CN114665058A - Preparation method of lithium ion battery anode material lithium iron manganese phosphate - Google Patents
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Abstract
The invention relates to a preparation method of lithium ion battery anode material lithium iron manganese phosphate, which comprises the following steps: (1) weighing a certain amount of lithium source, manganese source, iron source and phosphorus source, adding a carbon source, taking absolute ethyl alcohol as a dispersing agent, and placing in a ball milling tank for grinding to obtain a precursor; (2) controlling the heating rate to be 5-12 ℃/min, heating the precursor to 250-350 ℃ in the inert gas atmosphere, and calcining to obtain a pre-sintered product; (3) adding a carbon source into the pre-sintered product again, taking absolute ethyl alcohol as a dispersing agent, and placing the mixture into a ball milling tank for grinding to perform secondary carbon coating; (4) and (4) controlling the heating rate to be 5-12 ℃/min, calcining the sample obtained in the step (3) in an inert gas atmosphere at 550-750 ℃, and cooling the furnace to room temperature to obtain the secondary carbon-coated lithium manganese iron phosphate material. The invention adopts an improved high-temperature solid phase method to prepare the lithium iron manganese phosphate material, wherein secondary carbon coating plays roles in refining crystal grains and enhancing electron and ion transmission, so that the material shows good electrochemical performance.
Description
Technical Field
The invention belongs to a preparation method of a battery anode material in the field of materials, and particularly relates to a preparation method of a lithium ion battery anode material lithium iron manganese phosphate.
Background
Since the Goodenough topic group in LiMPO4Since the development work done on (M ═ Fe, Mn, Co, and Ni) series positive electrode materials, a large number of researchers have been added to this research line. Wherein the lithium iron phosphate (LiFePO)4) Because of the advantages of high theoretical capacity, good cycle performance, excellent safety performance, wide raw material source, low cost, environmental protection and the like, the lithium-ion battery has wide attention paid by people, but compared with Li+The electrode potential of/Li is 3.4V, and the low energy density is difficult to meet the requirement of a high-power battery. Lithium manganese iron phosphate (LiMn)xFe1-xPO4) As in LiFePO4Upgraded version of (2) with LiFePO4The orthorhombic olivine crystal structure has the characteristics of excellent thermal stability and low oxidability, and the working voltage of the orthorhombic olivine crystal structure is 4.1V which is much higher than that of LiFePO43.4V, and is positioned in a stable electrochemical window of an organic electrolyte system, and the energy density of the electrolyte system is compared with that of LiFePO4The lift is about 20 percent. Therefore, high performance LiMnxFe1-xPO4Is expected to realize LiFePO4The partial replacement of the power battery has very important significance for improving the energy density of the power battery. However, the lower electron conductivity and ion diffusion rate result in LiMnxFe1-xPO4The large current charging and discharging performance is poor. In addition, the structural stability of the material is poor, the electrochemical cycling stability of the material is reduced, and the commercial application of the material is limited.
For LiMnxFe1-xPO4The problem of poor conductivity of the material, at present, a great deal of research is devoted to improving the electrochemical performance of the material, and the method comprises the steps of particle size nanocrystallization, surface conductive carbon coating, metal cation doping and the like; wherein a highly conductive material is used for LiMnxFe1-xPO4Surface coating is considered to be effective in promoting LiMnxFe1-xPO4Important methods for rate capability and cycle life, commonly used to improve LiMnxFe1-xPO4The electrochemical performance of (2). For LiMnxFe1-xPO4The carbon coating can inhibit the growth of crystal particles and reduce the diffusion distance of lithium ions on one hand, and the carbon has excellent conductivity on the other hand, thereby being beneficial to the transmission of electrons and improving the electronic conductivity of the material. At present, the preparation of carbon-coated LiMn has been reportedxFe1-xPO4The material mainly comprises a sol-gel method, a hydrothermal method, a solid phase method, a spray pyrolysis method and the like. In the common methods, the sol-gel method uses high cost of raw materials and long production period; the conditions of a hydrothermal method are not easy to control, the purity of the synthesized product is not high, and the large-scale production is difficult to realize; compared with the two methods, the solid phase method has the advantages of wide raw material source, low cost, high yield, simple process and the like, and can be used for LiMnxFe1-xPO4The practical commercialization of the positive electrode material is crucial.
CN113929073A discloses a method for preparing carbon-coated lithium manganese iron phosphate by a solid phase method, and compared with the existing lithium manganese iron phosphate and ternary materials, the prepared lithium manganese iron phosphate has the advantages of lower cost and higher voltage platform, and meanwhile, the obtained lithium manganese iron phosphate has good electrical property and cycle stability.
CN103956491B relates to a lithium iron manganese phosphate anode material of a lithium ion battery and a preparation method thereof, the carbon-coated lithium iron manganese phosphate anode material prepared by the solid phase method has higher discharge voltage platform and discharge specific capacity, and also has better electronic conductivity than lithium manganese phosphate, and the material performance is obviously improved.
The solid phase method is widely applied as the most conventional carbon coating method, but the method is difficult to finely control the phase structure and the microstructure of a final product, so that the conditions of easy particle aggregation, uneven particle size distribution, incomplete carbon layer coating and the like are caused, and the rate performance and the cycle stability of the lithium manganese iron phosphate cannot be fully improved. Thus, the preparation of LiMn in the solid phase methodxFe1-xPO4How to further reduce the particle size of the product and form uniformly dispersed particles with complete carbon coating, so that the lithium ion battery anode material with higher electrochemical performance is obtained is the key point.
Disclosure of Invention
The invention aims to solve the problems of particle agglomeration, uneven size distribution and incomplete carbon layer coating easily caused in the solid-phase method for preparing LiMnxFe1-xPO4, and provides an improved method for preparing a secondary carbon-coated LiMnxFe1-xPO4 positive electrode material by a high-temperature solid-phase method. According to the invention, a secondary coating process with low cost is introduced into a traditional high-temperature solid phase method to form particles with small size and good dispersibility, and a uniform and compact carbon conducting layer is obtained, so that the ion diffusivity and the electronic conductivity of the LiMnxFe1-xPO4 material are further improved, and the purpose of improving the electrochemical performance of the material is achieved.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of lithium ion battery anode material lithium iron manganese phosphate is characterized by comprising the following steps:
(1) weighing a certain amount of lithium source, manganese source, iron source and phosphorus source according to the mass ratio of 1.0-1.2: 0.6:0.4:1.0, then adding 10-25% by mass of carbon source, placing the mixture in a ball milling tank, adding absolute ethyl alcohol as a dispersing agent, grinding and dispersing for 4-6 h at the rotating speed of 280-400 r/min, drying and grinding the uniformly mixed slurry to obtain precursor powder;
(2) controlling the heating rate to be 5-12 ℃/min, heating the precursor powder obtained in the step (1) to 250-350 ℃ in an inert gas atmosphere, pre-burning at a constant temperature for 2-5 h, and cooling along with a furnace to obtain a pre-sintered product;
(3) taking out the pre-sintered product, grinding the pre-sintered product, adding a carbon source with the mass fraction of 3-10%, uniformly mixing, and performing ball milling on the prepared sample in an absolute ethyl alcohol medium at the speed of 280-400 r/min for 2-4 h to perform secondary carbon coating;
(4) controlling the heating rate to be 5-12 ℃/min, calcining the mixture powder obtained in the step (3) at 550-750 ℃ for 3-12 h under the protection of inert gas atmosphere, and cooling to room temperature along with the furnace to obtain the lithium iron manganese phosphate cathode material coated with carbon twice.
The lithium source in the step (1) is one or two of lithium carbonate and lithium hydroxide.
The manganese source in the step (1) is one or more of manganese carbonate, manganese sulfate, manganese oxalate and manganese acetate.
The iron source in the step (1) is one or more of ferrous nitrate, ferrous oxalate, ferrous sulfate and ferrous chloride.
The phosphorus source in the step (1) is one or two of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
The carbon source in the steps (1) and (3) is one or more of glucose, citric acid, carbon nano tubes and polyethylene glycol.
The inert gas in the steps (2) and (4) is nitrogen or argon.
Advantageous effects
(1) According to the invention, a secondary carbon coating process with low cost is introduced into the traditional high-temperature solid phase method, so that on one hand, agglomeration of sintered products can be prevented, and particles with small size and good dispersibility are formed; on the other hand, a more uniform and compact carbon coating layer can be obtained. The reduction of the particle size can not only shorten the diffusion distance of lithium ions and enable the processes of the lithium ions to be more smooth in insertion and removal, but also increase the specific surface area of the material, so that the anode material is fully infiltrated by electrolyte, the interface transfer impedance of the anode material is reduced, and the conduction of ions is facilitated. Meanwhile, the abundant carbon conducting layers provide convenient paths for the transmission of electrons, and the improvement of the electron and ion transmission rates is beneficial to the improvement of the electrochemical performance of the lithium iron manganese phosphate material.
(2) The structural formula of the lithium iron manganese phosphate material for the positive electrode of the lithium ion battery prepared by the improved method is LiMn0.6Fe0.4PO4The manganese element occupies 60 percent of the content of the transition metal element, and the working voltage is 4.1V, so that the manganese-based composite material has the advantage of high energy density; excellent discharge capacity and cycle stability at a high temperature of 55 ℃; the excellent electrochemical performance enables the power battery to meet the requirements of high power and high energy density.
Drawings
Fig. 1 is an XRD spectrogram of the lithium iron manganese phosphate material obtained in example 1 of the present invention.
Fig. 2 is a TEM image of the lithium iron manganese phosphate material obtained in example 1 of the present invention.
Fig. 3 is a first charge-discharge curve diagram of the lithium iron manganese phosphate material obtained in example 1 and comparative example 1 of the present invention at a 0.1C magnification.
Fig. 4 is a charge-discharge curve diagram of the lithium iron manganese phosphate material obtained in embodiment 1 at 0.1C, 0.2C, 0.5C, and 1C magnification.
Fig. 5 is a cycle performance diagram of the lithium iron manganese phosphate material obtained in example 1 of the present invention at 55 ℃.
Detailed Description
The technical solution of the present invention is further illustrated by the following embodiments. It should be apparent to those skilled in the art that the following descriptions are only a part of the embodiments of the present invention, but not all embodiments of the present invention, and are only provided to assist understanding of the present invention, and should not be construed as specifically limiting the present invention.
Example 1
The embodiment provides a modified lithium iron manganese phosphate cathode material, and a preparation method of the modified lithium iron manganese phosphate cathode material comprises the following steps:
taking lithium carbonate, manganese sulfate, ferrous oxalate and ammonium dihydrogen phosphate as raw materials, weighing the raw materials according to the stoichiometric ratio of the molar ratio of lithium, manganese, iron and phosphorus of 1.0-1.2: 0.6:0.4:1, adding 20 mass percent of polyethylene glycol and 5 mass percent of carbon nano tubes, and ball-milling the raw materials in an absolute ethyl alcohol medium at the rotating speed of 400r/min for 6 hours to fully and uniformly mix the raw materials. And taking out the prepared mixture, and drying the mixture in a forced air drying oven at 80 ℃ for 6h to obtain precursor powder. And putting the precursor into a program-controlled tube furnace, heating to 350 ℃ at a heating rate of 5 ℃/min under the protection of high-purity argon, and presintering for 3 h. Adding 10% by mass of polyethylene glycol into the pre-sintered product, performing ball milling on the obtained sample in an absolute ethyl alcohol medium at a rotating speed of 400r/min for 6h to perform secondary carbon coating on the surface, heating to 650 ℃ at a heating speed of 5 ℃/min, sintering for 12h, and cooling to room temperature along with the furnace to obtain the secondary carbon-coated lithium manganese iron phosphate cathode material.
Example 2
The embodiment provides a modified lithium iron manganese phosphate cathode material, and a preparation method of the modified lithium iron manganese phosphate cathode material comprises the following steps:
taking lithium carbonate, manganese acetate, ferrous sulfate and ammonium dihydrogen phosphate as raw materials, weighing the raw materials according to the stoichiometric ratio of the molar ratio of lithium, manganese, iron and phosphorus of 1.0-1.2: 0.6:0.4:1, adding 20 mass percent of glucose and 5 mass percent of carbon nano tubes, and ball-milling the raw materials in an absolute ethyl alcohol medium at the rotating speed of 400r/min for 6 hours to fully and uniformly mix the raw materials. And taking out the prepared mixture, and drying the mixture in a forced air drying oven at 80 ℃ for 6h to obtain precursor powder. And putting the precursor into a program-controlled tube furnace, heating to 350 ℃ at a heating rate of 5 ℃/min under the protection of high-purity argon, and presintering for 3 h. Adding 10% of glucose by mass into the pre-sintered product, ball-milling the obtained sample in an absolute ethyl alcohol medium at a rotating speed of 400r/min for 6h to perform secondary carbon coating on the surface, heating to 650 ℃ at a heating speed of 5 ℃/min, sintering for 12h, and cooling to room temperature along with the furnace to obtain the secondary carbon-coated lithium manganese iron phosphate cathode material.
Example 3
The embodiment provides a modified lithium iron manganese phosphate cathode material, and a preparation method of the modified lithium iron manganese phosphate cathode material comprises the following steps:
lithium carbonate, manganese carbonate, ferrous nitrate and diammonium phosphate are used as raw materials, the raw materials are weighed according to the stoichiometric ratio of the molar ratio of lithium to manganese to iron to phosphorus of 1.0-1.2: 0.6:0.4:1, citric acid with the mass fraction of 20% and carbon nano tubes with the mass fraction of 5% are added, and the raw materials are subjected to ball milling for 6 hours in an absolute ethyl alcohol medium at the rotating speed of 400r/min, so that the raw materials are fully and uniformly mixed. And taking out the prepared mixture, and drying the mixture in a forced air drying oven at 80 ℃ for 6h to obtain precursor powder. And putting the precursor into a program-controlled tube furnace, heating to 350 ℃ at a heating rate of 5 ℃/min under the protection of high-purity argon, and presintering for 3 h. Adding 10% citric acid by mass into the pre-sintered product, ball-milling the obtained sample in an absolute ethyl alcohol medium at a rotating speed of 400r/min for 6h to perform secondary carbon coating on the surface, heating to 650 ℃ at a heating speed of 5 ℃/min, sintering for 12h, and cooling to room temperature along with the furnace to obtain the secondary carbon-coated lithium manganese iron phosphate cathode material.
Comparative example 1
The comparative example is different from example 1 only in that no 10% by mass of polyethylene glycol is added to the pre-sintered product to carry out the surface secondary carbon coating of the material, and other conditions and parameters are completely the same as those of example 1.
Comparative example 2
The comparative example differs from example 2 only in that no 10% by mass of glucose was added to the pre-sintered product to carry out the surface secondary carbon coating of the material, and the other conditions and parameters were exactly the same as those of example 2.
Comparative example 3
The comparative example differs from example 3 only in that no citric acid with a mass fraction of 10% was added to the pre-sintered product to carry out the surface secondary carbon coating of the material, and the other conditions and parameters were exactly the same as those of example 3.
Material characterization:
phase analysis was performed on the lithium iron manganese phosphate material prepared in example 1 using a japanese D/max-2500/PC type X-ray diffractometer, and the results are shown in fig. 1, where the diffraction peak and LiMn of the prepared sample0.6Fe0.4PO4Corresponding to the standard map (PDF #13-0336) and belonging to orthorhombic crystalsAn olivine structure of the system; no impurity peak appears in the map, which indicates that the sample prepared in the embodiment is pure-phase lithium manganese iron phosphate; no diffraction peak was detected for carbon, indicating that carbon is present in an amorphous form.
The morphology and microstructure of the lithium iron manganese phosphate material prepared in example 1 are observed by using a Japanese electron JEM-2100F type high-resolution transmission electron microscope, and the result is shown in FIG. 2, wherein the prepared sample is of a spheroidal structure, and the average size of particles is 100-200 nm; the carbon is coated on the surface of the material uniformly and completely, and the thickness of the coated carbon layer is about 2-3 nm; the product prepared in comparative example 1 has a non-uniform morphology, shows a large block shape, and is incompletely coated with a carbon layer, so that the transport of electrons may be affected in the uncoated portion during the charge and discharge processes, and the capacity may not be fully contributed.
Performance analysis:
uniformly mixing the lithium iron manganese phosphate positive electrode material prepared in the embodiment and the comparative example, a Carbon Nanotube (CNT) conductive agent, a carbon black (Super P) conductive agent and a polyvinylidene fluoride (PVDF) binder according to a mass ratio of 94:1:2:3, dropping N-methylpyrrolidone (NMP) to adjust the mixed solution to a proper concentration, and homogenizing. And uniformly coating the slurry on an aluminum foil, drying at 100 ℃, rolling by using a roll machine, then preparing a pole piece with the diameter of 12mm by using a sheet punching machine, weighing, and deducting the mass of the aluminum foil to obtain the mass of the active substance.
After the pole piece is dried in vacuum at 120 ℃ for 12h, a metal lithium piece is taken as a counter electrode, a Celgard2400 polypropylene microporous membrane is taken as a diaphragm, 1mol/L LiPF6/(EC + EMC + DMC) (volume ratio of 1:1:1) is taken as electrolyte, and a CR2032 type button cell is assembled in a high-purity argon glove box.
The electrochemical performance test of the CR2032 type button cell is carried out by adopting a Wuhan blue electricity CT2001A type cell test system: (1) specific capacity test: charging the battery to 4.5V at constant current and constant voltage by adopting 0.1C, stopping the current to be 0.02C, then discharging to 2.5V by using 0.1C, and calculating the discharging specific capacity of the battery; (2) and (3) testing the cycle performance: charging the battery to 4.5V at constant current and constant voltage by adopting 0.1C, stopping current to be 0.02C, then discharging to 2.5V by using 0.1C, finishing circulation for 50 circles, and carrying out comparative analysis on the capacity retention rate of the battery; (3) and (3) rate performance test: and respectively charging the battery to 4.5V at constant current and constant voltage by adopting 0.1C, 0.2C, 0.5C and 1C, stopping the current to be 0.02C, then respectively discharging the battery to 2.5V by applying 0.1C, 0.2C, 0.5C and 1C, and calculating the rate discharge specific capacity of the battery. The test results are shown in tables 1 and 2:
table 1 shows the results of the charge and discharge performance tests of the lithium iron manganese phosphate material with secondary carbon coating obtained in the example and the lithium iron manganese phosphate material with primary carbon coating obtained in the comparative example.
Table 2 shows the results of the rate performance tests of the lithium iron manganese phosphate material coated with carbon twice obtained in the example and the lithium iron manganese phosphate material coated with carbon once obtained in the comparative example.
Compared with the comparative examples, the invention adopts the improved high-temperature solid phase method, and adds the carbon source again for secondary carbon coating after the sample is presintered, thereby not only preventing the agglomeration phenomenon of the sintered product and obtaining particles with small size and good dispersibility, but also forming a more uniform and compact carbon coating layer. On one hand, the smaller particle size can shorten the diffusion distance of ions, so that the embedding and removing processes are smoother, the interface transfer impedance of the material can be reduced, and the conduction of the ions is facilitated; on the other hand, the abundant carbon conducting layers provide a convenient path for electron transmission, and effectively enhance ion diffusion and electron conductivity, so that the lithium iron manganese phosphate material coated with carbon on the second side has electrochemical performance superior to that of the lithium iron manganese phosphate material coated with carbon on the first side, and the lithium iron manganese phosphate material can meet the requirements of high power and high energy density of a power battery.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A preparation method of lithium ion battery anode material lithium iron manganese phosphate is characterized by comprising the following steps: by a modification technology, a secondary carbon coating process is introduced into a traditional high-temperature solid phase method, and the method comprises the following specific steps:
(1) weighing a certain amount of lithium source, manganese source, iron source and phosphorus source according to the mass ratio of 1.0-1.2: 0.6:0.4:1.0, then adding 10-25% by mass of carbon source, placing the mixture in a ball milling tank, adding absolute ethyl alcohol as a dispersing agent, grinding and dispersing for 4-6 h at the rotating speed of 280-400 r/min, drying and grinding the uniformly mixed slurry to obtain precursor powder;
(2) controlling the heating rate to be 5-12 ℃/min, heating the precursor powder obtained in the step (1) to 250-350 ℃ in an inert gas atmosphere, pre-burning at a constant temperature for 2-5 h, and cooling along with a furnace to obtain a pre-sintered product;
(3) taking out the pre-sintered product, grinding the pre-sintered product, adding a carbon source with the mass fraction of 3-10%, uniformly mixing, and performing ball milling on the prepared sample in an absolute ethyl alcohol medium at the speed of 280-400 r/min for 2-4 h to perform secondary carbon coating;
(4) controlling the heating rate to be 5-12 ℃/min, calcining the mixture powder obtained in the step (3) at 550-750 ℃ for 3-12 h under the protection of inert gas atmosphere, and cooling to room temperature along with the furnace to obtain the lithium iron manganese phosphate cathode material coated with carbon twice.
2. The method for preparing the lithium iron manganese phosphate as the positive electrode material of the lithium ion battery according to claim 1, which is characterized in that: the lithium source in the step (1) is one or two of lithium carbonate and lithium hydroxide.
3. The method for preparing the lithium iron manganese phosphate as the positive electrode material of the lithium ion battery according to claim 1, which is characterized in that: the manganese source in the step (1) is one or more of manganese carbonate, manganese sulfate, manganese oxalate and manganese acetate.
4. The method for preparing lithium iron manganese phosphate as the positive electrode material of the lithium ion battery according to claim 1, which is characterized by comprising the following steps: the iron source in the step (1) is one or more of ferrous nitrate, ferrous oxalate, ferrous sulfate and ferrous chloride.
5. The method for preparing the lithium iron manganese phosphate as the positive electrode material of the lithium ion battery according to claim 1, which is characterized in that: the phosphorus source in the step (1) is one or two of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
6. The method for preparing the lithium iron manganese phosphate as the positive electrode material of the lithium ion battery according to claim 1, which is characterized in that: the carbon source in the steps (1) and (3) is one or more of glucose, citric acid, carbon nano tubes and polyethylene glycol.
7. The method for preparing the lithium iron manganese phosphate as the positive electrode material of the lithium ion battery according to claim 1, which is characterized in that: the inert gas in the steps (2) and (4) is nitrogen or argon.
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| CN115180608A (en) * | 2022-07-26 | 2022-10-14 | 江西赣锋锂电科技股份有限公司 | Preparation method of spherical lithium iron manganese phosphate with high tap density |
| CN115196611A (en) * | 2022-07-26 | 2022-10-18 | 江西赣锋锂电科技股份有限公司 | Low-cost lithium iron phosphate and preparation method of lithium manganese iron phosphate |
| CN115304045A (en) * | 2022-08-29 | 2022-11-08 | 西藏锂时代科技有限公司 | Application of lithium iron manganese phosphate as electrode material in brine electrochemical lithium extraction |
| CN115535991A (en) * | 2022-09-28 | 2022-12-30 | 深圳中芯能科技有限公司 | Nanocrystalline phosphoric acid series anode material and preparation method thereof |
| CN115632120A (en) * | 2022-11-01 | 2023-01-20 | 湖南东舟能源有限公司 | Preparation method of quick conductive modified lithium iron manganese phosphate, battery positive plate and battery |
| CN115632120B (en) * | 2022-11-01 | 2023-07-04 | 湖南东舟能源有限公司 | Preparation method of quick conductive modified lithium manganese iron phosphate, battery positive plate and battery |
| CN115849327A (en) * | 2022-12-13 | 2023-03-28 | 广东邦普循环科技有限公司 | Lithium manganese iron phosphate cathode material and preparation method thereof |
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