CN111422925B - High-nickel ternary cathode material, preparation method thereof, lithium ion battery and electric automobile - Google Patents
High-nickel ternary cathode material, preparation method thereof, lithium ion battery and electric automobile Download PDFInfo
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- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention provides a high-nickel ternary cathode material, a preparation method thereof, a lithium ion battery and an electric automobile, wherein the method comprises the following steps: performing first calcination on a mixture of a high-nickel ternary positive electrode precursor, a lithium source and a dopant to obtain a first calcination product; performing second calcination on the mixture of the first calcined product and the coating agent to obtain a second calcined product; washing and drying the second calcined product in sequence to obtain a washed product; and carrying out third calcination on the water washing product to obtain the high-nickel ternary cathode material. According to the method, the dependence on a surface coating agent during the third calcination is eliminated through the cooperation of the previous working procedures, namely, the coating treatment is not carried out by adopting any surface coating agent, and only the simple annealing treatment is carried out, so that the high-nickel ternary cathode material with excellent cycle performance is successfully prepared on the premise of not sacrificing the specific capacity, and the method not only reduces the complexity of the preparation process, but also reduces the preparation cost.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a high-nickel ternary cathode material, a preparation method thereof, a lithium ion battery and an electric automobile.
Background
Lithium ion batteries have been developed for decades as a green energy provider throughout the life. Currently, mainstream positive electrode materials in the market are roughly classified into lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickel cobalt manganese oxide and the like, and each of the positive electrode lithium ion compounds has advantages and disadvantages. In order to solve the respective problems of the materials, the research field at present is dedicated to develop a nickel-cobalt-manganese ternary material (NCM), and the material is expected to integrate the advantages of three elements of Ni, co and Mn and reject the defect of a single lithium ion compound, so as to create a lithium ion positive electrode material with high specific capacity, long cycle life, safety and environmental protection. The method is also the mainstream development direction of the power lithium ion battery applied to the field of automobiles at present. The high-nickel ternary cathode material has higher nickel content and higher specific capacity, so the research direction of the ternary cathode material gradually approaches to the high-nickel direction. However, the high nickel content increases the specific capacity, and also causes the cycle stability to be remarkably reduced due to the high oxidizability of nickel ions.
Because, the related technology of the current high nickel ternary cathode material still needs to be improved.
Disclosure of Invention
The present invention is directed to solving, at least in part, one of the technical problems in the related art. Therefore, the invention aims to provide a high-nickel ternary cathode material with high specific capacity and good cycling stability, and a preparation method and application thereof.
In one aspect of the invention, a method of making a high-nickel ternary cathode material is provided. According to an embodiment of the invention, the method comprises: performing first calcination on a mixture of a high-nickel ternary positive electrode precursor, a lithium source and a dopant to obtain a first calcination product; performing second calcination on the mixture of the first calcined product and the coating agent to obtain a second calcined product; washing and drying the second calcined product in sequence to obtain a washed product; and carrying out third calcination on the water washing product to obtain the high-nickel ternary cathode material. According to the method, the dependence on a surface coating agent during the third calcination is eliminated through the cooperation of the previous working procedures, namely, the coating treatment is not carried out by adopting any surface coating agent, and only the simple annealing treatment is carried out, so that the high-nickel ternary cathode material with excellent cycle performance is successfully prepared on the premise of not sacrificing the specific capacity, and the method not only reduces the complexity of the preparation process, but also reduces the preparation cost.
According to an embodiment of the present invention, a ratio of an amount of a substance of lithium in the lithium source to a sum of amounts of substances of nickel, cobalt, and manganese in the high-nickel ternary positive electrode precursor is 1.02 to 1.06.
According to the embodiment of the invention, the dosage of the dopant is 2000-4000ppm based on the mass of the high-nickel ternary positive electrode precursor.
According to the embodiment of the invention, the temperature rise rate of the first calcination is 2-4 ℃/min, the heat preservation temperature is 750-800 ℃, the heat preservation time is 10-15 h, the oxygen content of the calcination atmosphere is more than or equal to 97%, and the cooling mode is furnace cooling.
According to the embodiment of the present invention, the coating agent is used in an amount of 1000 to 2000ppm based on the mass of the first calcined product.
According to the embodiment of the invention, the temperature rise rate of the second calcination is 2-4 ℃/min, the heat preservation temperature is 600-700 ℃, the heat preservation time is 7-15 h, the oxygen content of the calcination atmosphere is more than or equal to 97%, and the cooling mode is furnace cooling.
According to an embodiment of the present invention, the mass ratio of water to the second calcined product in the water washing step is 2; the washing time is 10-20 minutes.
According to an embodiment of the present invention, the temperature of the drying is 130 to 180 ℃.
According to the embodiment of the invention, the temperature rise rate of the third calcination is 2-4 ℃/min, the first heat preservation temperature is 120-150 ℃, the first heat preservation time is 1-3 h, the second heat preservation temperature is 270-330 ℃, the second heat preservation time is 6-10 h, the oxygen content of the calcination atmosphere is more than or equal to 97%, and the cooling mode is furnace cooling.
According to an embodiment of the invention, the high-nickel ternary positive electrode precursor comprises a polycrystalline high-nickel ternary positive electrode precursor.
According to the embodiment of the invention, the nickel content in the high-nickel ternary cathode precursor is more than or equal to 80%.
According to an embodiment of the invention, the high-nickel ternary positive electrode precursor comprises Ni (1-x-y) Co x Mn y (OH) 2 ,0.05≤x≤0.15，0.05≤y≤0.15，x+y≤0.2。
According to an embodiment of the invention, the lithium source comprises at least one of lithium hydroxide monohydrate and lithium carbonate.
According to an embodiment of the present invention, the dopant comprises a zirconium-containing compound comprising at least one of nano-zirconia and zirconium hydroxide.
According to an embodiment of the present invention, the coating agent includes an aluminum-containing compound including at least one of nano aluminum oxide and aluminum hydroxide.
In another aspect of the invention, a high nickel ternary positive electrode material is provided. According to the embodiment of the invention, the high-nickel ternary cathode material is prepared by the method. The high-nickel ternary cathode material prepared by the method ensures higher specific capacity and obviously improves the cycling stability.
According to an embodiment of the invention, the high nickel ternary positive electrode material meets at least one of the following conditions: the discharge specific capacity of 0.1C at normal temperature is more than or equal to 207mAh/g; the retention rate of the resin is not less than 96% after 50-week circulation at the temperature of 45 ℃.
In yet another aspect of the invention, a lithium ion battery is provided. According to an embodiment of the invention, the lithium ion battery comprises the high nickel ternary cathode material described above. The ion battery has high specific capacity and good cycling stability.
In yet another aspect of the present invention, an electric vehicle is provided. According to an embodiment of the present invention, the electric vehicle includes the lithium ion battery described above. The electric vehicle has all the features and advantages of the lithium ion battery, which are not described in detail herein.
Drawings
Fig. 1 is a schematic flow diagram of a method of preparing a high nickel ternary positive electrode material according to one embodiment of the present invention.
Detailed Description
The following describes in detail embodiments of the present invention. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The present invention has been completed based on the following findings and recognition by the inventors:
aiming at the problem that the cycling stability of the high-nickel ternary cathode material is reduced along with the increase of the nickel content, researchers propose to dope and modify the surface of the high-nickel ternary cathode material to improve the stability of the crystal structure and the surface structure of the high-nickel ternary cathode material, and further improve the cycle retention rate of the high-nickel ternary cathode material in the cycle process of the lithium ion battery. Specifically, for the high-nickel ternary cathode material, after the precursor, the lithium hydroxide and the dopant are uniformly mixed and calcined at a high temperature, because the residual alkaline substances (such as lithium hydroxide, lithium carbonate and the like) on the surface of the high-nickel ternary cathode material are high, and the content of nickel is high, the residual alkaline substances are high, and cannot be processed and used (the slurry stability of the cathode material is poor, and the battery preparation link cannot be smoothly performed), the residual alkaline substances on the surface of the high-nickel ternary cathode material are generally removed by adopting a water washing mode in the industry, however, the water washing can corrode the surface of the high-nickel ternary cathode material, so that the stability of the surface structure of the high-nickel ternary cathode material is reduced, and the washed material needs to be coated with a layer of relatively stable compound subsequently, so as to repair the unstable surface structure of the washed material. However, the specific capacity of the high-nickel ternary cathode material is often sacrificed to improve the cycle retention rate of the lithium ion battery, because the surface coating agent has low reactivity, and although it is helpful to improve the structural stability of the material, the specific capacity of the material is reduced. And often only pay attention to improving the cycle retention rate of the lithium ion battery at normal temperature (25 ℃), but the cycle retention rate of the lithium ion battery at high temperature (45 ℃) is not obviously improved as the cycle retention rate of the lithium ion battery at normal temperature. Based on the findings, the inventor aims to provide a high-nickel ternary cathode material capable of effectively improving the cycling stability on the premise of not sacrificing the specific capacity, and after intensive research and exploration, the inventor finds that after the precursor material is sequentially doped, coated and washed, the precursor material is directly calcined without a coating agent, and the high-nickel ternary cathode material with high specific capacity and good cycling stability can be obtained through the comprehensive effect of all the steps.
In view of the above, in one aspect of the present invention, a method of making a high nickel ternary cathode material is provided. According to an embodiment of the invention, referring to fig. 1, the method comprises the steps of:
s100: and carrying out first calcination on the mixture of the high-nickel ternary positive electrode precursor, the lithium source and the dopant to obtain a first calcined product.
According to the embodiment of the invention, the high-nickel ternary positive electrode precursor used in the step can be a polycrystalline material, i.e. a polycrystalline highNickel ternary positive electrode precursor (meaning high nickel ternary positive electrode precursor particles are stacked from many primary particles, rather than a single entity). In some embodiments, the nickel content in the high-nickel ternary positive electrode precursor is greater than or equal to 80%, specifically, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, and the like. More specifically, the high-nickel ternary cathode precursor may include Ni (1-x-y) Co x Mn y (OH) 2 ,0.05≤x≤0.15，0.05≤y≤0.15，x+y≤0.2。
According to the embodiment of the present invention, the lithium source may be used as long as it can effectively react with the precursor to obtain the lithium-containing compound, and specifically, the lithium source includes at least one of lithium hydroxide monohydrate and lithium carbonate. Therefore, the method is easy to react, and the obtained product has good electrical property, wide material source and easy obtaining.
According to the embodiment of the invention, the doping element in the adopted dopant can enter the interior of the positive electrode material and exist in the positive electrode material in a mosaic or alternative mode to improve the electrical property of the positive electrode material, and particularly, the dopant comprises a zirconium-containing compound, and the zirconium-containing compound comprises at least one of nano zirconium oxide and zirconium hydroxide. Therefore, the electrical property of the cathode material can be well improved, and the cathode material with better use effect is obtained.
According to an embodiment of the present invention, a ratio of an amount of a substance of lithium in the lithium source to a sum of amounts of substances of nickel, cobalt, and manganese in the high-nickel ternary positive electrode precursor is 1.02 to 1.06:1, specifically 1.02. Within this ratio range, a relatively stable lithium intercalation compound is produced, and if too small, the lithium content becomes insufficient and sufficient effective capacity cannot be provided. If the lithium-nickel ratio is too large, larger lithium-nickel mixed discharge can be caused, and excessive lithium residual compounds can be generated, so that the physical, chemical and electrochemical properties are influenced.
According to the embodiment of the invention, the dosage of the dopant is 2000-4000ppm, specifically 2000ppm, 2200ppm, 2500ppm, 2800ppm, 3000ppm, 3200ppm, 500ppm, 800ppm, 4000ppm and the like based on the mass of the high-nickel ternary cathode precursor. Within the proportion range, a compound with stable structure can be favorably formed, the dopant can play an effective role of inlaying or replacing, and if the proportion is too small, the crystal structure of the anode material cannot be effectively improved. If the amount of the dopant is too large, the amount of the dopant may be too large, and the main element composition of the positive electrode material may be changed, which may cause adverse effects such as lattice distortion.
According to the embodiment of the invention, the temperature rise rate of the first calcination is 2-4 ℃/min (specifically, 2 ℃/min, 3 ℃/min, 4 ℃/min and the like), the heat preservation temperature is 750-800 ℃ (specifically, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃, 800 ℃ and the like), the heat preservation time is 10-15 h (specifically, 10h, 11h, 12h, 13h, 14h, 15h and the like), the oxygen content of the calcination atmosphere is more than or equal to 97%, and the cooling mode is furnace cooling. Under this calcination condition, help generating stable crystal structure, if the programming rate can cause the unable even conduction effectively of heat too fast, influence the homogeneity of whole reaction, programming rate can prolong reaction time too slowly, and the increase in cost, the too high overburning that causes of holding temperature, destroy the crystal structure of anodal material, holding temperature is low can't carry out effectual chemical reaction excessively, holding time overlength anodal material's granule increases too greatly, increase the energy consumption, holding time too short can cause the synthesis reaction insufficient, influence each aspect performance of material.
According to the embodiment of the invention, after the first calcined product is obtained, the first calcined product can be subjected to roller crushing and ultracentrifugal grinding and crushing treatment (two modes of grinding the first calcined product by a roller crusher and a centrifugal crusher are respectively adopted, so that the effects of changing bulk into powder and changing powder into micropowder can be respectively achieved), and then the first calcined product with a proper particle size is obtained by sieving, and large-particle-size particles which can cause abnormal performance are removed. The size of the screened screen can be flexibly selected according to actual requirements, and in some specific embodiments, the screened screen can pass through a 400-mesh screen.
S200: and carrying out second calcination on the mixture of the first calcined product and the coating agent to obtain a second calcined product.
According to the embodiment of the invention, in the step, the coating agent can coat the outer surface of the first calcined product obtained in the previous step, so that the first calcined product can be protected, the corrosion resistance in the subsequent water washing step can be realized, the surface structure stability of the obtained high-nickel ternary cathode material can be improved, the surface activity is high, and the specific capacity of the cathode material cannot be influenced too much. In some embodiments, the capping agent comprises an aluminum-containing compound comprising at least one of nano aluminum oxide and aluminum hydroxide. Therefore, the effect of corrosion resistance is good, and the specific capacity of the positive electrode material is not influenced too much.
According to an embodiment of the present invention, the coating agent is used in an amount of 1000 to 2000ppm, specifically, 1100ppm, 1200ppm, 1300ppm, 1400ppm, 1500ppm, 1600ppm, 1700ppm, 1800ppm, 1900ppm, 2000ppm, etc., based on the mass of the first calcined product. Within the dosage range, the protective effect of the coating agent is good, the surface structure stability of the obtained positive electrode material is good, the surface activity is high, if the dosage is too small, the protective effect is relatively poor, the surface structure stability of the obtained positive electrode material is relatively poor, if the dosage is too large, the surface activity can be influenced, and the specific capacity of the obtained positive electrode material is reduced.
According to the embodiment of the invention, the temperature rise rate of the second calcination is 2-4 ℃/min (specifically, 2 ℃/min, 3 ℃/min, 4 ℃/min, and the like), the holding temperature is 600-700 ℃ (specifically, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃, 700 ℃, and the like), the holding time is 7-15 h (specifically, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, and the like), the oxygen content of the calcination atmosphere is greater than or equal to 97%, and the cooling manner is furnace cooling. Under this calcination condition, help generating stable coating, if the programming rate can cause the unable even conduction effectively of heat too fast, influence the homogeneity of whole cladding reaction, programming rate can prolong reaction time too slowly, and the increase in cost, the too high overburning that causes of holding temperature, the crystal structure of the coating of destruction, holding temperature crosses lowly can't carry out effectual chemical reaction, the holding time overlength can lead to the inside infiltration of cladding element toward the positive pole material granule, influence the cladding effect, and increase the energy consumption, the holding time short excessively can cause the coating reaction insufficient, influence the structural stability of material.
S300: and washing and drying the second calcined product in sequence to obtain a washed product.
According to an embodiment of the present invention, in this step, water washing can effectively remove basic residual substances in the second calcined product, and the workability is good, specifically, the mass ratio of water to the second calcined product in the water washing step is from 2; the washing time is 10 to 20 minutes (specifically, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, 16 minutes, 17 minutes, 18 minutes, 19 minutes, 20 minutes, etc.). In the proportion range, the alkaline residual substances can be effectively removed completely, the corrosion to the surface structure of the second calcined product is small, the improvement of the surface structure stability of the obtained anode material is facilitated, the removal of the alkaline residual substances is not facilitated if the water consumption is too small or the time is too short, the surface corrosion effect on the second calcined product is strong if the water consumption is too large or the time is too long, and the improvement of the surface structure stability of the obtained anode material is not facilitated.
According to the embodiment of the present invention, the drying may be vacuum drying, and the specific drying temperature may be 130 to 180 ℃ (for example, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, etc.).
S400: and carrying out third calcination on the water washing product to obtain the high-nickel ternary cathode material.
According to the embodiment of the present invention, in this step, a surface coating agent is not needed, and only annealing treatment needs to be directly performed, specifically, after the alkaline residual substance is cleaned, the original alkaline residual substance is directly exposed, and annealing treatment is performed, so that the coating layer obtained in step S200 performs supplementary repair on the exposed surface, and in addition, the exposed surface itself tends to be transformed into a crystal surface that can exist stably.
In some embodiments, the temperature increase rate of the third calcination is 2 to 4 ℃/min (specifically, 2 ℃/min, 3 ℃/min, 4 ℃/min, etc.), the first keeping temperature is 120 to 150 ℃ (specifically, 120 ℃, 130 ℃, 140 ℃, 150 ℃, etc.), the first keeping time is 1 to 3h (specifically, 1h, 2h, 3h, etc.), the second keeping temperature is 270 to 330 ℃ (specifically, 270 ℃, 280 ℃, 90 ℃,300 ℃, 310 ℃, 320 ℃, 330 ℃, etc.), the second keeping time is 6 to 10h (specifically, 6h, 7h, 8h, 9h, 10h, etc.), the oxygen content of the calcination atmosphere is greater than or equal to 97%, and the cooling manner is furnace cooling. Under the calcining condition, the self-repairing and coating layer repairing of the exposed surface after water washing can be facilitated, if the heating rate is too fast, the expected repairing effect cannot be achieved, if the heating rate is too slow, the repairing process is prolonged, lithium ions can be caused to migrate outwards, because the lithium ion concentration of the exposed surface after water washing is lower than that of the inside of the material, the cost can be increased, if the heat preservation temperature is too high, the lithium ions can be aggravated to migrate outwards, alkaline substances are generated again, if the heat preservation temperature is too low, the expected repairing effect cannot be achieved, if the heat preservation time is too long, the lithium ions can be caused to migrate outwards, the alkaline substances are generated again, the cost can be increased, and if the heat preservation time is too short, the expected repairing effect cannot be achieved.
In the present specification, the first holding temperature, the first holding time, the second holding temperature, and the second holding time refer to holding at the first holding temperature for the first holding time, and then holding at the second holding temperature for the second holding time.
According to the method, the dependence on a surface coating agent during the third calcination is eliminated through the cooperation of the previous working procedures, namely, the coating treatment is not carried out by adopting any surface coating agent, and only the simple annealing treatment is carried out, so that the high-nickel ternary cathode material with excellent cycle performance is successfully prepared on the premise of not sacrificing the specific capacity, and the method not only reduces the complexity of the preparation process, but also reduces the preparation cost.
In another aspect of the invention, a high nickel ternary positive electrode material is provided. According to the embodiment of the invention, the high-nickel ternary cathode material is prepared by the method. The high-nickel ternary cathode material prepared by the method ensures higher specific capacity and obviously improves the cycling stability.
According to an embodiment of the invention, the high nickel ternary positive electrode material meets at least one of the following conditions: the 0.1C discharge specific capacity at normal temperature is more than or equal to 207mAh/g (specifically 207mAh/g, 208mAh/g, 209mAh/g, 210mAh/g and the like); the 50-week cycle retention rate is not less than 96% (specifically, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, etc.) at 45 ℃.
In yet another aspect of the present invention, a lithium ion battery is provided. According to an embodiment of the invention, the lithium ion battery comprises the high nickel ternary cathode material described above. The ion battery has high specific capacity and good cycling stability.
It is understood that the lithium ion battery may include necessary structures and components of a conventional lithium ion battery, such as a positive electrode sheet, a negative electrode sheet, a separator, an electrolyte, a case, etc., in addition to the aforementioned high nickel ternary positive electrode material, which may be mixed with a conductive agent, a binder, etc. into a slurry and then coated on a metal foil to constitute a positive electrode sheet.
In yet another aspect of the present invention, an electric vehicle is provided. According to an embodiment of the invention, the electric vehicle comprises the lithium ion battery. The electric vehicle has all the features and advantages of the lithium ion battery, which are not described in detail herein.
It is understood that, besides the lithium ion battery mentioned above, the electric vehicle may further include structures and components necessary for a conventional electric vehicle, such as a vehicle body, an engine, a tire, a frame, and the like, which can be specifically referred to the conventional technology and are not described in detail herein.
The following describes embodiments of the present invention in detail.
Example 1:
1. uniformly mixing lithium hydroxide monohydrate, a high-nickel ternary positive electrode precursor and a nano zirconia dopant according to the weight sum of Li/Me (nickel, cobalt and manganese) =1.04 and the doping proportion =2000 ppm;
2. putting the uniformly mixed materials into an atmosphere furnace, setting the heating rate to be 2 ℃/min, preserving the heat for 10 hours at 760 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the oxygen content is more than or equal to 97%;
3. carrying out double-roller crushing, ultracentrifugal grinding and crushing on the material obtained by primary calcination, and then sieving by using a 400-mesh sieve;
4. uniformly mixing the sieved material with a nano aluminum oxide coating agent according to the coating proportion =1000 ppm;
5. putting the uniformly mixed materials into an atmosphere furnace, setting the heating rate to be 2 ℃/min, preserving the heat for 10 hours at 600 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the oxygen content is more than or equal to 97 percent;
6. and (3) washing the material after secondary sintering, wherein the mass ratio of the deionized water to the high-nickel ternary cathode material is 1:1, washing for 20 minutes, and then drying the washed materials in vacuum at 150 ℃;
7. putting the dried material into an atmosphere furnace, preserving heat for 1.5h at 120 ℃, preserving heat for 7.5h at 300 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the oxygen content is more than or equal to 97 percent;
8. and sieving the material sintered for the third time by a 400-mesh sieve, and then packaging to obtain the finished high-nickel ternary cathode material with excellent high-temperature cycle performance.
And (3) mixing the obtained high-nickel ternary positive electrode material, SP (superfine carbon powder) and PVDF (polyvinylidene fluoride) according to a mass ratio of 92:4:4, preparing the button half cell by adopting a metal lithium sheet as a negative electrode. The performance obtained by the test is as follows: the specific discharge capacity at 0.1C under normal temperature is 209.2mAh/g, and the cycle retention rate at high temperature (45 ℃) for 50 weeks is 97.5%.
Example 2:
1. uniformly mixing lithium hydroxide monohydrate, a high-nickel ternary positive electrode precursor and a nano zirconia dopant according to Li/Me =1.04 and a doping proportion =2000 ppm;
2. putting the uniformly mixed materials into an atmosphere furnace, preserving the heat for 10 hours at 760 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the oxygen content is more than or equal to 97 percent;
3. carrying out double-roller crushing, ultracentrifugal grinding and crushing on the material obtained by primary sintering, and then sieving by using a 400-mesh sieve;
4. uniformly mixing the sieved material with a nano aluminum oxide coating agent according to the coating proportion =1000 ppm;
5. putting the uniformly mixed materials into an atmosphere furnace, preserving the heat for 10 hours at the temperature of 600 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the oxygen content is more than or equal to 97 percent;
6. and (3) washing the material after secondary sintering, wherein the mass ratio of the deionized water to the high-nickel ternary cathode material is 1.5:1, washing for 20 minutes, and then drying the washed materials in vacuum at 150 ℃;
7. putting the dried material into an atmosphere furnace, preserving heat for 1.5h at 120 ℃, preserving heat for 7.5h at 300 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the oxygen content is more than or equal to 97 percent;
8. and sieving the material sintered for the third time by a 400-mesh sieve, and then packaging to obtain the finished high-nickel ternary cathode material with excellent high-temperature cycle performance.
And (3) mixing the obtained high-nickel ternary cathode material, SP and PVDF according to a weight ratio of 92:4:4, preparing the button half cell by adopting a metal lithium sheet as a negative electrode. The performance obtained by the test is that the 0.1C specific discharge capacity at normal temperature is 207.1mAh/g, and the cycle retention rate at high temperature (45 ℃) for 50 weeks is 96.5%.
Example 3:
1. uniformly mixing lithium hydroxide monohydrate, a high-nickel ternary positive electrode precursor and a nano zirconia dopant according to Li/Me =1.06 and a doping proportion =2000 ppm;
2. putting the uniformly mixed materials into an atmosphere furnace, preserving heat for 10 hours at 780 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the oxygen content is more than or equal to 97 percent;
3. carrying out double-roller crushing, ultracentrifugal grinding and crushing on the material obtained by primary sintering, and then sieving by using a 400-mesh sieve;
4. uniformly mixing the sieved material with a nano aluminum oxide coating agent according to the coating proportion =1000 ppm;
5. putting the uniformly mixed materials into an atmosphere furnace, preserving heat for 10 hours at 650 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the oxygen content is more than or equal to 97 percent;
6. and (3) washing the material after secondary sintering, wherein the mass ratio of the deionized water to the high-nickel ternary cathode material is 1:1, washing for 20 minutes, and then drying the washed materials in vacuum at 150 ℃;
7. putting the uniformly mixed materials into an atmosphere furnace, preserving heat for 1.5h at the temperature of 120 ℃, preserving heat for 7.5h at the temperature of 300 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the oxygen content is more than or equal to 97 percent;
8. and sieving the material sintered for the third time by a 400-mesh sieve, and then packaging to obtain the finished high-nickel ternary cathode material with excellent high-temperature cycle performance.
And (3) mixing the obtained high-nickel ternary cathode material, SP and PVDF according to a ratio of 92:4:4, preparing the button half cell by adopting a metal lithium sheet as a negative electrode. The performance obtained by testing is that the 0.1C specific discharge capacity at normal temperature is 211.4mAh/g, and the high-temperature (45 ℃) cycle retention rate at 50 weeks is 96.2%.
Example 4:
1. uniformly mixing lithium hydroxide monohydrate, a high-nickel ternary positive electrode precursor and a nano zirconia dopant according to the proportion that Li/Me =1.06 and the doping proportion =2000 ppm;
2. putting the uniformly mixed materials into an atmosphere furnace, preserving heat for 10 hours at 780 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the oxygen content is more than or equal to 97 percent;
3. carrying out double-roller crushing, ultracentrifugal grinding and crushing on the material obtained by primary sintering, and then sieving by using a 400-mesh sieve;
4. uniformly mixing the sieved material with a nano-alumina coating agent according to the coating proportion =1000 ppm;
5. putting the uniformly mixed materials into an atmosphere furnace, preserving heat for 15 hours at the temperature of 600 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the oxygen content is more than or equal to 97 percent;
6. and (3) washing the material after secondary sintering, wherein the mass ratio of the deionized water to the high-nickel ternary cathode material is 1.5:1, washing for 20 minutes, and then drying the washed materials in vacuum at 150 ℃;
7. putting the dried material into an atmosphere furnace, preserving heat for 1.5h at 120 ℃, preserving heat for 7.5h at 300 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the oxygen content is more than or equal to 97%;
8. and sieving the material sintered for the third time by a 400-mesh sieve, and then packaging to obtain the finished high-nickel ternary cathode material with excellent high-temperature cycle performance.
And (3) mixing the obtained high-nickel ternary cathode material, SP and PVDF according to a weight ratio of 92:4:4, preparing the button half cell, and adopting a metal lithium sheet as a negative electrode. The performance obtained by the test is that the specific discharge capacity of 0.1C at normal temperature is 212.1mAh/g, and the high-temperature (45 ℃) cycle at 50 weeks is 97%.
Comparative example 1:
1. uniformly mixing lithium hydroxide monohydrate, a high-nickel ternary positive electrode precursor and a nano zirconia dopant according to the proportion that Li/Me =1.04 and the doping proportion =2000 ppm;
2. putting the uniformly mixed materials into an atmosphere furnace, preserving the heat for 10 hours at 760 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the oxygen content is more than or equal to 97 percent;
3. carrying out double-roller crushing, ultracentrifugal grinding and crushing on the material obtained by primary sintering, and then sieving by using a 400-mesh sieve;
4. uniformly mixing the sieved material with a nano aluminum oxide coating agent according to the coating proportion =1500 ppm;
5. putting the uniformly mixed materials into an atmosphere furnace, preserving heat for 7 hours at the temperature of 600 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the oxygen content is more than or equal to 97 percent;
6. and (3) washing the material after secondary sintering, wherein the mass ratio of the deionized water to the high-nickel ternary cathode material is 1.5:1, washing for 20 minutes, and then drying the washed materials in vacuum at 150 ℃;
7. uniformly mixing the washed and dried material with boric acid according to the coating proportion =1000 ppm; putting the uniformly mixed materials into an atmosphere furnace, preserving heat for 10 hours at 300 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the oxygen content is more than or equal to 97 percent;
8. and sieving the material sintered for the third time by a 400-mesh sieve, and then packaging to obtain the finished high-nickel ternary cathode material with excellent high-temperature cycle performance.
And (3) mixing the obtained high-nickel ternary cathode material, SP and PVDF according to a weight ratio of 92:4:4, preparing the button half cell, and adopting a metal lithium sheet as a negative electrode. The performance obtained by the test is that the 0.1C specific discharge capacity at normal temperature is 206mAh/g, and the 50-week high-temperature (45 ℃) cycle is 95%.
From the results of the above examples 1 to 4 and the comparative example 1, it can be seen that, compared with the comparative example 1, the cycle retention rate of 50 weeks is also significantly improved while the specific capacity of the cathode material prepared by the method of the present invention is higher, at 45 ℃, which effectively indicates that the cycle retention rate of the cathode material prepared by the method of the present invention can be effectively improved while the specific capacity is not sacrificed.
In the description of the present invention, it is to be understood that the terms "first", "second", and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to imply that the number of technical features indicated are in fact significant. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (12)
1. A method for preparing a high-nickel ternary cathode material is characterized by comprising the following steps:
performing first calcination on a mixture of a high-nickel ternary positive electrode precursor, a lithium source and a dopant to obtain a first calcination product;
performing second calcination on the mixture of the first calcined product and the coating agent to obtain a second calcined product;
washing and drying the second calcined product in sequence to obtain a washed product;
carrying out third calcination on the water-washed product to obtain a high-nickel ternary cathode material,
wherein, the first and the second end of the pipe are connected with each other,
the ratio of the quantity of lithium in the lithium source to the sum of the quantities of nickel, cobalt and manganese in the high-nickel ternary positive electrode precursor is 1.02 to 1.06,
based on the mass of the high-nickel ternary positive electrode precursor, the dosage of the dopant is 2000-4000ppm,
the temperature rise rate of the first calcination is 2 to 4 ℃/min, the heat preservation temperature is 750 to 800 ℃, the heat preservation time is 10 to 15h, the oxygen content of the calcination atmosphere is more than or equal to 97 percent, the cooling mode is furnace cooling,
the amount of the coating agent is 1000 to 2000ppm based on the mass of the first calcined product,
the temperature rise rate of the second calcination is 2 to 4 ℃/min, the heat preservation temperature is 600 to 700 ℃, the heat preservation time is 7 to 15h, the oxygen content of the calcination atmosphere is more than or equal to 97 percent, the cooling mode is furnace cooling,
the mass ratio of water to the second calcined product in the water washing step is 2 to 1; the washing time is 10 to 20 minutes,
the heating rate of the third calcination is 2 to 4 ℃/min, the first heat preservation temperature is 120 to 150 ℃, the first heat preservation time is 1 to 3 hours, the second heat preservation temperature is 270 to 330 ℃, the second heat preservation time is 6 to 10 hours, the oxygen content of the calcination atmosphere is more than or equal to 97 percent, and the cooling mode is furnace cooling.
2. The method according to claim 1, wherein the drying temperature is 130 to 180 ℃.
3. The method of claim 1, wherein the high-nickel ternary positive electrode precursor comprises a polycrystalline high-nickel ternary positive electrode precursor.
4. The method of claim 1, wherein the high-nickel ternary positive electrode precursor has a nickel content of 80% or greater.
5. The method of claim 1, wherein the high-nickel ternary positive electrode precursor comprises Ni (1-x-y) Co x Mn y (OH) 2 ,0.05≤x≤0.15，0.05≤y≤0.15，x+y≤0.2。
6. The method of claim 1, wherein the lithium source comprises at least one of lithium hydroxide monohydrate and lithium carbonate.
7. The method of claim 1, wherein the dopant comprises a zirconium-containing compound comprising at least one of nano-zirconia and zirconium hydroxide.
8. The method of claim 1, wherein the capping agent comprises an aluminum-containing compound comprising at least one of nano aluminum oxide and aluminum hydroxide.
9. A high-nickel ternary positive electrode material, which is prepared by the method according to any one of claims 1 to 8.
10. The high-nickel ternary positive electrode material according to claim 9, characterized in that at least one of the following conditions is satisfied:
the 0.1C specific discharge capacity at normal temperature is more than or equal to 207mAh/g;
the retention rate of 50-week circulation is not less than 96% under the condition of 45 ℃.
11. A lithium ion battery comprising the high-nickel ternary positive electrode material of claim 9 or 10.
12. An electric vehicle comprising the lithium ion battery of claim 11.
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| CN112259727B (en) * | 2020-09-29 | 2022-05-17 | 格林美（无锡）能源材料有限公司 | Method for reducing content of miscellaneous lithium in high-nickel cathode material |
| CN113666430A (en) * | 2021-07-30 | 2021-11-19 | 蜂巢能源科技有限公司 | Lithium-rich cathode material, preparation method thereof and lithium ion battery |
| CN114725371A (en) * | 2022-04-20 | 2022-07-08 | 天津巴莫科技有限责任公司 | High-nickel single crystal positive electrode material, preparation method thereof, lithium ion battery and all-solid-state battery |
| CN115367810A (en) * | 2022-07-18 | 2022-11-22 | 广东风华新能源股份有限公司 | Preparation process of positive electrode material, positive electrode and battery |
| CN115911337B (en) * | 2023-01-06 | 2023-06-23 | 宜宾锂宝新材料有限公司 | High-nickel positive electrode material, preparation method thereof and battery |
| CN115863653B (en) * | 2023-01-30 | 2023-07-18 | 四川新能源汽车创新中心有限公司 | Method for realizing uniform coating of primary particle surface and obtained positive electrode material |
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