CN115738894B - Lithium ion battery anode material with superlattice structure and nozzle and method for preparing lithium ion battery anode material - Google Patents
Lithium ion battery anode material with superlattice structure and nozzle and method for preparing lithium ion battery anode material Download PDFInfo
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Abstract
The invention discloses a superlattice structure lithium ion battery anode material, a nozzle for preparing the same and a method thereof. The nozzle for preparing the lithium ion battery anode material with the superlattice structure comprises an air inlet pipe, a nozzle tip and a plurality of feeding pipes; the nozzle tip includes a core, a gas distributor, and a shell; a plurality of material channels which are not communicated with each other are arranged in a core body fixed at the end part of an air inlet pipe, the top end of each material channel is correspondingly connected with one inlet pipe, the tail end of each material channel is an arc-shaped discharge hole, and the discharge holes are distributed on the same ring and are not communicated with each other; the gas distributor is an annular frustum fixed on the periphery of the core body, a plurality of gas channels on the gas distributor surround the periphery of an annular formed by the discharge port, the shell surrounds the periphery of the gas distributor, and the end part of the shell is gradually reduced into a nozzle opening. The invention also discloses the prepared lithium ion battery anode material with the superlattice structure and a method, and the method is simple and has little pollution.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a lithium ion battery anode material with a superlattice structure, a nozzle for preparing the lithium ion battery anode material and a method for preparing the lithium ion battery anode material.
Background
In recent years, electrochemical energy storage has been a very vigorous development as a national strategic emerging industry for dealing with environmental pollution and energy crisis, and will be a greater role in the future. The lithium ion battery is one of the electrochemical energy storage representatives of new energy with excellent comprehensive performance at present, has been widely applied to markets of electric vehicles, energy storage power stations, communication and digital electronic products and the like, can also play an important role in the fields of aviation, aerospace, military and the like, and is a novel green chemical power supply which is vigorously developed at home and abroad.
The anode material is one of the key core materials of the lithium ion battery, and directly determines the technical performance level of the battery. The currently commercialized positive electrode materials mainly include layered LiMO 2 (M is one or more of Ni, co, mn and the like), spinel type LiMn 2 O 4 And olivine type LiFePO 4 However, these positive electrode materials have certain defects in different degrees, so that the lithium ion battery cannot meet the requirements of various application fields and markets for products. For example, liCoO 2 The problems of cobalt resource shortage and high cost are faced; spinel-structured LiMn 2 O 4 In the recycling process, the Jahn-Teller effect of crystal form transformation and the dissolution of manganese ions are easy to occur, so that the battery capacity is quickly attenuated, and the high-temperature performance is poor; layered positive electrode material LiNi 1-x- y Co x Mn y O 2 Although the synergistic effect of Ni, co and Mn can be exerted, the actual specific capacity is not greatly broken through, and the safety problem is large; olivine-type LiFePO 4 The low specific capacity and tap density results in a limited energy density of the battery. In summary, these lithium ion positive electrode materials are currently difficult to meet the ever-increasing market demand.
The superlattice material can exert the advantages of different phase structures, and realize the synergistic effect between material structures/components. The coprecipitation method is one of the mainstream industrial preparation methods at present, and can be used for preparing gradient materials, composite materials, superlattice materials and the like. For example, CN107785551B discloses a layered oxide cathode material with gradient proportion of phase structure; CN108483516A discloses a lithium ion battery anode material with a superlattice ordered structure and a synthesis method thereof; CN111106331B discloses a layered-spinel phase composite positive electrode material and a preparation method thereof. However, the disadvantages of the coprecipitation method are: the reaction process needs to strictly control the conditions of pH value, concentration, reaction temperature, reaction atmosphere and the like of the solution, a large amount of strong base and strong acid needs to be used during preparation, the reaction time is long, and a large amount of waste gas, waste water and waste residues are generated simultaneously.
Disclosure of Invention
The purpose of the invention is: the nozzle for preparing the lithium ion battery anode material with the superlattice structure is simple in method and less in waste gas, waste water and waste residues.
The technical scheme of the invention is as follows:
a nozzle for preparing a lithium ion battery anode material with a superlattice structure comprises an air inlet pipe, a nozzle tip and a plurality of feeding pipes; the nozzle tip comprises a core, a gas distributor, and a shell; the core body is fixed at the end part of the air inlet pipe, a plurality of material channels which are not communicated with each other are arranged in the core body, the top end of each material channel is correspondingly connected with one feed pipe, the tail end of each material channel forms an arc-shaped discharge hole at the outlet end face of the core body, and the discharge holes are distributed on the same circular ring and are not communicated with each other; the gas distributor is an annular frustum fixed on the periphery of the core body, a plurality of gas channels are uniformly distributed on the gas distributor, the gas channels are communicated with the gas inlet pipe, and the plurality of gas channels surround the periphery of a circular ring formed by the plurality of discharge holes; the shell is fixed at the end part of the air inlet pipe in a sealing mode, the shell surrounds the periphery of the air distributor in an annular mode, the end part of the shell is gradually contracted and provided with a nozzle opening, and the diameter of the nozzle opening is larger than that of a circular ring formed by the discharge holes.
The nozzle for preparing the lithium ion battery anode material with the superlattice structure is characterized in that a plurality of material channels which are not communicated with each other are arranged in a core body, the top end of each material channel is correspondingly connected with one feeding pipe, and the tail end of each material channel forms an arc-shaped discharging hole on the outlet end face of the core body, so that when the lithium ion battery anode material is prepared, all components in raw materials are prepared into slurry or solution with incompletely same element types or contents, then the slurry or solution is respectively fed from different feeding pipes and reaches different arc-shaped discharging holes after passing through the material channels which are not communicated with each other on the core body; meanwhile, high-pressure gas in the gas inlet pipe is sprayed out from a plurality of gas channels surrounding the periphery of the circular discharge hole after being divided by the gas distributor. During spray drying, the high-pressure gas atomizes the materials flowing out of different discharge ports, the materials are fused at the end face of a nozzle opening, and then the materials are dried by hot air in a spray drying system to be prepared into particles. Because different discharge ports of the nozzle for preparing the lithium ion battery anode material with the superlattice structure are arranged on the same ring and are not communicated with each other, particles formed by spray drying are formed by atomizing, fusing and drying materials containing incompletely identical elements and sprayed from two discharge ports, and the formed particles are precursor particles which are uniform and ordered on a macroscopic scale and are doped with disordered structures of various elements on a microscopic scale. The precursor particles are different from precursor particles formed by coprecipitation, and the precursor particles formed by the coprecipitation method exist in a state that all elements are uniformly mixed with each other in an ion mode in a solution before precipitation, and the uniform mixing degree is an atomic level, so that the formed precursor particles are uniform in both a microscopic mode and a macroscopic mode; according to the nozzle for the lithium ion battery anode material with the superlattice structure, due to the fact that the element components of materials sprayed from different discharge ports which are arranged on the same ring are not identical, when precursor particles are formed, elements in each particle are arranged orderly in a macroscopic view, but are unevenly distributed on an atomic level, but grow into thin layers periodically and alternately on a nanoscale according to a certain rule, and when the precursor particles are sintered at a high temperature, lithium in the materials, other metal elements and oxygen realize ordered growth of a micro-nano crystal domain; after high-temperature sintering, the formed lithium ion battery positive electrode material has a superlattice structure formed by multiple components and/or structures. When the precursor of the lithium ion battery anode material with the superlattice structure is prepared by the nozzle, all elements of raw materials for forming the lithium ion battery anode material are divided into two or more components with different elements which are not completely the same, and then pulping, spraying, fusing and drying are carried out on the components, so that water-soluble raw materials can be used for selecting the raw materials to be dissolved and then sprayed, such as metal hydrochloride, metal nitrate, soluble sulfate, metal carbonate and the like; non-water-soluble raw materials such as insoluble metal oxides, metal hydroxides and the like can also be used, and when the lithium-ion battery is used, the raw materials are crushed, ground to be in a nanometer size, then slurried and sprayed, and meanwhile, the lithium source is directly mixed with other metal elements before granulation, so that the method is simple, and waste gas, waste water and waste residues are less; in the coprecipitation method for preparing the precursor, ammonia water and alkali liquor are added into an aqueous solution, and complicated processes such as stirring, heating, precipitation and washing are required, and more pollution such as waste gas and waste water is caused.
The discharge ports of the nozzle are not communicated and are distributed on the same circular ring, so that the material can form round layered particles, and the materials consisting of different elements can alternately grow in different thin layers, so that the prepared precursor particles form a superlattice structure after high-temperature sintering. The nozzle opening of shell tip convergent is favorable to high-pressure gas to carry out effectual friction and shearing to the material in, carries out cyclic annular parcel to the material to make more round granule.
Preferably, the number of the feeding pipes is two, namely a first feeding pipe and a second feeding pipe; the number of the material channels is two, and the two material channels are respectively a first material channel and a second material channel; the first feeding pipe is communicated with the first material channel, and the second feeding pipe is communicated with the second material channel. The two feeding pipes and the two material channels are arranged, so that the condition for preparing the precursor of the lithium ion battery anode material with the superlattice structure can be realized, namely two thin layers with incompletely same element distribution are formed by using different raw materials and grow alternately regularly. Of course, three or more feed tubes and feed channels may be used, as appropriate, depending on the desired electrical properties of the desired lithium ion battery positive electrode material.
The invention also provides a method for preparing the lithium ion battery anode material with the superlattice structure by adopting the nozzle, which comprises the following steps of:
step one, preparing a dispersion liquid A and a dispersion liquid B
Preparing a dispersion liquid A and a dispersion liquid B by using a compound of a lithium element and a compound of an M element, wherein the total amount of the lithium element and the M element in the dispersion liquid A and the dispersion liquid B conforms to a chemical formula Li a ＭO x Medium stoichiometric ratio, wherein: a =0.5-1.5,2 ≤ x ≤ 2.5, M is at least one of nickel, cobalt, manganese and aluminum, and the kinds or contents of M elements contained in the dispersion liquid A and the dispersion liquid B are not completely the same;
step two, spray fusion granulation
Simultaneously introducing the dispersion liquid A and the dispersion liquid B into the first feeding pipe and the second feeding pipe respectively, spraying out from the first discharging port and the second discharging port, carrying out spray fusion, and drying and granulating;
step three, sintering
Keeping the temperature of the produced particles at 450-600 ℃ for 3-10h; then continuously heating to 600-1000 ℃, and sintering for 5-30h. In the method, the dispersion liquid A and the dispersion liquid B prepared in the step one have components with different types or contents, when spray granulation is carried out in the step two, the dispersion liquid A and the dispersion liquid B are respectively introduced into a first feed pipe and a second feed pipe and are sprayed out from a first discharge port and a second discharge port, spray drying granulation is carried out, the formed particles are precursor particles which are uniform and ordered in macroscopical view and are doped with elements with disordered structures in microcosmic view, the elements in the precursor particles are periodically and alternately grown into thin layers according to a certain rule, and after sintering in the step three, peaks with a superlattice structure appear in an XRD image of the lithium ion battery anode material prepared by oxidizing the M element and lithium ions.
In addition, because the method of the invention adopts spray granulation when preparing the lithium ion battery cathode material with a superlattice structure, lithium ions are uniformly mixed in the particles of the precursor during granulation, and the problems of non-uniformity and the like caused by lithium ion diffusion do not exist in the sintering process.
The lithium ion battery anode material with the superlattice structure prepared by the invention has a more stable structure in the charge-discharge cycle process of the lithium ion battery, the cycle life of the battery is long, the specific capacity is high, the electronic conductivity and the ionic conductivity of the battery are high, and the rate capability of the battery is improved.
Preferably, the dispersion medium of the dispersion liquid a and the dispersion liquid B is water or ethanol.
Preferably, the solids content of both dispersion a and dispersion B is 15 to 50wt%. The use of the dispersion liquid A and the dispersion liquid B each having a solid content of 15 to 50% by weight makes it difficult to clog a nozzle at the time of spraying.
Preferably, the particle size of the dispersed phase in the dispersion liquid A and the dispersion liquid B is 1nm to 700nm. The particle size of the dispersed phase is too large, which is not beneficial to the migration of each ion in the sintering process and influences the uniformity of the prepared material.
Preferably, during spray granulation, the pressure of the airflow atomizer is 0.1-1.0Mpa, the air inlet temperature is 150-300 ℃, and the air outlet temperature is 70-150 ℃. The pressure, the air inlet temperature and the air outlet temperature of the atomizer are favorable for rapid granulation, the regularity of formed alternate thin layers is good, and the comprehensive performance of the prepared battery material is better.
The invention also provides the lithium ion battery anode material with the superlattice structure prepared by the method.
The invention has the technical effects that:
the nozzle for preparing the lithium ion battery anode material with the superlattice structure is used for preparing precursor particles by spray drying materials with incompletely same element components through different material feeding pipes and material channels which are not communicated with each other on the core body and a fusion granulation technical means, the precursor particles are formed by alternately growing thin layers with different element compositions, and the nozzle is simple in preparation process and small in pollution. The lithium ion battery anode material sintered by the precursor particles has a superlattice structure, has a stable structure in the charge-discharge cycle process of the lithium ion battery, and is good in electronic conductivity and ionic conductivity, the rate capability of the battery is improved, and the energy density of the battery is high.
Drawings
Fig. 1 is a longitudinal sectional view of a nozzle for preparing a positive electrode material of a lithium ion battery having a superlattice structure according to example 1.
Fig. 2 isbase:Sub>A sectional view taken along linebase:Sub>A-base:Sub>A of fig. 1.
Fig. 3 is a front view of the core.
Fig. 4 is a top view of fig. 3.
Fig. 5 is a front view of the gas distributor.
Fig. 6 is an axial cross-sectional view of the gas distributor.
Fig. 7 is a top view of fig. 5.
Fig. 8 is an XRD pattern of the lithium ion battery positive electrode material with superlattice structure prepared in example 2.
Fig. 9 is a scanning electron microscope image of the lithium ion battery cathode material prepared in example 2.
Fig. 10 is an XRD pattern of the positive electrode material for lithium ion battery prepared in comparative example 1.
Fig. 11 is an EDS diagram of the positive electrode material for a lithium ion battery prepared in comparative example 1.
Fig. 12 is an XRD chart of the lithium ion battery cathode material with superlattice structure prepared in example 3.
Fig. 13 is an XRD pattern of the lithium ion battery cathode material with superlattice structure prepared in example 4.
Fig. 14 is an XRD pattern of the lithium ion battery cathode material with superlattice structure prepared in example 5.
Fig. 15 is an XRD pattern of the lithium ion battery cathode material prepared in comparative example 4.
Fig. 16 is an XRD pattern of the lithium ion battery positive electrode material prepared in example 6.
In the figure:
1. an air inlet pipe; 2. a nozzle tip; 21. a core body; 211. A first material passage; 212. a second material passage; 213. a first discharge port; 214. a second discharge port; 22. a gas distributor; 221. a gas channel; 23. a housing; 231. a nozzle opening; 3. a first feed tube; 4. a second feed tube.
Detailed Description
The present invention will be described in detail with reference to the following examples and drawings.
Example 1
Fig. 1 isbase:Sub>A longitudinal sectional view ofbase:Sub>A nozzle for producingbase:Sub>A positive electrode material ofbase:Sub>A lithium ion battery havingbase:Sub>A superlattice structure according to this embodiment, fig. 2 isbase:Sub>A sectional view taken alongbase:Sub>A linebase:Sub>A-base:Sub>A of fig. 1, fig. 3 isbase:Sub>A front view ofbase:Sub>A core, fig. 4 isbase:Sub>A top view of fig. 3, fig. 5 isbase:Sub>A front view ofbase:Sub>A gas distributor, fig. 6 is an axial sectional view of the gas distributor, and fig. 7 isbase:Sub>A top view of fig. 5.
As shown in fig. 1 and fig. 4, the nozzle for preparing a positive electrode material of a lithium ion battery with a superlattice structure in the present embodiment includes an air inlet pipe 1, a nozzle tip 2, a first feeding pipe 3, and a second feeding pipe 4. The nozzle tip 2 comprises a core 21, a gas distributor 22 and a shell 23; the core body 21 is fixed at the end part of the air inlet pipe 1, and a first material passage 211 and a second material passage 212 which are not communicated with each other are arranged in the core body 21; the top end of the first material passage 211 is connected with the first feeding pipe 3, and the top end of the second material passage 212 is connected with the second feeding pipe 4. As shown in fig. 2 and 3, an arc-shaped first discharge port 213 is formed at the end of the first material passage 211 on the outlet end face of the core body 21, an arc-shaped second discharge port 214 is formed at the end of the second material passage 212 on the outlet end face of the core body 21, and the first discharge port 213 and the second discharge port 214 are arranged on the same ring and are not communicated with each other. As shown in fig. 1, 5, 6, and 7, the gas distributor 22 is an annular frustum fixed on the outer periphery of the core body 21, a plurality of gas channels 221 are uniformly distributed on the gas distributor 22, the gas channels 221 are communicated with the gas inlet pipe 1, and the plurality of gas channels 221 surround the outer periphery of a circular ring formed by the first discharge port 213 and the second discharge port 214; the housing 23 is fixed at the end of the gas inlet pipe 1 in a sealing manner, the housing 23 surrounds the gas distributor 22 in an annular manner, the end of the housing 23 is tapered and provided with a nozzle opening 231, and the diameter of the nozzle opening 231 is larger than the diameter of the ring formed by the first discharge hole 213 and the second discharge hole 214.
The nozzle for preparing the lithium ion battery cathode material with the superlattice structure in the embodiment adopts two feeding pipes and two material channels, and the first discharging hole 213 and the second discharging hole 214 are distributed on the same circular ring and are not communicated with each other. Of course, a plurality of material channels and a plurality of feeding pipes can be arranged, and a plurality of discharging holes which are distributed on the same circular ring and are not communicated with each other are formed.
The working principle is as follows: when preparing the lithium ion battery anode material with a superlattice structure, respectively introducing a dispersion liquid A and a dispersion liquid B from a first feeding pipe 3 and a second feeding pipe 4, wherein the dispersion liquid A and the dispersion liquid B are prepared by a compound of a lithium element and a compound of an M element, and the total amount of the lithium element and the M element in the dispersion liquid A and the dispersion liquid B conforms to a chemical formula Li a ＭO x Medium stoichiometric ratio, wherein: a =0.5-1.5,2 ≤ x ≤ 2.5, M is at least one of nickel, cobalt, manganese and aluminum, and the kinds or contents of M elements contained in the dispersion liquid A and the dispersion liquid B are not completely the same; the dispersion liquid A and the dispersion liquid B respectively enter through a first feeding pipe 3 and a second feeding pipe 4, are sprayed out from a first discharging port 213 and a second discharging port 214, simultaneously, high-pressure gas enters from a gas inlet pipe 1 and is sprayed out through a plurality of gas channels 221 on a gas distributor 22, the plurality of gas channels 221 surround the peripheries of the first discharging port 213 and the second discharging port 214 which form the same circular ring, the dispersion liquid A and the dispersion liquid B are atomized through the high-pressure gas after being sprayed out, the fusion is carried out at the end face of a nozzle 231, and then the particles are made into particles after being dried through hot air in a spray drying system; after high-temperature sintering, the formed lithium ion battery positive electrode material has a superlattice structure formed by multiple components and/or structures.
Example 2
The nozzle for the lithium ion battery cathode material with the superlattice structure in the embodiment 1 is adopted to prepare the lithium ion battery cathode material with the superlattice structure, and the method comprises the following steps:
step one, preparing a dispersion liquid A and a dispersion liquid B
Preparing a dispersion liquid A; the mixture aqueous solution is prepared by using lithium hydroxide, nickel sulfate, cobalt sulfate and aluminum trichloride, wherein the molar ratio of lithium, nickel, cobalt and aluminum elements is 10.
Preparing a dispersion liquid B; preparing a mixture aqueous solution by using lithium hydroxide, nickel sulfate, cobalt sulfate and manganese sulfate, wherein the molar ratio of lithium, nickel, cobalt and manganese elements is 10.
Step two, spray granulation
Using the nozzle for preparing the lithium ion battery cathode material with the superlattice structure provided in example 1, simultaneously introducing the dispersion liquid a and the dispersion liquid B into the first feeding pipe 3 and the second feeding pipe 4 at the same flow rate, respectively, and spraying out from the first discharging port 213 and the second discharging port 214, with an air flow atomizer, the air inlet temperature of a spray drying chamber being 200 ℃, the air outlet temperature being 100 ℃, and the air flow spraying pressure being 0.3MPa, and performing spray drying to obtain lithium ion battery cathode material precursor particles.
Step three, sintering
Sintering the obtained precursor particles of the lithium ion battery anode material for 3 hours in the atmosphere of oxygen, wherein the sintering temperature is 450 ℃. Then heating to 850 ℃ at the heating rate of 5 ℃/min, and keeping the temperature at 850 ℃ to continue sintering for 30 hours. And crushing, grading and demagnetizing the sintered material to obtain the lithium ion battery anode material with the superlattice structure.
XRD analysis is carried out on the obtained lithium ion battery cathode material, figure 8 is an XRD diagram, and it can be seen from figure 8 that the X-ray diffraction peaks of the material obtained in the embodiment correspond to standard cards one by one and no impurity peak appears, and the material has high crystallinity, and simultaneously, a characteristic peak of a superlattice (superlattice) ordered structure appears between 21 and 30 degrees. Therefore, this example successfully prepared a positive electrode material of a lithium ion battery having a superlattice structure.
Fig. 9 is a scanning electron micrograph of the obtained lithium ion battery cathode material with a superlattice structure, and as can be seen from fig. 9, the prepared lithium ion battery cathode material has a spherical structure.
Comparative example 1
Preparing the lithium ion battery anode material.
Step one, coprecipitation preparation of precursor particles
Preparing a nickel sulfate, cobalt sulfate, aluminum trichloride and manganese sulfate mixed metal salt solution, a 2.0mol/L ammonia water solution and a 2.0mol/L precipitant sodium hydroxide solution, wherein the molar ratio of Ni to Co to Al to Mn = 13.
0.5mol/L ammonia water solution is added into the reaction kettle to be used as reaction bottom liquid. In N 2 The reaction base solution was heated to 80 ℃ under the protection of an atmosphere, and then the mixed metal salt solution, the aqueous ammonia solution and the sodium hydroxide solution were gradually added to the stirred (stirring speed 400 r/min) reaction vessel through a metering pump at a flow rate ratio of 1.0mL/min:1.0mL/min:5 mL/min. The pH value of the whole reaction system is controlled to be 12, and reaction supernatant is continuously pumped out of the reaction kettle through a filtering and liquid-pumping device so as to control the liquid level in the reaction kettle to be constant. And after the reaction is finished for 24 hours, filtering, cleaning, and drying at 150 ℃ under a vacuum condition to obtain precursor powder of the lithium ion battery anode material.
Step two, sintering
Weighing the precursor powder of the lithium ion battery anode material, adding lithium hydroxide, and uniformly mixing, wherein the element molar ratio of lithium: (nickel + cobalt + manganese + aluminum) =1, and then sintering is performed by the same method as the third step in example 2, so as to prepare the lithium ion battery cathode material.
XRD analysis is carried out on the obtained lithium ion battery cathode material, figure 10 is an XRD pattern, and the typical alpha-NaFeO is shown in figure 10 2 A layered crystal structure without a characteristic peak of a superlattice structure. EDS analysis was performed on the obtained lithium ion battery positive electrode material, FIG. 11 is an EDS diagram, and as can be seen from FIG. 11, liNi was formed 0.65 Co 0.175 Mn 0.15 Al 0.025 O 2 The layered positive electrode material of (1).
Example 3
The nozzle for the lithium ion battery cathode material with the superlattice structure in the embodiment 1 is adopted to prepare the lithium ion battery cathode material with the superlattice structure, and the method comprises the following steps:
step one, preparing a dispersion liquid A and a dispersion liquid B
Preparing a dispersion liquid A; preparing a mixture aqueous solution by using lithium hydroxide, nickel sulfate, cobalt sulfate and manganese sulfate, wherein the molar ratio of lithium, nickel, cobalt and manganese elements is 10.
Preparing a dispersion liquid B; and (2) preparing a mixture aqueous solution by using lithium hydroxide and manganese sulfate, wherein the molar ratio of lithium to manganese elements is 1.
Step two, spray granulation
Spray granulation was performed by the same method as in example 2 using the nozzle for preparing a lithium ion battery positive electrode material having a superlattice structure provided in example 1 with an air flow atomizer, to obtain lithium ion battery positive electrode material precursor particles.
Step three, sintering
Sintering the obtained precursor particles of the lithium ion battery anode material for 10 hours in the atmosphere of oxygen, wherein the sintering temperature is 450 ℃. Then heating to 900 ℃ at the heating speed of 5 ℃/min, and keeping the temperature at 900 ℃ to continue sintering for 10 hours. And crushing, grading and demagnetizing the sintered material to obtain the lithium ion battery anode material with the superlattice structure.
XRD analysis is carried out on the obtained lithium ion battery anode material, figure 12 is an XRD (X-ray diffraction) diagram, and figure 12 shows that the X-ray diffraction peaks of the material obtained in the embodiment correspond to standard cards one by one, no impurity peak appears, and the material has high crystallinity. On the basis of having a layered structure and a spinel structure, a characteristic peak of a superlattice (superlattice) ordered structure occurs at the same time between 21 and 30 °. Therefore, this example successfully produced a positive electrode material having a superlattice structure.
Comparative example 2
Preparing the lithium ion battery anode material.
Step one, preparing precursor particles by coprecipitation
Preparing a mixed metal salt solution of nickel sulfate, cobalt sulfate and manganese sulfate, 2.0mol/L ammonia water solution and 2.0mol/L precipitant sodium hydroxide solution, wherein the molar ratio of Ni to Co to Mn = 5.
The remaining steps in step one are exactly the same as in comparative example 1.
Step two, sintering
Weighing the precursor powder of the lithium ion battery anode material, adding lithium hydroxide, and uniformly mixing, wherein the element molar ratio of lithium: and (2) (nickel + cobalt + manganese) =2, and then sintering is performed by the same method as the third step in example 3, so as to prepare the lithium ion battery cathode material.
From EDS analysis and XRD analysis, it can be seen that comparative example 2 obtained a chemical formula of Li 0.66 Ni 0.16 Co 0.06 Mn 0.76 O 2 The material of (1), which is a lithium-oxygen compound lacking a lithium phase and does not have a superlattice structure.
Example 4
The nozzle for the lithium ion battery anode material with the superlattice structure in the embodiment 1 is adopted to prepare the lithium ion battery anode material with the superlattice structure, and the method comprises the following steps:
step one, preparing a dispersion liquid A and a dispersion liquid B
Preparing a dispersion liquid A; lithium carbonate, manganese acetate and nickel acetate with the particle size of 1-700 nm are added with water to prepare a water dispersion liquid, wherein the molar ratio of lithium, manganese and nickel elements is 6.
Preparing a dispersion liquid B; lithium carbonate, manganese acetate and nickel acetate with the particle size of 1-500 nm are added with water to prepare a dispersion liquid, wherein the molar ratio of lithium, manganese and nickel elements is (2).
Step two, spray granulation
Spray granulation was performed by the same method as in example 2 using the nozzle for preparing a lithium ion battery positive electrode material having a superlattice structure provided in example 1 with an air flow atomizer, to obtain lithium ion battery positive electrode material precursor particles.
Step three, sintering
Sintering the obtained precursor particles of the lithium ion battery anode material for 10 hours in the atmosphere of oxygen, wherein the sintering temperature is 450 ℃. Then heating to 900 ℃ at the heating rate of 5 ℃/min, and keeping the temperature of 900 ℃ to continue sintering for 10 hours. And crushing, grading and demagnetizing the sintered material to obtain the lithium ion battery anode material with the superlattice structure.
XRD analysis is performed on the obtained lithium ion battery positive electrode material, fig. 13 is an XRD chart, and it can be seen from fig. 13 that X-ray diffraction peaks of the material obtained in this example correspond to standard cards one to one, no impurity peak appears, and the material has high crystallinity. On the basis of having a layered structure and a spinel structure, a characteristic peak of a superlattice (superlattice) ordered structure appears between 21 and 30 °. Therefore, this example successfully prepared a positive electrode material having a superlattice structure.
Comparative example 3
Preparing the lithium ion battery anode material.
Step one, preparing precursor particles by coprecipitation
Preparing a nickel sulfate and manganese sulfate mixed metal salt solution with a molar ratio of Ni to Mn =1 and a total concentration of 2.0mol/L, a 2.0mol/L ammonia water solution and a 2.0mol/L precipitant sodium hydroxide solution.
The remaining steps in step one are exactly the same as in comparative example 1.
Step two, sintering
Weighing the precursor powder of the lithium ion battery anode material, adding lithium hydroxide, and uniformly mixing, wherein the element molar ratio of lithium: (nickel + manganese) =5, and then sintering is performed by the same method as the third step in example 4, so as to prepare the lithium ion battery cathode material.
As can be seen from EDS analysis and XRD analysis, this comparative example obtained a chemical formula of Li 0.83 Mn 0.75 Ni 0.25 O 2 The positive electrode material of (1). The material is a lithium-oxygen compound lacking a lithium phase and does not have a superlattice structure.
Example 5
The nozzle for the lithium ion battery cathode material with the superlattice structure in the embodiment 1 is adopted to prepare the lithium ion battery cathode material with the superlattice structure, and the method comprises the following steps:
step one, preparing a dispersion liquid A and a dispersion liquid B
Preparing a dispersion liquid A; the mixture aqueous solution is prepared by using lithium hydroxide, nickel sulfate and cobalt sulfate, wherein the molar ratio of lithium, nickel and cobalt elements is 5.
Preparing a dispersion liquid B; preparing a mixture aqueous solution by using lithium hydroxide, nickel sulfate and manganese sulfate, wherein the molar ratio of lithium, nickel and manganese elements is 5.
Step two, spray granulation
Spray granulation was performed by the same method as in example 2 using the nozzle for preparing a lithium ion battery positive electrode material having a superlattice structure provided in example 1 with an air flow atomizer, to obtain lithium ion battery positive electrode material precursor particles.
Step three, sintering
Sintering the obtained precursor particles of the lithium ion battery anode material for 3 hours in the atmosphere of oxygen, wherein the sintering temperature is 450 ℃. Then heating to 700 ℃ at the heating rate of 5 ℃/min, and keeping the temperature at 700 ℃ to continue sintering for 10 hours. And crushing, grading and demagnetizing the sintered material to obtain the lithium ion battery anode material with the superlattice structure.
XRD analysis is carried out on the obtained lithium ion battery cathode material, figure 14 is an XRD diagram, and figure 14 shows that the X-ray diffraction peaks of the material obtained in the embodiment correspond to standard cards one by one without impurity peaks, and the material has high crystallinity, and simultaneously has characteristic peaks of a superlattice (superlattice) ordered structure between 21 and 30 degrees. Therefore, this example successfully produced a positive electrode material having a superlattice structure.
Comparative example 4
Step one, preparing precursor particles by coprecipitation
Preparing a mixed metal salt solution of nickel sulfate, cobalt sulfate and manganese sulfate, 2.0mol/L ammonia water solution and 2.0mol/L precipitant sodium hydroxide solution, wherein the molar ratio of Ni to Co to Mn = 8. The remaining steps in step one are exactly the same as in comparative example 1.
Step two, sintering
Weighing the precursor powder of the lithium ion battery anode material, adding lithium hydroxide, and uniformly mixing, wherein the element molar ratio of lithium: (nickel + cobalt + manganese) =1, and then sintering is performed by the same method as the third step in example 5, so as to prepare the lithium ion battery cathode material.
XRD analysis is carried out on the obtained lithium ion battery anode material, figure 15 is an XRD figure, and it can be seen from figure 15 that X-ray diffraction peaks of the material obtained by the comparative example correspond to standard cards one by one and no impurity peak appears, and the material has high crystallinity, no superlattice structure peak appears and no superlattice structure exists.
Example 6
The nozzle for the lithium ion battery cathode material with the superlattice structure in the embodiment 1 is adopted to prepare the lithium ion battery cathode material with the superlattice structure, and the method comprises the following steps:
step one, preparing a dispersion liquid A and a dispersion liquid B
Preparing a dispersion liquid A; lithium hydroxide and manganese sulfate are used for preparing a mixture aqueous solution, wherein the molar ratio of lithium to manganese elements is 2.
Preparing a dispersion liquid B; and preparing a mixture aqueous solution by using lithium hydroxide and manganese sulfate, wherein the molar ratio of lithium to manganese elements is 1.
Step two, spray granulation
Spray granulation was performed by the same method as in example 2 using the nozzle for preparing a lithium ion battery positive electrode material having a superlattice structure provided in example 1 with an air flow atomizer, to obtain lithium ion battery positive electrode material precursor particles.
Step three, sintering
Sintering the obtained precursor particles of the lithium ion battery anode material for 10 hours in the air atmosphere, wherein the sintering temperature is 450 ℃. Then, the temperature is increased to 780 ℃ at the temperature increasing speed of 5 ℃/min, and the sintering is continued for 10 hours after the temperature is maintained at 780 ℃. And crushing, grading and demagnetizing the sintered material to obtain the lithium ion battery anode material with the superlattice structure.
XRD analysis is carried out on the obtained lithium ion battery anode material, figure 16 is an XRD (X-ray diffraction) diagram, and it can be seen from figure 16 that X-ray diffraction peaks of the material obtained in the embodiment correspond to standard cards one by one, no impurity peak appears, and the material has high crystallinity. On the basis of having a layered structure and a spinel structure, a characteristic peak of a superlattice (superlattice) ordered structure appears between 21 ° and 30 ° at the same time. Therefore, this example successfully prepared a positive electrode material having a superlattice structure.
Comparative example 5
Step one, coprecipitation preparation of precursor particles
Manganese sulfate metal salt solution with the total concentration of 2.0mol/L, 2.0mol/L ammonia water solution and 2.0mol/L precipitator sodium hydroxide solution are prepared. The remaining steps in step one are exactly the same as in comparative example 1.
Step two, sintering
Weighing the precursor powder of the lithium ion battery anode material, adding lithium hydroxide, and uniformly mixing, wherein the element molar ratio of lithium: and (3) manganese =1, and then sintering the mixture by the same method as the third step in the example 6 to obtain the lithium ion battery cathode material.
As can be seen from EDS analysis and XRD analysis, lithium manganate (LiMnO) having a layered structure is obtained in this manner 2 ) It is apparent that the material does not have a superlattice structure and is different from the material obtained in example 6.
Example 7
The nozzle for the lithium ion battery cathode material with the superlattice structure in the embodiment 1 is adopted to prepare the lithium ion battery cathode material with the superlattice structure, and the method comprises the following steps:
step one, preparing a dispersion liquid A and a dispersion liquid B
Preparing a dispersion liquid A; crushing lithium carbonate, nickel hydroxide and cobaltosic oxide, grinding the crushed materials into particles with the particle size of 1nm-700nm, adding water to prepare mixed slurry, wherein the molar ratio of lithium, nickel and cobalt elements is 5.
Preparing a dispersion liquid B; crushing lithium carbonate, nickel hydroxide and manganese carbonate, grinding the crushed materials into particles with the particle size of 1nm-700nm, adding water to prepare mixed slurry, wherein the molar ratio of lithium, nickel and manganese elements is 5.
Step two, spray granulation
Using the nozzle for preparing the lithium ion battery cathode material with the superlattice structure provided in example 1, simultaneously introducing the dispersion liquid a and the dispersion liquid B into the first feeding pipe 3 and the second feeding pipe 4 at the same flow rate, respectively, and spraying out from the first discharging port 213 and the second discharging port 214, with an air flow atomizer, the air inlet temperature of a spray drying chamber being 150 ℃, the air outlet temperature being 70 ℃, and the air flow spraying pressure being 0.1MPa, and performing spray drying and granulation to obtain lithium ion battery cathode material precursor particles.
Step three, sintering
Sintering the obtained precursor particles of the lithium ion battery anode material for 6 hours in the atmosphere of oxygen, wherein the sintering temperature is 500 ℃. Then heating to 850 ℃ at the heating rate of 5 ℃/min, and keeping the temperature at 700 ℃ to continue sintering for 30 hours. The sintered material is crushed, graded and demagnetized to obtain the lithium ion battery anode material, and XRD test shows that the lithium ion battery anode material has a superlattice structure.
Example 8
The nozzle for the lithium ion battery cathode material with the superlattice structure in the embodiment 1 is adopted to prepare the lithium ion battery cathode material with the superlattice structure, and the method comprises the following steps:
step one, preparing a dispersion liquid A and a dispersion liquid B
Preparing a dispersion liquid A; and preparing a mixture aqueous solution by using lithium hydroxide and manganese sulfate so that the molar ratio of lithium to manganese elements is 1.
Preparing a dispersion liquid B; preparing a mixture aqueous solution by using lithium hydroxide, nickel sulfate and manganese sulfate, wherein the molar ratio of lithium, nickel and manganese elements is 1.
Step two, spray granulation
Using an airflow atomizer, using the nozzle for preparing a lithium ion battery cathode material with a superlattice structure provided in example 1, simultaneously introducing the dispersion liquid a and the dispersion liquid B into the first feeding pipe 3 and the second feeding pipe 4 at the same flow rate, respectively, and spraying out from the first discharging port 213 and the second discharging port 214, wherein the inlet air temperature of the spray drying chamber is 300 ℃, the outlet air temperature is 150 ℃, the airflow spray pressure is 1.0MPa, and spray drying is performed to obtain lithium ion battery cathode material precursor particles.
Step three, sintering
Sintering the obtained precursor particles of the lithium ion battery anode material for 10 hours in the atmosphere of oxygen, wherein the sintering temperature is 450 ℃. Then heating to 720 ℃ at a heating speed of 5 ℃/min, and keeping the temperature at 720 ℃ to continue sintering for 10 hours. The sintered material is crushed, graded and demagnetized to obtain the lithium ion battery anode material, and XRD test shows that the lithium ion battery anode material has a superlattice structure.
Example 9
The nozzle for the lithium ion battery cathode material with the superlattice structure in the embodiment 1 is adopted to prepare the lithium ion battery cathode material with the superlattice structure, and the method comprises the following steps:
step one, preparing a dispersion liquid A and a dispersion liquid B
Preparing a dispersion liquid A; an aqueous mixture solution is prepared by using lithium hydroxide, nickel sulfate and cobalt sulfate, wherein the molar ratio of lithium, nickel and cobalt elements is 10.
Preparing a dispersion liquid B; the mixture aqueous solution is prepared by using lithium hydroxide, nickel sulfate and aluminum trichloride, wherein the molar ratio of lithium, nickel and aluminum elements is 10.
Step two, spray granulation
Spray granulation was performed by the same method as in example 2 using the nozzle for preparing a lithium ion battery positive electrode material having a superlattice structure provided in example 1 with an air flow atomizer, to obtain lithium ion battery positive electrode material precursor particles.
Step three, sintering
Sintering the obtained precursor particles of the lithium ion battery anode material for 10 hours in the atmosphere of oxygen, wherein the sintering temperature is 450 ℃. Then heating to 780 ℃ at the heating rate of 5 ℃/min, and keeping the temperature at 700 ℃ to continue sintering for 10 hours. The sintered material is crushed, graded and demagnetized to obtain the lithium ion battery anode material, and XRD test shows that the lithium ion battery anode material has a superlattice structure.
Example 10
The nozzle for the lithium ion battery cathode material with the superlattice structure in the embodiment 1 is adopted to prepare the lithium ion battery cathode material with the superlattice structure, and the method comprises the following steps:
step one, preparing a dispersion liquid A and a dispersion liquid B
Preparing a dispersion liquid A; grinding lithium hydroxide, nickel oxide and manganese sulfate into particles with the particle size of 1-700 nm, adding water, and preparing mixed slurry, wherein the molar ratio of lithium to nickel to manganese is 2.
Preparing a dispersion liquid B; grinding lithium hydroxide and manganous-manganic oxide into particles with the particle size of 1nm-700nm, adding water, and preparing mixed slurry to ensure that the molar ratio of lithium to manganese elements is 2.
Step two, spray granulation
Spray granulation was performed by the same method as in example 2 using the nozzle for preparing a lithium ion battery positive electrode material having a superlattice structure provided in example 1 with an air flow atomizer, to obtain lithium ion battery positive electrode material precursor particles.
Step three, sintering
Sintering the obtained precursor particles of the lithium ion battery anode material for 10 hours in the atmosphere of oxygen, wherein the sintering temperature is 450 ℃. Then heating to 900 ℃ at the heating rate of 5 ℃/min, and keeping the temperature of 900 ℃ to continue sintering for 10 hours. The sintered material is crushed, graded and demagnetized to obtain the lithium ion battery anode material, and XRD test shows that the lithium ion battery anode material has a superlattice structure.
Example 11
The nozzle for the lithium ion battery cathode material with the superlattice structure in the embodiment 1 is adopted to prepare the lithium ion battery cathode material with the superlattice structure, and the method comprises the following steps:
step one, preparing a dispersion liquid A and a dispersion liquid B
Preparing a dispersion liquid A; preparing a mixture aqueous solution by using lithium hydroxide, nickel sulfate, cobalt sulfate and manganese sulfate, wherein the molar ratio of lithium, nickel, cobalt and manganese elements is 3.
Preparing a dispersion liquid B; and (2) preparing a mixture aqueous solution by using lithium hydroxide and manganese sulfate, wherein the molar ratio of lithium to manganese elements is 2.
Step two, spray granulation
Spray granulation was performed by the same method as in example 2 using the nozzle for preparing a lithium ion battery positive electrode material having a superlattice structure provided in example 1 with an air flow atomizer, to obtain lithium ion battery positive electrode material precursor particles.
Step three, sintering
Sintering the obtained precursor particles of the lithium ion battery anode material for 10 hours in the atmosphere of oxygen, wherein the sintering temperature is 600 ℃. Then heating to 900 ℃ at the heating rate of 5 ℃/min, and keeping the temperature of 900 ℃ to continue sintering for 5 hours. The sintered material is crushed, graded and demagnetized to obtain the lithium ion battery anode material, and XRD test shows that the lithium ion battery anode material has a superlattice structure.
Example 12
The nozzle for the lithium ion battery cathode material with the superlattice structure in the embodiment 1 is adopted to prepare the lithium ion battery cathode material with the superlattice structure, and the method comprises the following steps:
step one, preparing a dispersion liquid A and a dispersion liquid B
Dispersion a and dispersion B were prepared in the same manner as in example 10.
Step two, spray granulation
The nozzle for preparing a positive electrode material of a lithium ion battery having a superlattice structure provided in example 1 was used with a gas flow atomizer, while the dispersion liquid a and the dispersion liquid B were mixed in a ratio of 3: and 2, respectively introducing the mixture into the first feeding pipe 3 and the second feeding pipe 4 according to the flow speed ratio, spraying the mixture out from the first discharging hole 213 and the second discharging hole 214, performing spray drying on the mixture to obtain precursor particles of the lithium ion battery anode material, wherein the inlet air temperature of the spray drying chamber is 200 ℃, the outlet air temperature is 100 ℃, and the airflow spray pressure is 0.3 MPa.
Step three, sintering
The lithium ion battery positive electrode material is obtained by crushing, grading and demagnetizing after being sintered by the same method as that of the embodiment 10, and the lithium ion battery positive electrode material has a superlattice structure as can be known from XRD (X-ray diffraction) tests.
Example 13
The nozzle for the lithium ion battery anode material with the superlattice structure in the embodiment 1 is adopted to prepare the lithium ion battery anode material with the superlattice structure, and the method comprises the following steps:
step one, preparing a dispersion liquid A and a dispersion liquid B
Preparing a dispersion liquid A; the method comprises the following steps of grinding lithium hydroxide, manganese dioxide, nickel hydroxide and cobaltosic oxide into particles with the particle size of 1-700 nm, adding water, and preparing mixed slurry, wherein the molar ratio of lithium, manganese, nickel and cobalt elements is (9).
Preparing a dispersion liquid B; grinding lithium carbonate and manganese dioxide into particles with the particle size of 1nm-700nm, adding water, and preparing mixed slurry so that the molar ratio of lithium to manganese elements is 1.
Step two, spray granulation
Spray granulation was performed by the same method as in example 2 using the nozzle for preparing a lithium ion battery positive electrode material having a superlattice structure provided in example 1 with an air flow atomizer, to obtain lithium ion battery positive electrode material precursor particles.
Step three, sintering
Sintering the obtained precursor particles of the lithium ion battery anode material for 10 hours in the atmosphere of oxygen, wherein the sintering temperature is 600 ℃. Then heating to 1000 ℃ at the heating rate of 5 ℃/min, and keeping the temperature at 900 ℃ to continue sintering for 10 hours. The sintered material is crushed, graded and demagnetized to obtain the lithium ion battery anode material, and XRD test shows that the lithium ion battery anode material has a superlattice structure.
Example 14
The nozzle for the lithium ion battery anode material with the superlattice structure in the embodiment 1 is adopted to prepare the lithium ion battery anode material with the superlattice structure, and the method comprises the following steps:
step one, preparing a dispersion liquid A and a dispersion liquid B
Preparing a dispersion liquid A; preparing a mixture aqueous solution by using lithium hydroxide, nickel sulfate and manganese sulfate, wherein the molar ratio of lithium, nickel and manganese elements is 2.
Preparing a dispersion liquid B; and preparing a mixture aqueous solution by using lithium hydroxide and manganese sulfate, wherein the molar ratio of lithium to manganese elements is 1.
Step two, spray granulation
Spray granulation was performed by the same method as in example 2 using the nozzle for preparing a lithium ion battery positive electrode material having a superlattice structure provided in example 1 with an air flow atomizer, to obtain lithium ion battery positive electrode material precursor particles.
Step three, sintering
Sintering the obtained precursor particles of the lithium ion battery anode material for 10 hours in the atmosphere of oxygen, wherein the sintering temperature is 450 ℃. Then heating to 750 ℃ at the heating speed of 5 ℃/min, and keeping the temperature at 750 ℃ to continue sintering for 10 hours. The sintered material is crushed, graded and demagnetized to obtain the lithium ion battery anode material, and XRD test shows that the lithium ion battery anode material has a superlattice structure.
And (3) testing:
1. battery fabrication
And respectively preparing the lithium ion battery anode materials prepared in each embodiment and each proportion into lithium ion batteries, and carrying out electrical property test. The manufacturing method of the lithium ion battery is as follows;
grinding and uniformly mixing the lithium ion battery positive electrode material, conductive carbon black and a binder polyvinylidene fluoride according to a mass ratio of 8. And (3) drying the aluminum foil coated with the slurry in an oven with the temperature of 80 ℃ by blowing for 2h, and then drying in a vacuum oven with the temperature of 110 ℃ for 12h to prepare the circular positive plate. The circular positive plateIs a positive electrode, a metal lithium sheet is a negative electrode, 1mol/l LiPF 6 EC: DMC =1 as electrolyte, polypropylene membrane as separator, assembled into 2032 type button cell in glove box filled with argon gas.
2. Electrical Performance testing
The resulting cell was tested for charge and discharge at 25 c and the results are reported in table 1.
TABLE 1
As can be seen from table 1, comparative example 1 and example 1 have the same composition of raw materials, and the prepared positive electrode materials of lithium ion batteries have the same composition in macroscopic view. The difference is that the comparative example 1 adopts a coprecipitation method in the prior art, and nickel, cobalt, aluminum and manganese in the prepared lithium ion battery anode material are uniformly distributed at an element level; the anode material of the lithium ion battery prepared in the embodiment 2 adopts the nozzle and the method provided by the invention, wherein the nickel, the cobalt, the aluminum and the manganese are uniform and ordered macroscopically, and each element is doped with a disordered superlattice structure microscopically. From the test performance of the prepared battery, the lithium ion battery prepared in the embodiment 2 has higher first coulombic efficiency, higher 0.2C and 1C specific capacities and better 100-time circulation capacity retention rate than the lithium ion battery prepared in the comparative example 1. In addition, comparative examples 2 and 3, comparative examples 3 and 4, comparative examples 4 and 5, and comparative examples 5 and 4 are 4 pairs of lithium ion battery positive electrode materials with the same raw materials and the same components, except that each pair of the comparative examples adopts a coprecipitation method in the prior art, each example adopts the nozzle and the method of the invention, and the lithium ion batteries prepared by each example have a superlattice structure; the same results can be seen from table 1, and the superlattice ion battery positive electrode material prepared by the method in each embodiment of the invention has higher first coulombic efficiency, higher 0.2C and 1C specific capacities, and better 100-cycle capacity retention rate.
It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the embodiments do not constitute the present invention
The definition is clear. In addition, the technical features involved in the respective embodiments of the present invention described above may be combined with each other as long as they do not conflict with each other. In addition, the above embodiments are only some embodiments of the present invention, not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention belong to the protection scope of the present invention.
Claims (8)
1. A nozzle for preparing a lithium ion battery anode material with a superlattice structure is characterized by comprising an air inlet pipe, a nozzle tip and a plurality of inlet pipes, wherein different inlet pipes are respectively used for feeding slurry or solution with incompletely same element types or element contents; the nozzle tip comprises a core, a gas distributor, and a shell; the core body is fixed at the end part of the air inlet pipe, a plurality of material channels which are not communicated with each other are arranged in the core body, the top end of each material channel is correspondingly connected with one feed pipe, the tail end of each material channel forms an arc-shaped discharge hole at the outlet end face of the core body, and the discharge holes are distributed on the same circular ring and are not communicated with each other; the gas distributor is an annular frustum fixed on the periphery of the core body, a plurality of gas channels are uniformly distributed on the gas distributor, the gas channels are communicated with the gas inlet pipe, and the plurality of gas channels surround the periphery of a circular ring formed by the plurality of discharge holes; the shell is fixed at the end part of the gas inlet pipe in a sealing mode, the shell surrounds the periphery of the gas distributor in an annular mode, the end part of the shell is gradually contracted and provided with a nozzle opening, and the diameter of the nozzle opening is larger than that of a circular ring formed by the discharge ports; the high-pressure gas atomizes the materials flowing out from different discharge ports, the materials are fused at the end face of a nozzle opening, and then the materials are dried by hot air in a spray drying system to be prepared into particles.
2. The nozzle for preparing the lithium ion battery cathode material with the superlattice structure according to claim 1, wherein the number of the feeding pipes is two, namely a first feeding pipe and a second feeding pipe; the number of the material channels is two, and the two material channels are respectively a first material channel and a second material channel; the first feeding pipe is communicated with the first material channel, and the second feeding pipe is communicated with the second material channel.
3. A method for preparing a lithium ion battery cathode material with a superlattice structure, which is characterized by adopting the nozzle of claim 2, and comprising the following steps:
step one, preparing a dispersion liquid A and a dispersion liquid B
Preparing a dispersion liquid A and a dispersion liquid B by using a compound of a lithium element and a compound of an M element, wherein the total amount of the lithium element and the M element in the dispersion liquid A and the dispersion liquid B conforms to a chemical formula Li a ＭO x Medium stoichiometric ratio, wherein: a =0.5-1.5,2 ≤ x ≤ 2.5, M is at least one of nickel, cobalt, manganese and aluminum, and the kinds or contents of M elements contained in the dispersion liquid A and the dispersion liquid B are not completely the same;
step two, spray fusion granulation
Simultaneously introducing the dispersion liquid A and the dispersion liquid B into the first feeding pipe and the second feeding pipe respectively, spraying out from the first discharging port and the second discharging port, carrying out spray fusion, and drying and granulating;
step three, sintering
Keeping the temperature of the produced particles at 450-600 ℃ for 3-10h; then continuously heating to 600-1000 ℃, and sintering for 5-30h.
4. The method for preparing a positive electrode material of a lithium ion battery with a superlattice structure according to claim 3, wherein a dispersion medium of the dispersion liquid A and the dispersion liquid B is water or ethanol.
5. The method for producing a positive electrode material for a lithium ion battery having a superlattice structure according to claim 3 or 4, wherein the solid contents of the dispersion liquid A and the dispersion liquid B are both 15 to 50wt%.
6. The method for preparing a positive electrode material for a lithium ion battery having a superlattice structure according to claim 3, wherein the particle size of the dispersed phase in the dispersion liquid A and the dispersion liquid B is 1nm to 700nm.
7. The method for preparing the lithium ion battery cathode material with the superlattice structure as claimed in claim 3, wherein during spray granulation, the pressure of an air flow atomizer is 0.1-1.0MPa, the air inlet temperature is 150-300 ℃, and the air outlet temperature is 70-150 ℃.
8. A lithium ion battery positive electrode material with a superlattice structure, which is prepared by the method of any one of claims 3 to 7.
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