CN109037614B - High-compaction single crystal nickel-cobalt-manganese ternary material and preparation method thereof - Google Patents
High-compaction single crystal nickel-cobalt-manganese ternary material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-compaction single crystal nickel-cobalt-manganese ternary material, which comprises the steps of preparing a precursor by adopting a coprecipitation method; mixing a lithium source, a coating agent and a precursor, and sintering for the first time to obtain an intermediate; mixing the intermediate with a lithium source in proportion, sintering for the second time and shaping to obtain a product; according to the invention, through the processes of solid phase coating and twice sintering, the average particle size of the ternary material is effectively improved, the specific surface area of the ternary material is reduced, the compaction density is further improved, the first charge-discharge capacity is improved, and the cycle performance of the ternary material battery is improved.
Description
Technical Field
The invention belongs to the field of lithium ion battery anode materials, and particularly relates to a high-compaction single crystal nickel-cobalt-manganese ternary material and a preparation method thereof.
Background
The nickel-cobalt-manganese ternary material has the advantages of high voltage platform, large reversible specific capacity, stable structure, good safety performance and the like, and is low in price; is a research hotspot of the anode material of the novel lithium ion battery at present. However, the nickel cobalt lithium manganate ternary material also has certain disadvantages in the practical application process, such as low coulombic efficiency, poor cycle performance, difficult control of components and morphology, low tap density and the like. The defects greatly influence the popularization and application of the nickel-cobalt-manganese ternary material.
In general, the compacted density of lithium cobaltate can reach 4.1g/cm3The compaction density of the nickel-cobalt-manganese ternary material as the lithium cobaltate substitute material is only 3.3-3.4g/cm3Low compaction density greatly affects the performance of lithium ion batteries. According to statistics, the compaction density is increased by 0.1g/cm every time3The volume energy density can be improved by 3 percent, so that the improvement of the compaction density has great significance for improving the nickel-cobalt-manganese ternary material lithium ion battery. Patent application CN201710994418.2 utilizes lithium carbonate and ternary precursorsThe D is prepared by the processes of mixing, doping, twice sintering, crushing and screening50The material is a ternary material with the particle size of 10-12 mu m, but after primary sintering, the material needs to be crushed, sieved, pulped, washed and dried again; the process is complex and the production cost is high. Another method for improving the compaction density is to control the morphology of the ternary material by doping, so as to achieve the purpose of improving the compaction density, and in patent document CN201510844880.5, the ternary material is prepared by adopting a process of primary sintering, doping, secondary sintering and liquid-phase coating of alumina, and the specific surface area of the ternary material is improved by controlling the morphology of the ternary material, so as to improve the tap density of the ternary material.
Disclosure of Invention
The invention aims to provide a high-compaction single crystal nickel-cobalt-manganese ternary material which has the characteristics of high compaction density, high first charge-discharge capacity and excellent cycle performance.
The technical problem to be solved by the invention is also to provide a preparation method of the high-compaction single crystal nickel-cobalt-manganese ternary material, which is simple in preparation process, regular in shape and high in compaction density.
In order to solve the technical problems and achieve corresponding technical effects, the invention provides a preparation method of a high-compaction single crystal nickel-cobalt-manganese ternary material, which comprises the following steps:
(1) preparation of Ni by coprecipitation1-x-yCoxMny(OH)2Wherein x is more than 0 and less than or equal to 0.3, y is more than 0 and less than or equal to 0.3, and (1-x-y) is more than 0 and less than or equal to 0.6;
(2) mixing the precursor, lithium carbonate and a coating agent according to a ratio to obtain a mixture, wherein the molar ratio of the precursor to the lithium carbonate is as follows: li: (Ni + Co + Mn): 1.01-1.08): 1;
(3) sintering the mixture for the first time to obtain an intermediate;
(4) mixing the intermediate with lithium carbonate according to a proportion;
(5) and carrying out secondary sintering on the uniformly mixed intermediate and lithium carbonate, and shaping to obtain the product.
As an improvement of the technical scheme, the coating agent is one or a combination of titanium dioxide, tetraethyl titanate and tetrabutyl titanate.
As an improvement of the technical scheme, the coating agent is titanium dioxide, and the addition amount of the coating agent is 0.05-0.5% of the total mass of the precursor and the lithium hydroxide.
As an improvement of the above technical solution, the primary sintering includes: the mixture is pre-sintered for 4-9h at 800 ℃ of 500-.
As an improvement of the technical scheme, the sintering temperature of the secondary sintering is 750-980 ℃, and the sintering time is 8-16 h.
As an improvement of the technical scheme, in the step (4), the adding amount of the lithium carbonate is 0.5-3% of the mass of the intermediate.
As an improvement of the technical scheme, the step (1) comprises the following steps:
(1.1) dissolving soluble nickel salt, soluble cobalt salt and soluble manganese salt in water to prepare a solution A; dissolving a precipitator in water to prepare a solution B; dissolving a complexing agent in water to prepare a solution C;
(1.2) adding the solution A, B, C into a reaction kettle simultaneously according to the weight ratio for reaction;
(1.3) filtering, washing and drying after the reaction is finished to obtain a precursor;
as an improvement of the above technical scheme, in the step (1.1), the soluble nickel salt is one or a combination of nickel sulfate, nickel chloride and nickel nitrate; the soluble cobalt salt is one or a combination of cobalt sulfate, cobalt chloride and cobalt nitrate; the soluble manganese salt is one or a combination of manganese sulfate, manganese chloride and manganese nitrate; the precipitator is sodium hydroxide or potassium hydroxide; the complexing agent is ammonia water; the molar concentration of the solution A is 1.0-2.5 mol/L; the molar concentration of the solution B is 4-8 mol/L; the molar concentration of the solution C is 3-5 mol/L; in the step (1.2), the solution A is solution B: solution C is (1.5-3.5): (3.5-5): 0.5-1.5.
As an improvement of the technical proposal, in the step (1.2), the reaction temperature is 40-100 ℃, and the reaction time is 40The pH value is controlled to be 8-11 in the reaction process after-50 h; n is introduced in the reaction process2As the protective gas, the flow of the protective gas is 8-20L/min.
Correspondingly, the invention also provides a high-compaction single crystal nickel-cobalt-manganese ternary material which is prepared by adopting the preparation method.
The implementation of the invention has the following beneficial effects:
the invention provides a high-compaction single crystal nickel-cobalt-manganese ternary material and a preparation method thereof, and the high-compaction single crystal nickel-cobalt-manganese ternary material adopts the processes of titanium oxide coating and secondary sintering. The method has the following specific advantages:
1. according to the invention, titanium oxide is adopted for coating, and a protective layer is formed on the surface of the ternary material, so that the passing rate of Ni and Mn is reduced, the dissolution of Ni and Mn in the circulation process is reduced, and the circulation performance of the ternary material is optimized.
2. The invention adopts the secondary sintering process, effectively improves the particle size and the compacted density of the ternary material, effectively improves the first charge-discharge capacity, and improves the capacity retention rate and the rate capability of the ternary material in the secondary sintering process.
3. The single crystal ternary material is prepared through coprecipitation reaction in a reasonable ratio, and processes of adding a lithium source twice and sintering twice; in the sintering reaction process, the conditions are reasonably controlled, so that the single crystal is well developed, the granularity is improved, and the compaction density is further improved.
4. The lithium carbonate is used as a lithium source, and has the advantages of strong reaction activity, small lithium content fluctuation and small corrosivity.
5. According to the invention, the process of adding the lithium source twice and sintering twice is adopted, the granularity of the ternary material is effectively controlled, the ternary material with uniform granularity distribution, larger average particle size and reasonable granularity distribution is prepared, the compaction density of the ternary material is improved, and the performance of the ternary material battery is improved.
Drawings
FIG. 1 is a scanning electron microscope image of a high compaction single crystal Ni-Co-Mn ternary material prepared by the present invention.
FIG. 2 is an XRD diagram of a high compaction single crystal nickel cobalt manganese ternary material prepared by the invention.
FIG. 3 is a particle size distribution curve diagram of the high compaction single crystal Ni-Co-Mn ternary material prepared by the present invention.
FIG. 4 is a comparison graph of the cycling stability of the high compacted single crystal Ni-Co-Mn ternary material prepared by the present invention and a common Ni-Co-Mn ternary material.
FIG. 5 is a first charge-discharge comparison graph of the high compaction single crystal nickel cobalt manganese ternary material prepared by the present invention and a common nickel cobalt manganese ternary material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a high-compaction single crystal nickel-cobalt-manganese ternary material, which comprises the following steps:
(1) preparation of Ni by coprecipitation1-x-yCoxMny(OH)2A precursor;
wherein: 0 < x < 0.3, 0 < y < 0.3, 0 < 1-x-y < 0.6, preferably 0 < x < 0.25, 0 < y < 0.25, 0 < 1-x-y < 0.5. The ternary material has the characteristic of good cycle performance.
The coprecipitation method is characterized by uniform mixing, and can be used for preparing ternary materials with various shapes such as a core-shell structure, a sphere shape, a nanometer flower and the like and uniform particle size distribution by controlling the concentration, the dropping speed, the stirring speed, the pH value and the reaction temperature of raw materials, so that the shape of the ternary material precursor is effectively ensured, and the compaction density is improved.
Preferably, the Ni is prepared by adopting a coprecipitation method1-x-yCoxMny(OH)2The precursor comprises the following steps:
(1.1) dissolving soluble nickel salt, cobalt salt and manganese salt in water to prepare a solution A; dissolving a precipitator in water to prepare a solution B; dissolving a complexing agent in water to prepare a solution C;
wherein the soluble nickel salt is one or a combination of nickel sulfate, nickel chloride and nickel nitrate; the soluble cobalt salt is one or a combination of cobalt sulfate, cobalt chloride and cobalt nitrate, and the soluble manganese salt is one or a combination of manganese sulfate, manganese chloride and manganese nitrate; can be well dissolved in water, and provides excellent conditions for subsequent coprecipitation reaction.
Preferably, the soluble nickel salt is nickel sulfate; the soluble cobalt salt is cobalt sulfate; the soluble manganese salt is manganese sulfate.
The precipitant is sodium hydroxide or potassium hydroxide; preferably sodium hydroxide; the complexing agent is ammonia water. The selection of the complexing agent and the precipitating agent has great influence on the shape of the ternary material precursor, the combination of the sodium hydroxide and the ammonia water can ensure the reasonable range of pH, the coprecipitation reaction speed is uniform, and the shape of the prepared ternary material precursor is regular.
The molar concentration of the solution A is 1.0-2.5mol/L, the molar concentration of the solution B is 4-8mol/L, and the molar concentration of the solution C is 3-5 mol/L; the concentration of the raw material solution is a key factor influencing the morphology of the ternary material precursor, the coprecipitation reaction speed is not easy to control due to the excessively high or excessively low concentration of the solution, and the morphology of the product cannot be controlled; preferably, the concentration of the solution A is preferably 1.3-2 mol/L; the concentration of the solution B is 4-6 mol/L; the concentration of the solution C is 3.5-5 mol/L.
(1.2) adding the solution A, B, C into a reaction kettle simultaneously according to the weight ratio for reaction;
the weight ratio of each solution is as follows: solution A, solution B: adding the solution C (1.5-3.5) and (3.5-5) and (0.5-1.5) into a reaction kettle for coprecipitation reaction; preferably, the ratio of solution A to solution B: and (3) 1 is used for solution C (2-3) and (3.75-5).
The coprecipitation reaction process conditions of the invention are as follows: the reaction temperature is 40-100 ℃, the reaction time is 40-50h, the stirring speed is 500-800rpm, and the pH value is controlled to be 8-11 in the reaction process; introducing N in the reaction process2As the protective gas, the flow rate is 8-20L/min. The person skilled in the art can follow the actual raw materialSelecting the process conditions of the production condition and the product performance.
(1.3) filtering, washing and drying after the reaction is finished to obtain a precursor;
after the reaction is finished, filtering the slurry, washing for a plurality of times, and removing hydroxide radicals attached to the surface of the precursor; drying to obtain the precursor.
(2) Mixing the precursor with lithium carbonate and a coating agent according to a ratio to obtain a mixture;
the invention has no special requirements on the components of the lithium source, and a person skilled in the art can select a suitable lithium source according to the actual production situation. In order to better exert the advantages of the invention, lithium carbonate is selected as a lithium source; common lithium sources in the production process include lithium carbonate, lithium hydroxide and lithium nitrate; the lithium nitrate can generate harmful gas in the using process; although lithium hydroxide is superior to lithium carbonate in terms of reactivity and reaction temperature, lithium hydroxide fluctuates more than lithium carbonate due to its lithium content and is more corrosive than lithium carbonate; therefore, the lithium carbonate with stable lithium content and low corrosiveness is selected as the lithium source.
Wherein the mol ratio of the lithium carbonate to the precursor is as follows: li: 1, (1.01-1.08) and 1, the doping amount of lithium determines the property of the product, and in combination with the subsequent process, the invention adopts a mode of doping Li twice, and less lithium is doped in the first doping process, so that the lithium can fully react with the precursor, the residual lithium in the finished product is effectively reduced, and the excellent performance of the product is ensured. Preferably, the molar ratio of the lithium carbonate to the precursor is: li: (Ni + Co + Mn): 1.02-1.05): 1.
In order to ensure sufficient reaction of lithium with the precursor, it is necessary to mix uniformly in the former stage, and in the present invention, the mixing is not particularly limited. In the invention, the mixing process is as follows: mixing for 20-60min by using a ball mill or a high-speed mixer; preferably, the mixing process is adopted, a ball mill is adopted for mixing and grinding for 20-60min, the mixing of the precursor, the lithium carbonate and the coating agent can be enhanced by adopting one ball mill, and in addition, the shape of the final product can be controlled, so that the final product is in a smooth ellipsoidal shape; preferably, the mixing process is mixing for 10-40min by using a high-speed mixer, compared with a ball mill, the high-speed mixer has good mixing effect and low energy consumption, and the mixing uniformity by using the high-speed mixer is also superior to that of the ball mill.
The coating agent is one or a combination of titanium dioxide, tetraethyl titanate and tetrabutyl titanate; the titanium dioxide is preferred, and the titanium coating can form a protective layer on the surface of the ternary material, so that the passing rate of Ni and Mn is reduced, the dissolution of Ni and Mn in the circulating process is reduced, and the circulating performance of the ternary material is optimized.
In the invention, when the coating agent is titanium dioxide, the adding amount of the coating agent is 0.05-0.5% of the total mass of the precursor and the lithium carbonate; when the coating amount of titanium dioxide is too high, the coating is too tight, which may hinder the dissolution of lithium ions, and when too low, it may not exert its effect, so that a reasonable coating range needs to be selected. Preferably, the adding amount of the titanium dioxide is 0.05-0.2% of the total mass of the precursor and the lithium carbonate, and the doping of the titanium dioxide can form a protective layer, so that the cycle performance of the ternary material is improved.
(3) Sintering the mixture for the first time to obtain an intermediate;
the mixture is placed into an atmosphere furnace for sintering, and the lithium carbonate and the precursor can fully react by sintering to obtain a uniform anode material, so that the performance of the ternary material is ensured; in order to ensure the excellent performance of the high-compaction single crystal nickel-cobalt-manganese ternary material, the invention adopts the following firing process conditions: pre-burning the mixture at 800 deg.c for 4-9 hr, and sintering at 980 deg.c for 10-20 hr in oxidizing atmosphere, preferably O2Or air as a shielding gas, more preferably O2。
The steps further include:
(3.1) carrying out primary sintering on the mixture;
(3.2) adding the sintered mixture into a high-speed crusher to crush the mixture to obtain an intermediate;
wherein the specific surface area of the sintered material in the step (3.1) is 0.5-0.7m2The precursor prepared by coprecipitation reaction has smaller granularity, so the relative granularity is smaller after one-time sintering,the specific surface area is higher.
After the primary sintering, the crushing is beneficial to subsequent mixing, and the lithium carbonate can be fully mixed with the once-fired intermediate, thereby being beneficial to the secondary sintering reaction.
(4) Mixing the intermediate with lithium carbonate according to a proportion;
the invention has no special requirements on the components of the lithium source, and a person skilled in the art can select a suitable lithium source according to the actual production situation. In order to better exert the advantages of the invention, lithium carbonate is selected as a lithium source; common lithium sources in the production process include lithium carbonate, lithium hydroxide and lithium nitrate; lithium nitrate can generate harmful gas in the using process; although lithium hydroxide is superior to lithium carbonate in terms of reactivity and reaction temperature, lithium hydroxide fluctuates more than lithium carbonate due to its lithium content and is more corrosive than lithium carbonate; therefore, the lithium carbonate with stable lithium content and low corrosiveness is selected as the lithium source.
Wherein the adding amount of the lithium carbonate is 0.5-3% of the mass of the intermediate. And a small amount of lithium carbonate is added to effectively supplement the loss of part of the lithium source in the primary sintering process, and simultaneously, the lithium added in the secondary sintering process can effectively and fully react with the formed intermediate to prevent lithium residues in the product.
According to the invention, a process of adding the lithium source twice is adopted, and a small amount of lithium source is added before one-time sintering, so that the lithium source can fully react with the precursor, and the residual lithium is reduced, thereby reducing the influence of the residual lithium on the appearance of the intermediate. Before secondary sintering, a small amount of lithium carbonate is added again, so that lithium can be effectively supplemented, and meanwhile, the added lithium source can be fully fused into product crystal lattices to form a product with a single crystal structure, and the compaction density of the product is improved.
In order to ensure sufficient reaction of lithium with the precursor, it is necessary to mix uniformly in the former stage, and in the present invention, the mixing is not particularly limited. In the invention, the mixing process is as follows: mixing for 20-60min by using a ball mill or a high-speed mixer; preferably, the mixing process is adopted, a ball mill is adopted for mixing and grinding for 20-60min, the mixing of the precursor, the lithium carbonate and the coating agent can be enhanced by adopting one ball mill, and in addition, the shape of the final product can be controlled, so that the final product is in a smooth ellipsoidal shape; preferably, the mixing process is mixing for 10-40min by using a high-speed mixer, compared with a ball mill, the high-speed mixer has good mixing effect and low energy consumption, and the mixing uniformity by using the high-speed mixer is also superior to that of the ball mill.
(5) Carrying out secondary sintering on the uniformly mixed intermediate and lithium carbonate, and shaping to obtain a product;
wherein the control parameters of the sintering process are as follows: the sintering temperature is 750-980 ℃, the sintering time is 8-16h, and the sintering is carried out in an oxidizing atmosphere. The specific surface area of the product after secondary sintering is controlled to be 0.3-0.6m2And the secondary sintering can effectively improve the granularity of the product, reduce the specific surface area, improve the compaction density which can reach 3.8g/cm3, and improve the energy density and the first charge-discharge capacity of the ternary material.
The shaping comprises the following steps: and crushing and sieving the sintered product by adopting a high-speed crusher to obtain the product. The specific surface area is further reduced after shaping, and can be controlled at 0.2-0.5m2(ii) in terms of/g. The specific surface area of the ternary material can be effectively reduced through secondary sintering and shaping, the compaction density is improved, and the energy density and the first charge-discharge capacity of the ternary material are improved.
Meanwhile, the preparation process of the coprecipitation precursor is adopted, so that the precursor has uniform granularity and regular appearance; the product with uniform particle size distribution is formed in the later stage; in the subsequent processing process, the means of adding the lithium source twice is adopted, so that the influence of residual lithium on the appearance and granularity of the product is reduced; moreover, the particle size of the intermediate is effectively increased by adopting a twice-firing process. Through the comprehensive effect of the process means, the product prepared by the method has the characteristics of narrow particle size distribution range, larger average particle size and small specific surface area, so that the compaction density is high, the energy density is high, and the first charge-discharge capacity is high.
Correspondingly, the invention provides a high-compaction single crystal nickel-cobalt-manganese ternary material which is prepared by adopting the preparation method.
The invention provides a high-compaction single crystal nickel-cobalt-manganese ternary material and a preparation method thereof.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The preparation method comprises the following steps:
(1) uniformly mixing nickel sulfate, cobalt sulfate and manganese sulfate according to the molar ratio of Ni, Co and Mn being 0.5:0.25:0.25 to obtain 1mol/L solution A. Weighing sodium hydroxide, and adding deionized water to prepare a solution B of 5 mol/L; weighing 20% strong ammonia water to prepare 3.6mol/L solution C.
(2) Respectively weighing 300g, 500g and 100g of the solution A, the solution B and the solution C, adding 1000g of pure water into a reactor, simultaneously adding the solution A, the solution B and the solution C into a reaction kettle, and controlling the stirring speed of the reaction kettle at 600 rpm. The reaction process needs to be protected by introducing nitrogen, the flow is 13L/min, the reaction temperature is kept at 50 ℃, the pH is kept at 8.5-10.5, and the reaction time is 45 h.
(3) And after the reaction is finished, carrying out suction filtration, washing and drying on the slurry to obtain a precursor.
(4) Weighing 1500g of lithium carbonate and the precursor according to the molar ratio of 1.05:1, adding 3g of nano-titanium oxide, and ball-milling for 1h by using a ball mill.
(5) Putting the uniformly mixed materials into an atmosphere furnace for sintering, and adopting a two-stage sintering process, wherein the pre-sintering temperature is 800 ℃ and the time is 6 hours; the sintering temperature is 920 ℃, and the time is 15 h. And crushing the sintered intermediate for 15s by using a high-speed crusher.
(6) 1600g of intermediate and 18g of lithium carbonate are taken and put into a ball mill for ball milling for 1 h.
(7) Sintering at 900 ℃ for 13h, crushing in a high-speed crusher for 8s, and sieving to obtain the finished ternary material.
The high-compaction nickel-cobalt-manganese ternary material produced by the process has the 0.1C charge capacity of 208mAh/g and the 1C charge capacity of 160 mAh/g; after 600 weeks of circulation, the capacity of the material can still reach 120mAh/g, and compared with a common nickel-cobalt-manganese ternary material, the circulation performance is improved by 27%.
Example 2
The preparation method comprises the following steps:
(1) nickel sulfate, cobalt sulfate and manganese sulfate were mixed uniformly in a molar ratio of Ni to Co to Mn of 0.5 to 0.2 to 0.3 to obtain 1.8mol/L solution a. Weighing sodium hydroxide, and adding deionized water to prepare a solution B of 5 mol/L; weighing 20% strong ammonia water to prepare 3.8mol/L solution C.
(2) 350g, 550g and 100g of the solution A, the solution B and the solution C are respectively weighed, 1500g of pure water is added into a reactor, the solution A, the solution B and the solution C are simultaneously added into a reaction kettle, and the stirring speed of the reaction kettle is controlled at 700 rpm. The reaction process needs to be protected by introducing nitrogen, the flow is 20L/min, the reaction temperature is kept at 60 ℃, the pH is kept at 9-11, and the reaction time is 48 h.
(3) And after the reaction is finished, carrying out suction filtration, washing and drying on the slurry to obtain a precursor.
(4) 620g of lithium carbonate and the precursor are weighed according to the molar ratio of 1.03:1, 1.24g of nano-scale titanium oxide is added, and the mixture is ball-milled for 50min by using a ball mill.
(5) Putting the uniformly mixed materials into an atmosphere furnace for sintering, and adopting a two-stage sintering process, wherein the pre-sintering temperature is 750 ℃ and the time is 5 hours; the sintering temperature is 950 ℃ and the time is 13 h. And crushing the sintered intermediate for 10s by using a high-speed crusher.
(6) 1500g of the intermediate and 22.5g of lithium carbonate are taken and put into a ball mill for ball milling for 30 min.
(7) Sintering at 850 ℃ for 16h, crushing in a high-speed crusher for 8s, and sieving to obtain the finished ternary material.
The high-compaction nickel-cobalt-manganese ternary material produced by the process has the 0.1C charge capacity of 200mAh/g and the 1C charge capacity of 145 mAh/g; after 600 weeks of circulation, the capacity of the material can still reach 98mAh/g, and compared with a common nickel-cobalt-manganese ternary material, the circulation performance is improved by 10%.
Example 3
The preparation method comprises the following steps:
(1) uniformly mixing nickel sulfate, cobalt sulfate and manganese sulfate according to the molar ratio of Ni, Co and Mn being 0.6:0.2:0.2 to obtain 1.3mol/L solution A. Weighing sodium hydroxide, and adding deionized water to prepare a solution B of 4 mol/L; weighing 20% strong ammonia water to prepare 4mol/L solution C.
(2) 350g, 450g and 120g of the solution A, the solution B and the solution C are respectively weighed, 2000g of pure water is added into a reactor, the solution A, the solution B and the solution C are simultaneously added into a reaction kettle, and the stirring speed of the reaction kettle is controlled at 800 rpm. The reaction process needs to be protected by introducing nitrogen, the flow is 15L/min, the reaction temperature is kept at 70 ℃, the pH is kept at 9-11, and the reaction time is 40 h.
(3) And after the reaction is finished, carrying out suction filtration, washing and drying on the slurry to obtain a precursor.
(4) Weighing 800g of lithium carbonate and the precursor according to the molar ratio of 1.04:1, adding 0.8g of nano-scale titanium oxide, and ball-milling for 50min by using a ball mill.
(5) Putting the uniformly mixed materials into an atmosphere furnace for sintering, and adopting a two-stage sintering process, wherein the pre-sintering temperature is 650 ℃ and the time is 9 hours; the sintering temperature is 960 ℃, and the time is 14 h. And crushing the sintered intermediate for 13s by using a high-speed crusher.
(6) 1500g of the intermediate and 30g of lithium carbonate are taken and put into a ball mill for ball milling for 50 min.
(7) Sintering at 960 deg.C for 9h, pulverizing in high speed pulverizer for 10s, and sieving to obtain the final ternary material.
The high-compaction nickel-cobalt-manganese ternary material produced by the process has the 0.1C charge capacity of 205mAh/g and the 1C charge capacity of 155 mAh/g; after 600 weeks of circulation, the capacity of the material can still reach 112mAh/g, and compared with the common nickel-cobalt-manganese ternary material, the circulation performance is improved by 21%.
Example 4
The preparation method comprises the following steps:
(1) uniformly mixing nickel sulfate, cobalt sulfate and manganese sulfate according to the molar ratio of Ni, Co and Mn being 0.5:0.25:0.25 to obtain 2mol/L solution A. Weighing sodium hydroxide, and adding deionized water to prepare a solution B of 5.9 mol/L; weighing 20% strong ammonia water to prepare 3.6mol/L solution C.
(2) 350g, 625g and 125g of the solution A, the solution B and the solution C are respectively weighed, 1800g of pure water is added into a reactor, the solution A, the solution B and the solution C are simultaneously added into a reaction kettle, and the stirring speed of the reaction kettle is controlled at 650 rpm. The reaction process needs to be protected by introducing nitrogen, the flow is 15L/min, the reaction temperature is kept at 80 ℃, the pH is kept at 9.5-11, and the reaction time is 43 hours.
(3) And after the reaction is finished, carrying out suction filtration, washing and drying on the slurry to obtain a precursor.
(4) Weighing 1000g of lithium carbonate and the precursor according to the molar ratio of 1.02:1, adding 0.5g of nano-scale titanium oxide, and ball-milling for 45min by using a ball mill.
(5) Putting the uniformly mixed materials into an atmosphere furnace for sintering, and adopting a two-stage sintering process, wherein the pre-sintering temperature is 750 ℃ and the time is 5 hours; the sintering temperature is 950 ℃ and the time is 13 h. And crushing the sintered intermediate for 10s by using a high-speed crusher.
(6) 1500g of the intermediate and 22.5g of lithium carbonate are taken and put into a ball mill for ball milling for 30 min.
(7) Sintering at 850 ℃ for 16h, crushing in a high-speed crusher for 8s, and sieving to obtain the finished ternary material.
The high-compaction nickel-cobalt-manganese ternary material produced by the process has the 0.1C charge capacity of 200mAh/g and the 1C charge capacity of 145 mAh/g; after 600 weeks of circulation, the capacity of the material can still reach 98mAh/g, and compared with a common nickel-cobalt-manganese ternary material, the circulation performance is improved by 10%.
The high-compaction nickel-cobalt-manganese ternary material produced by the process has the 0.1C charge capacity of 200mAh/g and the 1C charge capacity of 140 mAh/g; after 600 weeks of circulation, the capacity of the material can still reach 104mAh/g, and compared with the common nickel-cobalt-manganese ternary material, the circulation performance is improved by 15%.
Example 5
The preparation method comprises the following steps:
(1) uniformly mixing nickel sulfate, cobalt sulfate and manganese sulfate according to the molar ratio of Ni, Co and Mn being 0.5:0.25:0.25 to obtain 2mol/L solution A. Weighing sodium hydroxide, and adding deionized water to prepare a solution B of 5.9 mol/L; weighing 20% strong ammonia water to prepare 3.6mol/L solution C.
(2) 350g, 625g and 125g of the solution A, the solution B and the solution C are respectively weighed, 1800g of pure water is added into a reactor, the solution A, the solution B and the solution C are simultaneously added into a reaction kettle, and the stirring speed of the reaction kettle is controlled at 650 rpm. The reaction process needs to be protected by introducing nitrogen, the flow is 15L/min, the reaction temperature is kept at 80 ℃, the pH is kept at 9.5-11, and the reaction time is 43 hours.
(3) And after the reaction is finished, carrying out suction filtration, washing and drying on the slurry to obtain a precursor.
(4) Weighing 1000g of lithium carbonate and the precursor according to the molar ratio of 1.05:1, adding 1g of nano-titanium oxide, and ball-milling for 45min by using a ball mill.
(5) Putting the uniformly mixed materials into an atmosphere furnace for sintering, and adopting a two-stage sintering process, wherein the pre-sintering temperature is 800 ℃ and the time is 6 hours; the sintering temperature is 950 ℃ and the time is 13 h. And crushing the sintered intermediate for 10s by using a high-speed crusher.
(6) 1500g of the intermediate and 20g of lithium carbonate are taken and put into a ball mill for ball milling for 30 min.
(7) Sintering at 900 ℃ for 15h, crushing in a high-speed crusher for 10s, and sieving to obtain the finished ternary material.
The high-compaction nickel-cobalt-manganese ternary material produced by the process has the 0.1C charge capacity of 208mAh/g and the 1C charge capacity of 165 mAh/g; after 600 weeks of circulation, the capacity of the material can still reach 124mAh/g, and compared with a common nickel-cobalt-manganese ternary material, the circulation performance is improved by 30%.
FIGS. 1-5 show the results of testing the high compaction single crystal Ni-Co-Mn ternary material of the present invention. Referring to fig. 1, fig. 1 is an electron microscope image of a high compaction single crystal nickel-cobalt-manganese ternary material prepared by the embodiment of the invention, and as can be seen from fig. 1, the nickel-cobalt-manganese ternary material prepared by the invention has an ellipsoidal structure, a smooth surface and a uniform particle size. Referring to fig. 2, it can be seen from fig. 2 that the ternary material prepared by the reaction of the present invention has strong diffraction intensity and complete crystal form, and is a single crystal nickel-cobalt-manganese ternary material. Referring to fig. 3, fig. 3 is a particle size distribution diagram of a high-compaction single crystal nickel-cobalt-manganese ternary material prepared according to an embodiment of the present invention, and it can be seen from the diagram that the particle size distribution of the ternary material prepared according to the present invention is between 2 μm and 15 μm, the average particle size is 5.5 μm, the particle size distribution is uniform, the distribution range is concentrated, and the ternary material with high compaction density can be formed. Referring to fig. 4, fig. 4 is a comparison graph of the first charge capacity of the high-compaction single-crystal nickel-cobalt-manganese ternary material prepared by the present invention and the common nickel-cobalt-manganese ternary material, and it can be seen from the graph that the 0.1C charge capacity of the ternary material prepared by the present invention is 208mAh/g, and the 1C charge capacity is 160 mAh/g. Referring to fig. 5, fig. 5 is a comparison graph of the cycle performance of the high-compaction single crystal nickel-cobalt-manganese ternary material prepared by the invention and the common nickel-cobalt-manganese ternary material, and it can be seen from the graph that after 600 cycles, the capacity of the ternary material battery of the invention can reach 120mAh/g, but the common capacity is only 88mAh/g, and the cycle performance is improved by 27%.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. A preparation method of a high-compaction single crystal nickel-cobalt-manganese ternary material is characterized by comprising the following steps:
(1) preparation of Ni by coprecipitation1-x-yCoxMny(OH)2Wherein x is more than 0 and less than or equal to 0.3, y is more than 0 and less than or equal to 0.3, and (1-x-y) is more than 0 and less than or equal to 0.6;
(2) and (2) carrying out mixed grinding on the precursor, lithium carbonate and titanium dioxide for 20-60min by adopting a ball mill to obtain a mixture, wherein the molar ratio of the precursor to the lithium carbonate is as follows: li: 1, wherein the adding amount of titanium dioxide is 0.05-0.5 percent of the total mass of the precursor and lithium carbonate;
(3) sintering the mixture for the first time to obtain an intermediate; the primary sintering comprises the following steps: pre-sintering the mixture at 500-800 ℃ for 4-9h, and then sintering at 900-980 ℃ for 10-20 h;
(4) mixing the intermediate with lithium carbonate according to a proportion, wherein the adding amount of the lithium carbonate is 0.5-3% of the mass of the intermediate;
(5) carrying out secondary sintering on the uniformly mixed intermediate and lithium carbonate, and shaping to obtain a product;
the sintering temperature of the secondary sintering is 750-980 ℃, and the sintering time is 8-16 h;
the titanium dioxide is coated on the surface of the nickel-cobalt-manganese ternary material to form a protective layer.
2. The method for preparing a highly compacted single crystal nickel cobalt manganese ternary material as claimed in claim 1, wherein the step (1) comprises:
(1.1) dissolving soluble nickel salt, soluble cobalt salt and soluble manganese salt in water to prepare a solution A; dissolving a precipitator in water to prepare a solution B; dissolving a complexing agent in water to prepare a solution C;
(1.2) adding the solution A, B, C into a reaction kettle simultaneously according to the weight ratio for reaction;
and (1.3) filtering, washing and drying after the reaction is finished to obtain a precursor.
3. The method for preparing a high-compaction single-crystal nickel-cobalt-manganese ternary material as claimed in claim 2, wherein the soluble nickel salt in the step (1.1) is one or a combination of nickel sulfate, nickel chloride and nickel nitrate; the soluble cobalt salt is one or a combination of cobalt sulfate, cobalt chloride and cobalt nitrate; the soluble manganese salt is one or a combination of manganese sulfate, manganese chloride and manganese nitrate; the precipitator is sodium hydroxide or potassium hydroxide; the complexing agent is ammonia water; the molar concentration of the solution A is 1.0-2.5 mol/L; the molar concentration of the solution B is 4-8 mol/L; the molar concentration of the solution C is 3-5 mol/L; in the step (1.2), the weight ratio of each solution is that the solution A is: solution C is (1.5-3.5): (3.5-5): 0.5-1.5.
4. The method for preparing the high-compaction single-crystal nickel-cobalt-manganese ternary material as claimed in claim 2, wherein in the step (1.2), the reaction temperature is 40-100 ℃, the reaction time is 40-50h, and the pH value is controlled to be 8-11 in the reaction process; n is introduced in the reaction process2As the protective gas, the flow of the protective gas is 8-20L/min.
5. A highly compacted single crystal Ni-Co-Mn ternary material, characterized in that it is produced by the process according to any one of claims 1 to 4.
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| CN112635735A (en) * | 2020-12-21 | 2021-04-09 | 惠州亿纬锂能股份有限公司 | Nickel-cobalt lithium manganate precursor with coating structure, preparation method and application thereof |
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