CN114162879A - Micron-sized lithium ion battery cathode material and preparation method thereof - Google Patents
Micron-sized lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
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- 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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- 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
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention relates to the field of lithium ion battery anode materials, in particular to a micron-sized lithium ion battery anode material and a preparation method thereof, wherein the preparation raw materials of the micron-sized lithium ion battery anode material comprise a lithium source and a lithium ion battery anode material precursor, and the particle size D50 of the lithium source is 4-12 mu m. According to the lithium ion battery anode material, lithium carbonate and lithium hydroxide are used as a mixed lithium source, a eutectic body can be formed through heating, the reaction activation energy in the preparation process is reduced, the reaction temperature and the reaction time in the synthesis of the lithium ion battery anode material are reduced, the power density and the electric capacity of the battery are improved, the excellent cycling stability is achieved, the higher cycling capacity retention rate is achieved, and the service life of the battery is prolonged.
Description
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to H01M 4/48.
Background
At present, the lithium ion battery becomes a hot topic due to the rapidly-developed new energy automobile industry. CN201310675280 firstly prepares a solution by nickel sulfate, cobalt sulfate and manganese sulfate, regulates pH, bakes, dries to obtain a precursor, then mixes lithium carbonate, lithium fluoride and the precursor, bakes to obtain the ternary cathode material, and the cathode material has the characteristic of prolonging the cycle life of the battery, however, the reaction temperature is higher in the preparation process of the cathode material. CN201310233763 adopts nickel hydroxide, manganese carbonate, lithium hydroxide, and lithium carbonate to provide a positive electrode material after sintering, and similarly, the sintering temperature of the positive electrode material is too high, which not only affects the production efficiency, but also affects the subsequent use quality of the positive electrode material.
Disclosure of Invention
In view of the problems in the prior art, the first aspect of the present invention provides a micron-sized lithium ion battery cathode material, which comprises a lithium source and a lithium ion battery cathode material precursor, wherein the particle size D50 of the lithium source is 4-12 μm.
When the lithium source is a multi-component mixture, the particle size D50 of the lithium source is 4-12 μm in the application, which means the D50 particle size of the lithium source after the multi-component mixture.
D50: the cumulative percent particle size distribution for a sample at 50% corresponds to the particle size. Its physical meaning is that the particle size is greater than 50% of its particles and less than 50% of its particles, D50 also being referred to as the median or median particle size.
The precursor of the lithium ion battery positive electrode material in the application comprises but is not limited to lithium cobaltate LiCoO2And nickel cobalt manganese oxide Li (NixCoyMn)1-x-y)O2And nickel cobalt aluminum oxide Li (NixCoyAl)1-x-y)O2And nickel cobalt manganese aluminum oxide Li (NixCoyMnzAl)1-x-y-z)O2And a lithium-rich cathode material xLi2MnO3·(1-x)LiMnO2. Wherein x, y, z are any number less than 1.
In one embodiment, the lithium source is selected from one or more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium chloride, and lithium oxalate.
Preferably, the purity of the lithium carbonate is greater than or equal to 90 wt%, and the purity of the lithium hydroxide is greater than or equal to 50 wt%; more preferably, the purity of the lithium carbonate is 99.5 wt% or more, and the purity of the lithium hydroxide is 56 wt% or more.
Preferably, the lithium source comprises lithium carbonate and lithium hydroxide, and the weight ratio of the lithium source to the lithium hydroxide is 1: (0.25-1.5); more preferably, the weight ratio of the lithium carbonate to the lithium hydroxide is 1: 1.5.
in one embodiment, the lithium carbonate has a particle size D50 of 10 μm or less.
In one embodiment, the lithium hydroxide has a particle size D50 of 10 μm or less.
The second aspect of the invention provides a preparation method of the micron-sized lithium ion battery cathode material, which comprises the following steps:
(1) mixing lithium carbonate and lithium hydroxide, and then mixing with a lithium ion battery anode material precursor to form a lithium ion battery anode material precursor mixture;
(2) and roasting the precursor mixture of the lithium ion battery anode material to obtain the lithium ion battery anode material.
In one embodiment, the method of mixing lithium carbonate and lithium hydroxide comprises: the lithium carbonate and lithium hydroxide were mixed using a high speed mixer at a rate of 600-800r/min for 10-30 min.
Preferably, the method for mixing lithium carbonate and lithium hydroxide comprises the following steps: the lithium carbonate and lithium hydroxide were mixed for 20min at a rate of 800r/min using a high speed mixer.
In one embodiment, the temperature of the mixture is maintained at no more than 60 ℃ during the mixing of lithium carbonate and lithium hydroxide.
In one embodiment, the step (1) comprises: and mixing the lithium carbonate and the lithium hydroxide for 10-30min at the speed of 600-800r/min by using a high-speed mixer, and after adding the lithium ion positive electrode material precursor, mixing for 20-40min at the speed of 600-800r/min by using the high-speed mixer.
Preferably, the step (1) includes: the lithium carbonate and the lithium hydroxide were mixed at a rate of 800r/min for 20min using a high-speed mixer, and after the lithium ion positive electrode material precursor was added, the mixture was mixed at a rate of 800r/min for 30min using a high-speed mixer.
In one embodiment, the calcination temperature in step (2) is 800-.
In one embodiment, the step (2) comprises: the precursor mixture of the lithium ion battery anode material is roasted for 8-11h at the temperature of 800-950 ℃, and then is crushed, sieved and roasted again at the temperature of 750-850 ℃.
Preferably, the step (2) includes: roasting the precursor mixture of the lithium ion battery anode material at 800-950 ℃ for 8-11h, crushing, sieving, roasting again at 750-850 ℃ for 5-7h, crushing, and sieving to obtain the lithium ion battery anode material.
Preferably, the step (2) includes: and roasting the precursor mixture of the lithium ion battery anode material at 910 ℃ for 10h, crushing, sieving, roasting again at 800 ℃ for 6h, crushing, and sieving to obtain the lithium ion battery anode material.
The mode of pulverization in the present application is not particularly limited, and those skilled in the art can select the pulverization mode in a usual manner, and examples thereof include roll pulverization, jaw pulverization, mechanical pulverization, and air current pulverization.
In one embodiment, the mesh size of the screen is 325 mesh.
In one embodiment, the particle size D50 is maintained between 10.5 and 12.5 μm after crushing.
Preferably, the particle size D50 is maintained at 11.5 μm after grinding.
The atmosphere for calcination in this application is air or oxygen.
At present, in order to obtain a uniform crystal phase structure, a single lithium source is mostly used, however, the use of the single lithium source requires higher temperature and baking time for the baking temperature at the later stage, and the applicant unexpectedly finds that, among a plurality of lithium sources, lithium carbonate and lithium hydroxide are specifically selected while maintaining the weight ratio of 1: (0.25-1.5), in the later roasting process, roasting can be completed at a lower temperature in a shorter time, and the applicant guesses that the possible reason is that in the high-temperature roasting process, part of mixed lithium source is melted, the reaction is carried out between solid and liquid, the ion diffusion rate is obviously accelerated, the reaction activation energy in the preparation process is reduced, the reaction temperature and time can be effectively reduced, and the performance of the cathode material is improved.
In addition, the applicant has unexpectedly found that when the particle size of the single-component lithium source is less than 10 μm, the mixed lithium source D50 is 4-12 μm, and the material mixing temperature is kept not more than 60 ℃ during the mixing process, and the mixed material is mixed at the speed of 600-800r/min for a specific time by using a high-speed mixer, after the mixed material and the precursor are roasted under the specific conditions of the application, the structure of the cathode material can realize the mixture of single crystal, quasi-single crystal and aggregate, and the distribution state of the crystal phase of the mixture is proper, so that the better electrical property, especially the circulation stability at 45 ℃ is maintained in the structure of multiple crystal phases.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method, lithium carbonate and lithium hydroxide are used as a mixed lithium source, a eutectic body can be formed by heating, the reaction activation energy in the preparation process is reduced, the reaction temperature and the reaction time in the synthesis of the lithium ion battery anode material are reduced, the power density and the electric capacity of the battery are improved, and meanwhile, the preparation method has excellent cycle stability, higher cycle capacity retention rate and longer service life of the battery;
(2) the particle size of a single lithium source is controlled to be less than 10 mu m, the mixed lithium source D50 is controlled to be 4-12 mu m, the temperature of a mixed material is kept to be not more than 60 ℃ in the mixing process, meanwhile, a high-speed mixer is used for mixing for a specific time at the speed of 600-800r/min, after the mixed material and a precursor are roasted under the specific conditions, the structure of the positive electrode material can realize the mixture of single crystal, quasi-single crystal and an aggregate, and the distribution state of the crystal phase of the mixture is proper, so that better electrical property, especially 45 ℃ circulation stability, is maintained in a plurality of crystal phase structures.
Drawings
FIGS. 1 to 4 are SEM images of the lithium ion battery positive electrode materials obtained in examples 1 to 4 of the present application, respectively;
FIG. 5 is a first charge-discharge curve of a battery prepared from the lithium ion battery positive electrode material of examples 1-4 of the present application;
FIG. 6 is a cyclic charge and discharge curve of a battery prepared from the lithium ion battery positive electrode material of examples 1-4 of the present application;
FIG. 7 is a DSC curve of the positive electrode material of the lithium ion battery obtained in examples 1 to 3 of the present application.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
Examples
Example 1
Embodiment 1 of the present invention provides a micron-sized lithium ion battery cathode material, and the specific preparation method thereof is as follows:
(1) firstly, mixing lithium hydroxide and lithium carbonate by a high-speed mixer, wherein the mixing mass ratio of the lithium carbonate to the lithium hydroxide is 40%: 60%, mixing the mixture by using a high-speed mixer at a mixing rate of 800r/min for 20 minutes to form a eutectic of lithium hydroxide and lithium carbonate, keeping the temperature of the mixed material to be lower than 60 ℃ in the mixing process, then adding a precursor of a positive electrode material of a Jintong lithium ion battery NCM523 in Lanzhou, mixing the mixture by using the high-speed mixer at a mixing rate of 800r/min for 30 minutes to form a precursor mixture of the positive electrode material of the lithium ion battery;
(2) roasting the precursor mixture of the lithium ion battery anode material in a box type furnace at the roasting temperature of 910 ℃ for 10 hours to form a primary block material;
(3) crushing the roasted primary blocky material for 2 times by a pair of rollers, performing airflow crushing, controlling the particle size D50 to be 11.5 mu m, and simultaneously performing 325-mesh sieving to form a primary crushed material;
(4) roasting the primary crushed material for 6 hours in a box-type furnace at 800 ℃ to form secondary blocky material;
(5) and crushing the roasted secondary block material for 2 times by using a pair of rollers, performing airflow crushing, controlling the granularity D50 to be 11.5 mu m, and simultaneously performing magnetism removal and 325-mesh sieving to prepare the lithium ion battery anode material.
Wherein the particle size of the lithium hydroxide is 5.8 μm, the purity is 56.5 percent, and the lithium hydroxide is purchased from the Jiangxi lithium industry; lithium carbonate, having a particle size of 6.1 μm and a purity of 99.76%, was purchased from Jiangxi Toutong.
The weight ratio of the total weight of the lithium carbonate and the lithium hydroxide to the precursor of the positive electrode material of the lithium ion battery is 1: 2.4.
Example 2
Embodiment 2 of the present invention provides a micron-sized lithium ion battery cathode material, and the specific preparation method thereof is as follows:
(1) firstly, mixing lithium carbonate and a positive electrode material precursor of a Jintong NCM523 lithium ion battery in Lanzhou through a high-speed mixer at the mixing speed of 800r/min for 30 minutes to form a positive electrode material precursor mixture of the lithium ion battery.
(2) Roasting the precursor mixture of the lithium ion battery anode material in a box type furnace at the roasting temperature of 910 ℃ for 10 hours to form a primary block material;
(3) crushing the roasted primary blocky material for 2 times by a pair of rollers, performing airflow crushing, controlling the particle size D50 to be 11.5 mu m, and simultaneously performing 325-mesh sieving to form a primary crushed material;
(4) roasting the primary crushed material for 6 hours in a box-type furnace at 800 ℃ to form secondary blocky material;
(5) and crushing the roasted secondary block material for 2 times by using a pair of rollers, performing airflow crushing, controlling the granularity D50 to be 11.5 mu m, and simultaneously performing magnetism removal and 325-mesh sieving to prepare the lithium ion battery anode material.
Wherein the particle size of the lithium carbonate is 6.1 μm and is purchased from Jiangxiengtong.
The weight ratio of the lithium carbonate to the lithium ion battery positive electrode material precursor is 1: 2.4.
Example 3
Embodiment 3 of the present invention provides a micron-sized lithium ion battery cathode material, which is specifically prepared by the following steps:
(1) firstly, mixing lithium hydroxide and a positive electrode material precursor of a Jintong NCM523 lithium ion battery in Lanzhou through a high-speed mixer at the mixing speed of 800r/min for 30 minutes to form a positive electrode material precursor mixture of the lithium ion battery.
(2) Roasting the precursor mixture of the lithium ion battery anode material in a box type furnace at the roasting temperature of 910 ℃ for 10 hours to form a primary block material;
(3) crushing the roasted primary blocky material for 2 times by a pair of rollers, performing airflow crushing, controlling the particle size D50 to be 11.5 mu m, and simultaneously performing 325-mesh sieving to form a primary crushed material;
(4) roasting the primary crushed material for 6 hours in a box-type furnace at 800 ℃ to form secondary blocky material;
(5) and crushing the roasted secondary block material for 2 times by using a pair of rollers, performing airflow crushing, controlling the granularity D50 to be 11.5 mu m, and simultaneously performing magnetism removal and 325-mesh sieving to prepare the lithium ion battery anode material.
Wherein the particle size of lithium hydroxide is 5.8 μm, and is purchased from Ganfeng Li industry.
The weight ratio of the lithium hydroxide to the lithium ion battery anode material precursor is 1: 2.4.
Example 4
Embodiment 4 of the present invention provides a micron-sized lithium ion battery cathode material, which is specifically prepared by the following steps:
(1) firstly, mixing lithium hydroxide and lithium nitrate by a high-speed mixer, wherein the mixing mass ratio of the lithium nitrate to the lithium hydroxide is 40%: 60 percent, the mixing rate is 800r/min, the mixture is mixed for 20 minutes to form a eutectic of lithium hydroxide and lithium nitrate, the temperature of the mixed material is kept lower than 60 ℃ in the mixing process, then a precursor of a positive electrode material of a Jintong lithium ion battery NCM523 in Lanzhou is added, the mixture is mixed by a high-speed mixer, the mixing rate is 800r/min, and the mixture is mixed for 30 minutes to form a precursor mixture of the positive electrode material of the lithium ion battery;
(2) roasting the precursor mixture of the lithium ion battery anode material in a box type furnace at the roasting temperature of 910 ℃ for 10 hours to form a primary block material;
(3) crushing the roasted primary blocky material for 2 times by a pair of rollers, performing airflow crushing, controlling the particle size D50 to be 11.5 mu m, and simultaneously performing 325-mesh sieving to form a primary crushed material;
(4) roasting the primary crushed material for 6 hours in a box-type furnace at 800 ℃ to form secondary blocky material;
(5) and crushing the roasted secondary block material for 2 times by using a pair of rollers, performing airflow crushing, controlling the granularity D50 to be 11.5 mu m, and simultaneously performing magnetism removal and 325-mesh sieving to prepare the lithium ion battery anode material.
Wherein the particle size of the lithium hydroxide is 5.8 μm, the purity is 56.5 percent, and the lithium hydroxide is purchased from the Jiangxi lithium industry; lithium nitrate was purchased from Shandong Teng chemical Co., Ltd, battery grade, cat # 101.
The weight ratio of the lithium nitrate to the lithium hydroxide to the precursor of the positive electrode material of the lithium ion battery is 1: 2.4.
SEM images of the lithium ion battery positive electrode materials obtained in examples 1 to 4 are shown in fig. 1 to 4, respectively.
Performance evaluation
DSC analysis: DSC analysis was performed on the lithium ion battery positive electrode materials obtained in examples 1 to 3 using DSC thermal analyzers, respectively, wherein the temperature program of the instrument was 10 ℃/min. The obtained DSC curves are shown in FIG. 7, respectively.
As can be seen from fig. 7, the lithium ion battery positive electrode material obtained in example 1 has an absorption peak before 100 ℃, which is generated by water volatilization, and the DSC curve of the lithium ion positive electrode material in comparative example 3 has a small amplitude left-shifted, and the DSC curve of the lithium ion positive electrode material in comparative example 2 has a large amplitude left-shifted. Meanwhile, the lithium ion battery positive electrode material obtained in example 1 has an absorption peak at about 420 ℃, which is the decomposition absorption peak of the lithium ion battery positive electrode material obtained in example 1, the peak has a small amplitude left shift in a DSC curve of the lithium ion positive electrode material in comparative example 3, and the peak has a large amplitude left shift in a DSC curve of the lithium ion positive electrode material in comparative example 2, which has a difference of about 90 ℃. The lithium ion cathode material in the embodiment 1 has an absorption peak at about 715 ℃, the peak is a chemical reaction absorption peak, the DSC curve of the lithium ion cathode material in the comparative example 3 has a remarkable absorption peak, and the DSC curve of the lithium ion cathode material in the comparative example 2 has a small amplitude which is shifted to the left.
It can be seen from this that, in the lithium ion positive electrode material in example 1, the moisture volatilization absorption peak, the substance decomposition absorption peak, and the chemical reaction absorption peak are relatively shifted to the left compared to the single component, and the absorption peak generation temperature is reduced, so that the reaction can be performed at a relatively low temperature.
2. And (3) testing electrical properties: the lithium ion battery positive electrode materials in examples 1 to 4 were prepared into batteries respectively by the following methods: uniformly mixing the material or blank sample obtained in the embodiment, conductive carbon black and polyvinylidene fluoride in a solvent N-methyl pyrrolidone according to the weight ratio of 8:1:1, and coating an aluminum foil to form a pole piece; and (3) drying the prepared pole piece for 5 hours in a vacuum drying oven at 110 ℃ for later use. And rolling the pole piece on a rolling machine, and punching the rolled pole piece into a circular pole piece. The cell assembly was carried out in a glove box filled with argon, the electrolyte of the electrolyte was 1MLiPF6, the solvent was EC: DEC: DMC is 1:1:1 (volume ratio), and the metal lithium sheet is the counter electrode. The capacity test was performed on a blue CT model 2001A tester. And respectively carrying out charge and discharge tests on the prepared batteries, wherein the test voltage is 3.0-4.3V, the cycle test condition is 0.5CC/1.0CD, the cycle test conditions are 50 cycles, respectively recording the last discharge capacity, and dividing the last cycle discharge capacity by the first cycle discharge capacity to obtain the cycle retention rate.
Wherein, the first charge-discharge curve of the battery prepared by the lithium ion battery cathode material in the example 1 is shown in figure 5, and the cycle charge-discharge curve is shown in figure 6.
The first charge-discharge capacity and the cycle charge-discharge capacity retention ratio are shown in Table 1.
TABLE 1
Claims (10)
1. The micron-sized lithium ion battery cathode material is characterized in that the preparation raw materials comprise a lithium source and a lithium ion battery cathode material precursor, wherein the particle size D50 of the lithium source is 4-12 mu m.
2. The micron-sized lithium ion battery cathode material according to claim 1, wherein the lithium source is selected from one or more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium chloride and lithium oxalate.
3. The micron-sized lithium ion battery cathode material according to claim 2, wherein the lithium carbonate has a purity of 90 wt% or more; the purity of the lithium hydroxide is more than or equal to 50 wt%.
4. The micron-sized lithium ion battery positive electrode material according to claim 3, wherein the lithium source comprises lithium carbonate and lithium hydroxide in a weight ratio of 1: (0.25-1.5).
5. The preparation method of the micron-sized lithium ion battery cathode material according to claim 4, characterized by comprising the following steps:
(1) mixing lithium carbonate and lithium hydroxide, and then mixing with a lithium ion battery anode material precursor to form a lithium ion battery anode material precursor mixture;
(2) and roasting the precursor mixture of the lithium ion battery anode material to obtain the lithium ion battery anode material.
6. The method for preparing the micron-sized lithium ion battery cathode material according to claim 5, wherein the method for mixing the lithium carbonate and the lithium hydroxide comprises the following steps: the lithium carbonate and lithium hydroxide were mixed using a high speed mixer at a rate of 600-800r/min for 10-30 min.
7. The method for preparing the micron-sized lithium ion battery cathode material according to claim 6, wherein the temperature of the mixed material is kept to be not more than 60 ℃ during the mixing process of the lithium carbonate and the lithium hydroxide.
8. The method for preparing the micron-sized lithium ion battery cathode material according to claim 7, wherein the step (1) comprises the following steps: and mixing the lithium carbonate and the lithium hydroxide for 10-30min at the speed of 600-800r/min by using a high-speed mixer, and after adding the lithium ion positive electrode material precursor, mixing for 20-40min at the speed of 600-800r/min by using the high-speed mixer.
9. The method for preparing micron-sized lithium ion cathode material according to any one of claims 5 to 8, wherein the calcination temperature in the step (2) is 800-1100 ℃.
10. The method for preparing the micron-sized lithium ion positive electrode material according to claim 8, wherein the step (2) comprises: the precursor mixture of the lithium ion battery anode material is roasted for 8-11h at the temperature of 800-950 ℃, and then is crushed, sieved and roasted again at the temperature of 750-850 ℃.
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