, and then calcining to obtain the lithium-rich manganese-based positive electrode material.
2. The method according to claim 1, wherein the step S110 specifically includes:
dissolving nickel acetate, cobalt acetate and manganese acetate into a solvent according to a preset molar ratio, and stirring until the nickel acetate, the cobalt acetate and the manganese acetate are completely dissolved to obtain a first mixed solution;
adding a predetermined amount of a precipitant to the first mixed solution and dissolving and mixing to obtain a second mixed solution;
and placing the second mixed solution into a reaction kettle for solvothermal reaction, and cooling after the reaction is finished to obtain the precursor material.
3. The method of claim 2, wherein the predetermined molar ratio is based on the molecular formula of the precursor material being Mn0.54Ni0.13Co0.13(CO3)0.8The requirements of (2) are set.
4. The method of claim 2, wherein the precipitating agent is urea.
5. The preparation method according to claim 2, wherein the reaction temperature of the solvothermal reaction is 160-180 ℃ and the reaction time is 10-24 hours.
6. The method of claim 1, wherein in step S120, the pre-firing temperature is 450 ℃ to 550 ℃, and the pre-firing time is 6 hours to 10 hours.
7. The method according to any one of claims 1 to 6, wherein the step S130 specifically includes:
uniformly mixing a lithium salt compound, a magnesium salt compound and the pre-sintered product according to a preset reaction ratio to obtain a mixed material;
heating the mixed material to a preset temperature in an air atmosphere, and calcining to obtain the porous lithium-rich manganese-based positive electrode material;
wherein the predetermined temperature is 850-950 ℃, and the calcining time is 10-12 h.
8. The method according to claim 7, wherein the lithium salt compound is lithium carbonate and the magnesium salt compound is magnesium acetate.
9. The method according to claim 8, wherein the lithium-rich manganese-based positive electrode material has a molecular formula of Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2Wherein x is 0.01 to 0.05; the predetermined reaction proportion is that the molecular formula of the lithium-rich manganese-based positive electrode material is Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2The requirements of (2) are set.
10. The lithium-rich manganese-based positive electrode material prepared by the preparation method according to any one of claims 1 to 9.
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