CN111477865A - Method for producing lithium manganate in internal oxygen mode - Google Patents
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- C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
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Abstract
The invention discloses an internal oxygen type method for producing lithium manganate, which comprises the following steps of weighing lithium carbonate and manganese source according to the molar ratio of lithium to manganese, pouring the lithium carbonate and manganese source and zirconia balls into an inclined mixer according to the proportion for mixing, putting the mixture into a sagger, putting the sagger into a muffle furnace, introducing air for sintering, heating, sintering at constant temperature for a period of time, stopping introducing electricity after sintering is finished, stopping introducing air in a cooling section at 780-500 ℃, and introducing industrial oxygen for a period of time to enable L iMn2O4Slowly cooling in high oxygen content atmosphere to prevent oxygen-deficient solid solution L iMn2O4-generation of x; after the furnace temperature is reduced to 500 ℃, stopping introducing oxygen, changing into introducing air, and cooling to below 100 DEG C(ii) a And opening the furnace door to pour out the sintered material, crushing and sieving to obtain a finished product. The method provided by the invention fully utilizes the advantages that the performance of the lithium manganate prepared by taking manganous-manganic oxide as a raw material is good and the oxygen can be generated by taking manganese dioxide as a raw material, and improves the cost performance of the lithium manganate by making up for the deficiencies and taking synergistic effects.
Description
Technical Field
The invention relates to the technical field of battery material preparation, in particular to an internal oxygen type method for producing lithium manganate.
Background
The lithium manganate material is one of four anode materials of a lithium ion battery, the raw material for producing the lithium manganate material at present is mainly manganese dioxide, and the morphology, the specific surface area, the granularity and the distribution of the manganese dioxide, the content of impurities such as iron, sulfate radicals, sodium ions and the like cannot be effectively controlled, so that the lithium manganate material with high performance is difficult to produce, and the requirement of the lithium ion power battery is difficult to meet. In order to further improve the comprehensive performance, particularly the electrical performance, of lithium manganate, a large number of experimental researches are carried out by researchers at home and abroad, and research results prove that the capacity and the cycle performance of a battery for synthesizing lithium manganate by using manganous-manganic oxide as a manganese source are greatly improved, and the electrical performance is obviously superior to that of lithium manganate using electrolytic manganese dioxide as a manganese source. The main reason for improving the electrical property is that the manganous-manganic oxide and the lithium manganate have a spinel structure, and the structure change is relatively small in the sintering process, so that the caused internal stress is smaller, and the material structure is more stable. Therefore, it is a trend to produce high-end lithium manganate by using battery-grade trimanganese tetroxide instead of electrolytic manganese dioxide as a manganese source, and currently, domestic main power battery manufacturers such as Suzhou star constant power supply, Huizhou Yiwei lithium energy and the like specify to purchase lithium manganate using trimanganese tetroxide as the manganese source.
At present, the annual demand of battery grade trimanganese tetroxide is more than about 30000 tons, and along with the continuous use in the fields of power and energy storage, the demand is rising year by year, and the product has wide market prospect and higher economic benefit. With the continuous progress of the technology and the higher and higher requirements on the battery performance, the demand on battery-grade manganous manganic oxide is continuously increased, but external oxygen is needed for preparing the lithium manganate by using the manganous manganic oxide, but if oxygen is introduced in the whole sintering process, the cost is greatly increased, and in addition, the current lithium manganate is low in price, about 3 ten thousand yuan/ton, the loss is caused, the process is unreasonable in economy, and the reason for large-scale popularization is not yet, so that the oxygen supply problem of the process for preparing the lithium manganate by using the manganous manganic oxide needs to be solved at low cost, and the process is vital. Therefore, it is necessary to develop the research on the production technology and the large-scale industrialization of the battery grade trimanganese tetroxide.
Disclosure of Invention
The invention aims to: aiming at the problems, the method for preparing the lithium manganate by the internal oxygen method is provided, the method fully utilizes the advantages that the performance of the lithium manganate prepared by taking the trimanganese tetroxide as the raw material is good and the oxygen can be generated by taking the manganese dioxide as the raw material, and improves the cost performance of the lithium manganate by making up for the deficiencies of the advantages and the synergistic effect.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method for producing lithium manganate by an internal oxygen method comprises the following steps:
(1) weighing raw materials: weighing lithium carbonate and a manganese source according to the molar ratio of lithium to manganese, and then pouring the lithium carbonate and the manganese source into an inclined mixer to mix to obtain a mixture;
(2) mixing and screening: weighing zirconia balls according to a certain ball-to-material ratio, adding the zirconia balls into an inclined mixer, starting the mixer to mix uniformly, pouring out the mixture and the zirconia balls together, screening to separate the zirconia balls from the mixture, and filling the mixture into a sagger to be burnt;
(3) and (3) high-temperature sintering: placing the sagger filled with the mixture into a muffle furnace, introducing air for sintering to ensure that the oxygen content in the furnace atmosphere is less than 20 percent and CO2 gas is contained, firstly heating and then sintering at constant temperature for a period of time;
(4) and (3) oxygen protection cooling: after the sintering constant temperature time is up, closing a kiln power switch, stopping electrifying air in a cooling section at 780-adulterated temperature of 500 ℃, and introducing industrial oxygen for a period of time to ensure thatLiMn2O4Slowly cooling in high oxygen content atmosphere to prevent oxygen-deficient solid solution L iMn2O4-generation of x;
(5) air protection cooling: after the furnace temperature is reduced to 500 ℃, stopping introducing oxygen, changing into introducing air, and cooling to below 100 ℃;
(6) sample treatment: and opening the furnace door to pour out the sintered material after the furnace is cooled, crushing and sieving to obtain the finished product.
Further, in the step (1), the molar ratio of lithium to manganese is 0.5 to 0.6, and the manganese source includes manganese dioxide and trimanganese tetroxide, wherein the molar ratio of manganese dioxide is 80 to 90%.
Further, in the step (2), the mass of the zirconia balls is 1-3 times of that of the mixed material, the mixing time of the mixed material and the zirconia balls is 150-200min, and the sieve mesh number is 200 meshes.
Furthermore, the zirconia balls have three diameters, and the ratio of the three diameters from large to small is 3:4: 3.
Further, in the step (3), the heating rate is 3-5 ℃/min, the constant temperature is 780 ℃, and the constant temperature time is 10-20 h.
Further, in the step (4), the oxygen content of the industrial oxygen is more than 99.2%, and the oxygen flow is 1m3H, ensuring that the oxygen content in the furnace atmosphere is more than 90 percent, and leading in the oxygen for 1.5 to 3 hours.
Further, in the step (5), the air is introduced at an introduction flow rate of 2m3/h。
Further, in the step (6), the pulverization is carried out by manually carrying out pulverization for a plurality of times, and the mesh number of the sieving is 200 meshes.
The reaction principle is as follows: the test adopts a high-temperature solid-phase reaction method to prepare the lithium manganate, and the reaction of preparing the lithium manganate by using the trimanganese tetroxide is as follows:
reaction for preparing lithium manganate by manganese dioxide:
according to the method, when the manganous oxide is used for preparing the lithium manganate, oxygen is needed, the reaction for preparing the lithium manganate by using the manganese dioxide is to discharge the oxygen, if the manganese dioxide with a certain proportion is added when the manganous oxide is used for preparing the lithium manganate, the balance of oxygen supply and demand can be realized, namely, the oxygen requirement when the manganous oxide is used for preparing the lithium manganate can be basically met by supplying oxygen inside a reactant, external oxygen supply is basically not needed or a small amount of oxygen is supplemented from the outside, oxygen is supplied inside a material layer, the oxygen diffusion condition in the lithium manganate synthesis process is greatly improved, the oxygen distribution is uniform, the dispersion effect is good, the reaction is very favorable, the lithium manganate is completely crystallized and can improve the performance of the lithium manganate. On the contrary, in the lithium manganate synthetic process, if adopt outside oxygen suppliment, because the thickness and the resistance of bed of material, oxygen diffusion to bed of material is difficult, and oxygen supply is not enough, and the reactivity is poor, and lithium manganate develops the crystallization incompletely, and the performance defect, if adopt the oxygen boosting operation, will increase the oxygen expense, improves the manufacturing cost of lithium manganate greatly. According to theoretical calculation, the oxygen amount required by the reaction of preparing lithium manganate by using 1 mole of manganous manganic oxide is the oxygen amount released by the reaction of preparing lithium manganate by using 5 moles of manganese dioxide, namely the theoretical required amount of manganese dioxide is that the molar ratio of manganese dioxide is 83%. In consideration of the utilization rate of oxygen, the molar ratio of manganese dioxide is set to 81-90%.
In addition, to prevent oxygen-deficient solid solution L iMn2O4After the high-temperature sintering time is finished, industrial oxygen with the oxygen content of more than 99.5 percent is continuously introduced into the cooling section of 760 plus 500 ℃ during the front temperature reduction, so that the oxygen content in the furnace atmosphere is ensured to be more than 90 percent, and the oxygen introduction time is about 2 hours, so that L iMn is ensured2O4Slow cooling in high oxygen atmosphere ensures L iMn2O4Complete crystal development and prevention of hypoxia of L iMn2O4The formation of-x can improve the lithium manganateAnd (4) cycle performance.
The raw material for producing the lithium manganate material is mainly manganese dioxide, and the morphology, specific surface area, granularity and distribution of the manganese dioxide, and the content of impurities such as iron, sulfate radical, sodium ions and the like cannot be effectively controlled, so that the high-performance lithium manganate material is difficult to produce, and the requirements of a lithium ion power battery are difficult to meet. In order to further improve the comprehensive performance, particularly the electrical performance, of the lithium manganate, the battery capacity and the cycle performance of the lithium manganate synthesized by adopting the trimanganese tetroxide as a manganese source are greatly improved, and the electrical performance is obviously superior to that of the lithium manganate taking electrolytic manganese dioxide as a manganese source. The main reason for improving the electrical property is that the manganous-manganic oxide and the lithium manganate have a spinel structure, and the structure change is relatively small in the sintering process, so that the caused internal stress is smaller, and the material structure is more stable. Therefore, it has become a trend to replace a portion of the electrolytic manganese dioxide with battery grade trimanganese tetroxide as a manganese source to produce high-end lithium manganate.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
in order to fully utilize the advantages of good performance of the lithium manganate prepared by using manganous-manganic oxide as a raw material and the purpose of fully utilizing oxygen generated during the preparation of the lithium manganate by using manganese dioxide as a raw material, the method for preparing the lithium manganate has high cost performance by doping a manganese dioxide raw material into the manganous-manganic oxide raw material, wherein the molar ratio of the manganese dioxide is 81-90%. The oxygen generated inside the manganese dioxide is fully utilized when the manganese dioxide is used as the raw material to prepare the lithium manganate, the kiln is not filled with oxygen but only filled with air in the high-temperature sintering process, the oxygen content in the kiln is less than 20 percent in the sintering process, and the atmosphere contains CO simultaneously2Therefore, the production cost of the lithium manganate is greatly saved.
After the high-temperature sintering time is finished, in the cooling section of 780-500 ℃, introducing oxygen for protection cooling, introducing industrial oxygen to L iMn2O4Slow cooling in high oxygen atmosphere ensures L iMn2O4Complete crystal development and prevention of hypoxia of L iMn2O4The formation of-x can improve the lithium manganateAnd (4) cycle performance.
The lithium manganate produced by the technology has good performance and low cost, a sample is subjected to a power-on test, the 1C first discharge capacity reaches 125.21mAh/g, and after 50 times of charge-discharge circulation, the capacity retention rate is 95.60%, so that the performance of the lithium manganate prepared by taking manganese dioxide as a raw material is greatly superior to that of the lithium manganate prepared by taking manganese dioxide as a raw material.
Drawings
FIG. 1 is an XRD pattern of lithium manganate produced in example 2;
FIG. 2 is an electron micrograph of lithium manganate produced in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to preferred embodiments. It should be noted, however, that the numerous details set forth in the description are merely for the purpose of providing the reader with a thorough understanding of one or more aspects of the present invention, which may be practiced without these specific details.
Example 1
A method for producing lithium manganate by an internal oxygen method comprises the following steps:
step 1, weighing two manganese raw materials, wherein the weight of the two manganese raw materials is 1000 g based on the total weight of manganese dioxide and trimanganese tetroxide, 655.20 g of manganese dioxide raw material can be obtained according to the content of manganese dioxide in the manganese dioxide raw material, and 387.40 g of trimanganese tetroxide raw material can be obtained according to the content of trimanganese tetroxide in the trimanganese tetroxide raw material, so that 655.20 g of manganese dioxide raw material is weighed, 387.40 g of trimanganese tetroxide raw material is weighed, and the weighed manganese dioxide raw material and the trimanganese tetroxide raw material are poured into an inclined mixer.
And 2, weighing a lithium carbonate ingredient, namely taking the L i/Mn molar ratio of 0.52 according to the practical experience of production, calculating that the lithium carbonate raw material is 233.50 g according to the L i/Mn molar ratio of 0.52 and the lithium content in the lithium carbonate, and pouring the raw material and the two manganese raw materials into an inclined mixer for testing with the specification of 5L to mix.
And 3, mixing the raw materials, namely weighing 2552 g of zirconia balls according to a ball-to-material ratio of 2:1, wherein the ratio of balls with different sizes is phi 30: phi 20: phi 10 is 3:4:3, adding the weighed zirconia balls into an inclined mixer with the specification of 5L together, starting the mixer, taking the mixing time of 180 minutes according to experience, pouring out the balls after mixing, screening by using a 200-mesh screen to realize ball-to-material separation, and filling the mixed materials into an alumina sagger to be burnt.
And 4, step 4: and (3) introducing air for sintering: placing the sagger filled with the materials into a muffle furnace, and introducing air for sintering, wherein the sintering system is as follows: the heating speed is 3 ℃/min, the constant temperature is 780 ℃, the constant temperature time is 15 hours, the air flow is 2m3/h, and the oxygen content of the kiln is less than 20% in the sintering process.
And 5, introducing oxygen for protecting and cooling, namely closing a kiln power switch and stopping energization after the sintering constant temperature time is up, stopping introducing air after the high-temperature sintering time is finished and in the front cooling section of 780-500 ℃ after the high-temperature sintering time is finished, continuously introducing industrial oxygen with the oxygen content of more than 99.2 percent, wherein the oxygen flow is 1m3/h, the oxygen content in the atmosphere in the furnace is ensured to be more than 90 percent, and the oxygen introduction time is about 2 hours, so that L iMn is ensured to be L iMn2O4Slow cooling in high oxygen atmosphere ensures L iMn2O4Complete crystal development and prevention of hypoxia of L iMn2O4And the generation of-x can improve the cycle performance of lithium manganate.
Step 6: air cooling: after the temperature of the furnace is reduced to 500 ℃, the oxygen is stopped to be introduced, and the flow rate is 2m3Air/h, until the temperature is below 100 ℃.
And 7: treating a sintered sample: and after the furnace temperature is cooled to be below 100 ℃, opening the furnace door, pouring out the fired material, manually crushing, screening by using a 200-mesh analysis screen, manually crushing and screening for multiple times, then completely screening by using a 200-mesh screen, uniformly mixing undersize to obtain a qualified test sample, and testing the particle size, the first discharge capacity and the capacity retention rate after 50 cycles of the test sample to judge the test effect.
The granularity of a test sample is detected by a granularity meter to be D50 ═ 14.46um, the test sample is subjected to a deduction test, the 1C first discharge capacity reaches 123.79mAh/g, and after 50 times of charge-discharge circulation, the capacity retention rate is 94.75%.
Example 2
The molar ratio of manganese dioxide was 85%.
A method for producing lithium manganate by an internal oxygen method comprises the following steps:
step 1, weighing two manganese raw materials, wherein the weight of the two manganese raw materials is 1000 g based on the total weight of manganese dioxide and trimanganese tetroxide, 723.98 g of manganese dioxide raw material can be obtained according to the content of manganese dioxide in the manganese dioxide raw material, and 321.57 g of trimanganese tetroxide raw material can be obtained according to the content of trimanganese tetroxide in the trimanganese tetroxide raw material, so that 723.98 g of manganese dioxide raw material is weighed, 321.57 g of trimanganese tetroxide raw material is weighed, and the weighed manganese dioxide raw material and the trimanganese tetroxide raw material are poured into an inclined mixer.
And 2, weighing a lithium carbonate ingredient, namely taking the L i/Mn molar ratio of 0.52 according to the practical experience of production, calculating that the lithium carbonate raw material is 231.48 g according to the L i/Mn molar ratio of 0.52 and the lithium content in the lithium carbonate, and pouring the raw material and the two manganese raw materials into an inclined mixer for testing with the specification of 5L to mix.
And 3, mixing the raw materials, namely weighing 2550 g of zirconia balls according to a ball-to-material ratio of 2:1, wherein the ratio of balls with different sizes is phi 30: phi 20: phi 10 is 3:4:3, adding the weighed zirconia balls into an inclined mixer with the specification of 5L together, starting the mixer, taking the mixing time of 180 minutes according to experience, pouring out the balls after mixing, screening by using a 200-mesh screen to realize ball-to-material separation, and filling the mixed materials into a sagger for burning.
And 4, step 4: and (3) introducing air for sintering: placing the sagger filled with the materials into a muffle furnace, and introducing air for sintering, wherein the sintering system is as follows: the heating speed is 3 ℃/min, the constant temperature is 780 ℃, the constant temperature time is 15 hours, the air flow is 2m3/h, and the oxygen content of the kiln is less than 20% in the sintering process.
And 5, introducing oxygen for protection cooling, namely closing a kiln power switch after the sintering constant temperature time is up, stopping electrifying, and at the moment, L iMn for preventing oxygen-deficient solid solution2O4X is generated, thereby influencing the cycle of lithium manganateAfter the high-temperature sintering time is finished, when the temperature is reduced in the front, air is stopped to be introduced into a cooling section at 780-500 ℃, industrial oxygen with the oxygen content of more than 99.2 percent is continuously introduced, the oxygen flow is 1m3/h, the oxygen content in the furnace atmosphere is ensured to be more than 90 percent, and the oxygen introduction time is about 2 hours, so that L iMn2O4Slow cooling in high oxygen atmosphere ensures L iMn2O4Complete crystal development and prevention of hypoxia of L iMn2O4And the generation of-x can improve the cycle performance of lithium manganate.
Step 6: air cooling: after the temperature of the furnace is reduced to 500 ℃, the oxygen is stopped to be introduced, air with the flow rate of 2m3/h is introduced again, and the furnace is cooled to be below 100 ℃.
And 7: treating a sintered sample: and after the furnace temperature is cooled to be below 100 ℃, opening the furnace door, pouring out the fired material, manually crushing, screening by using a 200-mesh analysis screen, crushing and screening for multiple times, then completely screening by using a 200-mesh screen, uniformly mixing undersize to obtain a qualified test sample, and testing the particle size, the first discharge capacity and the capacity retention rate after 50 cycles of the test sample to judge the test effect.
The granularity of the sample is D50 ═ 14.18um through the detection of a granularity meter, the sample is subjected to a deduction test, the 1C first discharge capacity reaches 125.21mAh/g, and after 50 charging and discharging cycles, the capacity retention rate is 95.60%.
Example 3
The molar ratio of manganese dioxide is 90%.
A method for producing lithium manganate by an internal oxygen method comprises the following steps:
step 1, weighing two manganese raw materials, wherein the weight of the two manganese raw materials is 1000 g based on the total weight of manganese dioxide and trimanganese tetroxide, 820.12 g of manganese dioxide raw material can be obtained according to the content of manganese dioxide in the manganese dioxide raw material, and 226.82 g of trimanganese tetroxide raw material can be obtained according to the content of trimanganese tetroxide in the trimanganese tetroxide raw material, so that 820.12 g of manganese dioxide raw material is weighed, 226.82 g of trimanganese tetroxide raw material is weighed, and the weighed manganese dioxide raw material and the trimanganese tetroxide raw material are poured into an inclined mixer.
And 2, weighing a lithium carbonate ingredient, namely taking the L i/Mn molar ratio of 0.52 according to the practical experience of production, calculating that the lithium carbonate raw material is 228.03 g according to the L i/Mn molar ratio of 0.52 and the lithium content in the lithium carbonate, and pouring the lithium carbonate raw material and the above two manganese raw materials into an inclined mixer for test of 5L specification to mix.
And 3, mixing the raw materials, namely weighing 2550 g of zirconia balls according to a ball-to-material ratio of 2:1, wherein the ratio of balls with different sizes is phi 30: phi 20: phi 10 is 3:4:3, adding the weighed zirconia balls into an inclined mixer with the specification of 5L together, starting the mixer, taking the mixing time of 180 minutes according to experience, pouring out the balls after mixing, screening by using a 200-mesh screen to realize ball-to-material separation, and filling the mixed materials into an alumina sagger to be burnt.
And 4, step 4: and (3) introducing air for sintering: placing the sagger filled with the materials into a muffle furnace, and introducing air for sintering, wherein the sintering system is as follows: the heating rate is 3 ℃/min, the constant temperature is 780 ℃, the constant temperature time is 15 hours, and the air flow is 2m3And h, the content of the kiln oxygen in the sintering process is less than 20 percent.
And 5, introducing oxygen for protection cooling, namely closing a kiln power switch after the sintering constant temperature time is up, stopping electrifying, and at the moment, L iMn for preventing oxygen-deficient solid solution2O4After the high-temperature sintering time is finished, when the temperature is reduced in the front, air is stopped to be introduced into a cooling section at 780-500 ℃, industrial oxygen with the oxygen content of more than 99.2 percent is continuously introduced, the oxygen flow is 1m3/h, the oxygen content in the furnace atmosphere is ensured to be more than 90 percent, and the oxygen introduction time is about 2 hours, so that L iMn percent of the cycle performance of the lithium manganate is influenced2O4Slow cooling in high oxygen atmosphere ensures L iMn2O4Complete crystal development and prevention of hypoxia of L iMn2O4And the generation of-x can improve the cycle performance of lithium manganate.
Step 6: air cooling: after the temperature of the furnace is reduced to 500 ℃, the oxygen is stopped to be introduced, air with the flow rate of 2m3/h is introduced again, and the furnace is cooled to be below 100 ℃.
And 7: treating a sintered sample: and after the furnace temperature is cooled to be below 100 ℃, opening the furnace door, pouring out the fired material, manually crushing, screening by using a 200-mesh analysis screen, crushing and screening for multiple times, then completely screening by using a 200-mesh screen, uniformly mixing undersize to obtain a qualified test sample, and testing the particle size, the first discharge capacity and the capacity retention rate after 50 cycles of the test sample to judge the test effect.
In the above examples, the manganese dioxide raw material is electrolytic manganese dioxide produced by the china-university manganese-large-new manganese ore division, the particle size D50 is 14.05um, the manganese content is 59.64%, and the manganese dioxide content is 94.34% by conversion; the manganous manganic oxide raw material is battery grade manganous manganic oxide produced by Guizhou Convergence, the granularity D50 is 12.86um, the manganese content is 71.03 percent, and the content of the manganous manganic oxide is converted into 98.58 percent; the lithium carbonate is battery grade lithium carbonate produced by Sichuan long lithium and Huali, the particle size D50 is 6.81um, and the lithium content is 18.71%. The test data for the three samples produced in examples 1-3 are shown in table 1.
TABLE 1 test data for various examples
By combining the above examples, the lithium manganate produced by the production method of the present invention has good performance in all aspects, as shown in fig. 1, the XRD pattern of the lithium manganate produced in example 2 is shown, as shown in fig. 2, the electron micrograph of the lithium manganate produced in example 2 is shown, and the lithium manganate is completely developed. The whole production method has the following advantages:
1. in order to achieve the purposes of fully utilizing the advantages of good performance of the lithium manganate prepared by taking manganous-manganic oxide as a raw material and fully utilizing oxygen generated in the process of preparing the lithium manganate by taking manganese dioxide as a raw material, MnO is added into the lithium manganate2The molar ratio of the component (A) is 81-90%.
2. Oxygen is not introduced into the kiln, oxygen generated inside the kiln when manganese dioxide is used as a raw material for preparing lithium manganate is fully utilized, and only 2m of oxygen is introduced3The oxygen content of the kiln is less than 20% in the sintering process of air/h, so that the production cost of the lithium manganate is greatly saved.
3. When the temperature is reduced in the front, oxygen is introduced for protection and cooling, after the high-temperature sintering time is finished,closing a power switch of the kiln, stopping electrifying air in a cooling section of 780-500 ℃, and introducing industrial oxygen with the oxygen content of more than 99.2 percent, wherein the oxygen flow is 1m3Ensuring that the oxygen content in the furnace atmosphere is more than 90 percent and the oxygen introducing time is about 2 hours, so that L iMn is ensured2O4Slow cooling in high oxygen atmosphere ensures L iMn2O4Complete crystal development and prevention of hypoxia of L iMn2O4And the generation of-x can improve the cycle performance of lithium manganate.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (8)
1. A method for producing lithium manganate by an internal oxygen method is characterized in that: the method comprises the following steps:
(1) weighing raw materials: weighing lithium carbonate and a manganese source according to the molar ratio of lithium to manganese, and then pouring the lithium carbonate and the manganese source into an inclined mixer to mix to obtain a mixture;
(2) mixing and screening: weighing zirconia balls according to a certain ball material ratio, adding the zirconia balls into an inclined mixer, starting the mixer to mix uniformly, pouring out the mixture and the zirconia balls together, screening to separate the zirconia balls from the raw materials, and filling the mixture into a sagger for burning;
(3) and (3) high-temperature sintering: placing the sagger filled with the mixture into a muffle furnace, introducing air for sintering, heating, and sintering at constant temperature for a period of time;
(4) oxygen protection cooling, namely closing a kiln power switch after the sintering constant temperature time is up, stopping electrifying air in a cooling section at 780-plus-500 ℃, and introducing industrial oxygen for a period of time to ensure L iMn2O4Slowly cooling in the atmosphere with high oxygen content;
(5) air protection cooling: after the furnace temperature is reduced to 500 ℃, stopping introducing oxygen, changing into introducing air, and cooling to below 100 ℃;
(6) sample treatment: and opening the furnace door to pour out the sintered material after the furnace is cooled, crushing and sieving to obtain the finished product.
2. The method for producing lithium manganate by an internal oxygen method according to claim 1, wherein: in the step (1), the molar ratio of lithium to manganese is 0.5 to 0.6, and the manganese source comprises manganese dioxide and trimanganese tetroxide, wherein the molar ratio of manganese dioxide is 80 to 90%.
3. The method for producing lithium manganate by an internal oxygen method according to claim 1, wherein: in the step (2), the mass of the zirconia balls is 1-3 times of that of the mixture, the mixing time of the mixture and the zirconia balls is 150-200min, and the screening mesh number is 200 meshes.
4. The method for producing lithium manganate by an internal oxygen method according to claim 3, wherein: the zirconia ball has three diameters, and the ratio of the three diameters from large to small is 3:4: 3.
5. The method for producing lithium manganate by an internal oxygen method according to claim 1, wherein: in the step (3), the heating rate is 3-5 ℃/min, the constant temperature is 780 ℃, and the constant temperature time is 10-20 h.
6. The method for producing lithium manganate by an internal oxygen method according to claim 1, wherein: in the step (4), the oxygen content of the industrial oxygen is more than 99.2%, and the oxygen flow is 1m3H, ensuring that the oxygen content in the furnace atmosphere is more than 90 percent, and leading in the oxygen for 1.5 to 3 hours.
7. The method for producing lithium manganate by an internal oxygen method according to claim 1, wherein: in the step (5), the air is introduced at an introduction flow rate of 2m3/h。
8. The method for producing lithium manganate by an internal oxygen method according to claim 1, wherein: in the step (6), the pulverization is carried out by manual multiple pulverization, and the mesh number of the screening is 200 meshes.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113113595A (en) * | 2021-03-23 | 2021-07-13 | 安徽博石高科新材料股份有限公司 | Method for producing lithium manganate by composite raw materials |
| CN113120972A (en) * | 2021-03-22 | 2021-07-16 | 安徽博石高科新材料股份有限公司 | Preparation method of lithium-rich manganese-based material |
| CN115676893A (en) * | 2022-11-10 | 2023-02-03 | 焦作伴侣纳米材料工程有限公司 | Composite manganese source for lithium manganate, preparation method of composite manganese source, lithium manganate and application of composite manganese source |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5874058A (en) * | 1995-10-06 | 1999-02-23 | Kerr-Mcgee Chemical Llc | Method of preparing Li1+x MN2-x O4 for use as secondary battery electrode |
| EP0931022A1 (en) * | 1996-11-01 | 1999-07-28 | Kerr-Mcgee Chemical Corporation | METHOD OF PREPARING Li 1+x?Mn 2-x?O 4? FOR USE AS SECONDARY BATTERY ELECTRODE |
| CN101807682A (en) * | 2010-04-09 | 2010-08-18 | 曲阜毅威能源股份有限公司 | Power spinel lithium manganese oxide anode material and preparation method thereof |
| CN102916196A (en) * | 2012-10-30 | 2013-02-06 | 桑德环境资源股份有限公司 | Method for preparing lithium-manganate battery cathode material admixed with scandium by ion implanter |
| US20130122372A1 (en) * | 2010-07-16 | 2013-05-16 | Mitsui Mining & Smelting Co., Ltd. | Spinel-Type Lithium Transition Metal Oxide and Positive Electrode Active Material for Lithium Battery |
| CN103618078A (en) * | 2013-09-16 | 2014-03-05 | 无锡晶石新型能源有限公司 | Lithium manganate production method |
| CN104852062A (en) * | 2015-02-04 | 2015-08-19 | 广州鹏辉能源科技股份有限公司 | A waste lithium-manganese dioxide battery material recycling method |
| CN110817968A (en) * | 2019-11-24 | 2020-02-21 | 永州昊利新材料科技有限公司 | Method for producing high-cost-performance lithium manganate by mixing manganous-manganic oxide with manganese dioxide |
-
2020
- 2020-04-02 CN CN202010256569.XA patent/CN111477865B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5874058A (en) * | 1995-10-06 | 1999-02-23 | Kerr-Mcgee Chemical Llc | Method of preparing Li1+x MN2-x O4 for use as secondary battery electrode |
| EP0931022A1 (en) * | 1996-11-01 | 1999-07-28 | Kerr-Mcgee Chemical Corporation | METHOD OF PREPARING Li 1+x?Mn 2-x?O 4? FOR USE AS SECONDARY BATTERY ELECTRODE |
| CN101807682A (en) * | 2010-04-09 | 2010-08-18 | 曲阜毅威能源股份有限公司 | Power spinel lithium manganese oxide anode material and preparation method thereof |
| US20130122372A1 (en) * | 2010-07-16 | 2013-05-16 | Mitsui Mining & Smelting Co., Ltd. | Spinel-Type Lithium Transition Metal Oxide and Positive Electrode Active Material for Lithium Battery |
| CN102916196A (en) * | 2012-10-30 | 2013-02-06 | 桑德环境资源股份有限公司 | Method for preparing lithium-manganate battery cathode material admixed with scandium by ion implanter |
| CN103618078A (en) * | 2013-09-16 | 2014-03-05 | 无锡晶石新型能源有限公司 | Lithium manganate production method |
| CN104852062A (en) * | 2015-02-04 | 2015-08-19 | 广州鹏辉能源科技股份有限公司 | A waste lithium-manganese dioxide battery material recycling method |
| CN110817968A (en) * | 2019-11-24 | 2020-02-21 | 永州昊利新材料科技有限公司 | Method for producing high-cost-performance lithium manganate by mixing manganous-manganic oxide with manganese dioxide |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113120972A (en) * | 2021-03-22 | 2021-07-16 | 安徽博石高科新材料股份有限公司 | Preparation method of lithium-rich manganese-based material |
| CN113113595A (en) * | 2021-03-23 | 2021-07-13 | 安徽博石高科新材料股份有限公司 | Method for producing lithium manganate by composite raw materials |
| CN115676893A (en) * | 2022-11-10 | 2023-02-03 | 焦作伴侣纳米材料工程有限公司 | Composite manganese source for lithium manganate, preparation method of composite manganese source, lithium manganate and application of composite manganese source |
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