CN111244426A - Nickel-rich ternary cathode material, preparation method and lithium ion battery - Google Patents
Nickel-rich ternary cathode material, preparation method and lithium ion battery Download PDFInfo
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The invention discloses a nickel-rich ternary cathode material, a preparation method thereof and a lithium ion battery. The method comprises the following steps: mixing and sintering a nickel-rich ternary cathode material precursor, a first nano metal compound and lithium source powder to obtain first powder; mixing the first powder with a first coating agent to obtain a first coating material; performing second sintering treatment on the first coating material to obtain second powder; mixing the second powder with a second coating agent to obtain a second coating material; and carrying out third sintering treatment on the second coating material to obtain the nickel-rich ternary cathode material, wherein the first coating agent is an aqueous solution of a halogen compound, and the second coating agent is a second nano metal compound, or the first coating agent is a second nano metal compound, and the second coating agent is an aqueous solution of a halogen compound. Therefore, the nickel-rich ternary cathode material with high energy density, long cycle life, stable structure, good cycle performance and high safety performance can be obtained by using the method.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a nickel-rich ternary cathode material, a preparation method thereof and a lithium ion battery.
Background
In recent years, with rapid progress of technology, the new energy automobile industry is rapidly developed, and becomes the most important application field of lithium ion batteries. Although the lithium ion battery technology is also rapidly improved, the battery related technology is not perfect, and various faults are brought, and even a serious accident of automobile spontaneous combustion occurs. The demand for new and more reliable lithium ion batteries is extremely urgent, and the performances of high capacity, long endurance, safety, reliability and the like are the most important performance requirements of the current batteries. Therefore, it is imperative to develop a lithium ion battery with stable performance and higher energy density.
The nickel-rich ternary cathode material has higher discharge specific capacity than lithium cobaltate and the conventional ternary cathode material, the cost of raw materials is lower than that of the lithium cobaltate and the conventional ternary cathode material, the energy density of the battery can be remarkably improved, and the nickel-rich ternary cathode material has a huge application prospect in the fields of new energy automobile power batteries and consumer electronics.
However, the nickel-rich ternary cathode material, the preparation method thereof and the lithium ion battery still need to be improved.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems:
at present, the problems of unstable structure, poor cycle performance and low safety performance of the nickel-rich ternary cathode material generally exist. The inventors have intensively studied and found that the reason is mainly due to the poor structure and performance of the nickel-rich ternary cathode material. Specifically, the nickel-rich ternary cathode material has low reactivity, high surface free lithium and high residual alkali degree, so that the processing performance of the nickel-rich ternary cathode material is affected, the technical difficulty of battery manufacturing is increased, the residual lithium on the surface of the nickel-rich ternary cathode material is easy to generate a side reaction with an electrolyte to generate gas, and the collapse of a crystal structure in the material is caused, so that the cycle performance of the battery is obviously reduced, and even the battery is likely to have unsafe problems such as bulging, explosion, ignition and the like, so that the application and development of the nickel-rich ternary cathode material are severely limited.
The present invention is directed to alleviate or solve at least one of the above-mentioned problems to at least some extent, and provides a method for preparing a nickel-rich ternary cathode material, which achieves low residual alkalinity residue, good cycle performance, and excellent safety performance of the nickel-rich ternary cathode material.
In one aspect of the invention, a method of making a nickel-rich ternary cathode material is provided. The method comprises the following steps: (1) mixing a nickel-rich ternary positive electrode material precursor, a first nano metal compound and lithium source powder, and performing first sintering treatment to obtain first powder; (2) mixing the first powder with a first coating agent to obtain a first coating material; (3) performing second sintering treatment on the first coating material to form a first modified shell layer for coating the first powder so as to obtain second powder; (4) mixing the second powder with a second coating agent to obtain a second coating material; (5) and performing third sintering treatment on the second coating material to form a second modified shell layer for coating the second powder to obtain the nickel-rich ternary cathode material, wherein the first coating agent is an aqueous solution of a halogen compound, the second coating agent is a second nano metal compound, or the first coating agent is a second nano metal compound, and the second coating agent is an aqueous solution of a halogen compound. Therefore, the nickel-rich ternary cathode material with high energy density, long cycle life, stable structure, good cycle performance and high safety performance can be obtained by using the method, and the practicability of the nickel-rich ternary cathode material is greatly improved.
According to the embodiment of the present invention, the content of the halogen compound is 2.5% to 10% based on the total mass of the aqueous solution of the halogen compound. Therefore, the chemical stability of the final nickel-rich ternary cathode material can be improved, the material is protected from acid corrosion of electrolyte, the thermal stability and the electric cycle performance of the material are improved, the thickness of a modified shell layer formed by sintering the aqueous solution of the halogen compound is small, diffusion of lithium ions in the charging and discharging process is not blocked, and the specific discharge capacity of the material is effectively improved.
According to the embodiment of the invention, the ratio of the amount of the metal element in the second nano metal compound to the total amount of the ternary element in the nickel-rich ternary cathode material precursor is 0.1% -1.7%, wherein the ternary elements are nickel element, cobalt element and manganese element respectively, or the ternary elements are nickel element, cobalt element and aluminum element respectively. Therefore, the capability of the final nickel-rich ternary cathode material for resisting corrosion of hydrofluoric acid can be improved, metal ions in the material are prevented from being dissolved, the surface impedance of the material is reduced, the circulation stability of the material is improved, the structural stability of the material under high voltage is improved, and a modified shell layer formed by sintering the second nano metal compound is thinner, so that diffusion of lithium ions in the charging and discharging process can not be blocked, and the specific discharge capacity of the material is effectively improved.
According to an embodiment of the present invention, the mixing the nickel-rich ternary positive electrode material precursor, the first nanometal compound, and the lithium source powder in step (1) includes: premixing the nickel-rich ternary cathode material precursor, the first nano metal compound and the lithium source powder for 5-30min, and performing high-speed mixing on the premixed powder, wherein the high-speed mixing speed is 500-1500rpm, and the high-speed mixing time is 15-60 min; optionally, the temperature of the first sintering treatment is 750-950 ℃, and the time of the first sintering treatment is 10-25 h. Therefore, the precursor of the nickel-rich ternary cathode material can fully react with the lithium source powder, and the metal element doping modification of the nickel-rich ternary cathode material can be realized.
According to the embodiment of the invention, the ratio of the amount of the metal element in the first nanometal compound to the total amount of the ternary element in the nickel-rich ternary cathode material precursor is 0.1% -2%, wherein the ternary elements are nickel, cobalt and manganese respectively, or the ternary elements are nickel, cobalt and aluminum respectively. Therefore, the structural stability, the cycle performance and the thermal stability of the final nickel-rich ternary cathode material are improved.
According to the embodiment of the invention, the ratio of the amount of the lithium element in the lithium source powder to the total amount of the ternary elements in the nickel-rich ternary cathode material precursor is 1.01-1.2, wherein the ternary elements are nickel element, cobalt element and manganese element respectively, or the ternary elements are nickel element, cobalt element and aluminum element respectively. Therefore, the lithium source powder can be fully reacted with the nickel-rich ternary cathode material precursor, the excessive part of the lithium source powder is not excessive, and the raw material is saved.
According to the embodiment of the invention, the first powder is mixed with the aqueous solution of the halogen compound, or the second powder is mixed with the aqueous solution of the halogen compound, wherein the mixing temperature is 25-55 ℃, the mixing rotating speed is 15-50rpm, and the mixing time is 15-60 min. Therefore, the aqueous solution of the halogen compound can be well coated on the outer surface of the first powder or the second powder by mixing under the conditions, and a modified shell layer for coating the first powder or the second powder is formed by subsequent sintering treatment.
According to the embodiment of the invention, the first coating agent is an aqueous solution of the halogen compound, the temperature of the second sintering treatment is 200-450 ℃, and the time of the second sintering treatment is 1.5-5h, or the second coating agent is an aqueous solution of the halogen compound, the temperature of the third sintering treatment is 200-450 ℃, and the time of the third sintering treatment is 1.5-5 h. Thus, by performing the sintering treatment under the above-mentioned conditions, the halogen compound can be infiltrated into or adsorbed on the first powder or the second powder, and a modified shell layer having a uniform and dense thickness can be obtained.
According to the embodiment of the invention, the first powder and the second nano-metal compound are mixed, or the second powder and the second nano-metal compound are mixed, wherein the mixing comprises premixing and high-speed mixing in sequence, the premixing time is 15-30min, the high-speed mixing rotation speed is 500-1000rpm, and the high-speed mixing time is 15-30 min. Therefore, the second nano metal compound can be well coated on the outer surface of the first powder or the second powder by mixing under the conditions, and a modified shell layer for coating the first powder or the second powder is formed by subsequent sintering treatment.
According to the embodiment of the invention, the first coating agent is the second nano metal compound, the temperature of the second sintering treatment is 450-750 ℃, and the time of the second sintering treatment is 2.5-5h, or the second coating agent is the second nano metal compound, the temperature of the third sintering treatment is 450-750 ℃, and the time of the third sintering treatment is 2.5-5 h. Thus, the sintering treatment is performed under the above conditions, so that the second nano metal compound can be adsorbed on the second powder or the first powder, and a modified shell layer with uniform thickness and compactness can be obtained.
According to an embodiment of the present invention, the nickel-rich ternary positive electrode material precursor includes at least one of nickel cobalt manganese hydroxide and nickel cobalt aluminum hydroxide; optionally, the first nanometal compound and the second nanometal compound are each independently at least one selected from the group consisting of metal oxides, metal fluorides, metal chlorides, metal phosphates, and metal hydroxides, wherein the metal element includes at least one of Mg, Al, Zr, Mo, Ti, V, Fe, Na, K, Ca, Nb, Mn; optionally, the halogen compound comprises at least one of boric acid, hydrobromic acid, boron oxide, nickel fluoride, lithium fluoride, aluminum fluoride, sodium hypochlorite; optionally, the lithium source powder includes at least one of lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, and lithium acetate. Therefore, the raw materials are beneficial to improving the cycle performance, energy density and safety performance of the nickel-rich ternary cathode material.
In another aspect of the invention, a nickel-rich ternary cathode material is provided. According to the embodiment of the invention, the nickel-rich ternary cathode material is prepared by the method. Therefore, the nickel-rich ternary cathode material has the advantages of high energy density, long cycle life, stable structure, good cycle performance, high safety performance and the like, and the practicability of the nickel-rich ternary cathode material is greatly improved.
In another aspect of the present invention, a lithium ion battery is provided. According to an embodiment of the invention, the lithium ion battery comprises a positive electrode sheet comprising the nickel-rich ternary positive electrode material described above. Therefore, the lithium ion battery has all the characteristics and advantages of the nickel-rich ternary cathode material, and the description is omitted. In general, the lithium ion battery has the advantages of high energy density, good cycle performance, long cycle life, high safety performance and the like.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 shows a schematic flow diagram of a method of preparing a nickel-rich ternary cathode material according to one embodiment of the invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In one aspect of the invention, a method of making a nickel-rich ternary cathode material is provided. For the sake of understanding, the principle of the method for improving the performance of the nickel-rich ternary cathode material is briefly explained below:
according to the embodiment of the invention, firstly, the method dopes metal cations in the nickel-rich ternary positive electrode material, and the metal cations are doped into the material crystal lattice, so that the valence state of transition metal ions in the nickel-rich ternary positive electrode material is increased or decreased, holes or electrons are generated, the energy band structure of the material is changed, the conductivity of intrinsic electrons is improved, the Li/Ni mixed-discharging degree in the material is reduced, the crystal lattice is supported, the material structure is stabilized, and the electrochemical cycle performance and the thermal stability of the material are improved. And secondly, carrying out surface treatment on the first powder (powder formed by mixing and sintering the nickel-rich ternary cathode material precursor, the first nano metal compound and the lithium source powder) twice, so that the corrosion of the electrolyte to the nickel-rich ternary cathode material is reduced, the Co dissolution of the nickel-rich ternary cathode material in the electrolyte is obviously reduced, the interface resistance of the electrolyte and an electrode is also reduced, and the cycle performance and the safety and stability of the nickel-rich ternary cathode material are obviously improved. Therefore, the nickel-rich ternary cathode material with high energy density, long cycle life, stable structure, good cycle performance and high safety performance can be obtained by using the method, and the practicability of the nickel-rich ternary cathode material is greatly improved.
The specific steps of the method are described in detail below according to specific embodiments of the invention:
according to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: mixing a nickel-rich ternary positive electrode material precursor, a first nano metal compound and lithium source powder, and carrying out first sintering treatment to obtain first powder
According to the embodiment of the invention, in the step, the nickel-rich ternary cathode material precursor, the first nano metal compound and the lithium source powder are mixed and subjected to the first sintering treatment to obtain the first powder. Therefore, in the step, the precursor of the nickel-rich ternary cathode material and the lithium source powder can react to form a primary nickel-rich ternary cathode material, and in the step, the metal element doping modification of the primary nickel-rich ternary cathode material can be realized by using the first nano metal compound (the metal element is doped into the crystal of the primary nickel-rich ternary cathode material), so that the structural stability, the electrochemical cycle performance and the thermal stability of the final nickel-rich ternary cathode material are improved.
The primary nickel-rich ternary cathode material refers to a substance formed after a precursor of the nickel-rich ternary cathode material reacts with lithium source powder, and the primary nickel-rich ternary cathode material doped with a metal element is the first powder obtained in S100.
According to an embodiment of the present invention, mixing the nickel-rich ternary positive electrode material precursor, the first nano-metal compound, and the lithium source powder may include: firstly, a nickel-rich ternary cathode material precursor, a first nano metal compound and lithium source powder are premixed, and then the premixed powder is mixed at a high speed. Wherein, the premixing time can be 5-30min, such as 5min, 10min, 15min, 20min, 25min, 30min, the high-speed mixing rotation speed can be 500 plus 1500rpm, such as 500rpm, 800rpm, 1000rpm, 1200rpm, 1500rpm, the high-speed mixing time can be 15-60min, such as 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60 min. The inventor unexpectedly finds that premixing the three kinds of powder before high-speed mixing is beneficial to improving the structural stability, the cycle performance and the thermal stability of the final nickel-rich ternary cathode material.
According to an embodiment of the present invention, pre-mixing the nickel-rich ternary cathode material precursor, the first nano-metal compound, and the lithium source powder includes: firstly, premixing a nickel-rich ternary cathode material precursor and a first nano metal compound for 15-30min to fully mix the two kinds of powder, then adding lithium source powder into the premixed two kinds of powder, and then premixing for 5-30 min. Therefore, the three kinds of powder can be fully mixed, more uniform mixed powder is provided for the first sintering treatment, and the structural stability, the cycle performance and the thermal stability of the final nickel-rich ternary cathode material can be improved. The specific manner of premixing is not particularly limited, and for example, hand-shaking mixing may be used.
According to the embodiment of the invention, the powder obtained by mixing the nickel-rich ternary cathode material precursor, the first nano metal compound and the lithium source powder is subjected to first sintering treatment, the temperature of the first sintering treatment can be 750-950 ℃, such as 750 ℃, 800 ℃, 850 ℃, 900 ℃ and 950 ℃, the time of the first sintering treatment can be 10-25 hours, such as 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours and 25 hours, the first sintering treatment is solid-phase sintering performed in an oxygen atmosphere, and the powder subjected to the first sintering treatment is crushed, ground and sieved to obtain the first powder. Therefore, the first sintering treatment is carried out under the conditions, so that the precursor of the nickel-rich ternary cathode material can fully react with the lithium source powder, the doping of metal elements is realized, and the improvement of the lattice stability of the final nickel-rich ternary cathode material and the reduction of the residual alkalinity of the nickel-rich ternary cathode material are facilitated.
According to an embodiment of the present invention, the nickel-rich ternary positive electrode material precursor may include at least one of nickel cobalt manganese hydroxide and nickel cobalt aluminum hydroxide. The molecular formula of the precursor of the nickel-rich ternary cathode material can be NixCoyM(1-x-y)(OH)2Wherein x is more than or equal to 0.6 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.2, and M is one of Mn and Al. Therefore, the final nickel-rich ternary cathode material can obtain higher energy density. The crystal form of the nickel-rich ternary positive electrode material precursor is not particularly limited, and may be, for example, a polycrystalline form, or may also be a single crystal form.
The inventor finds that the modification of the nickel-rich ternary cathode material is usually the improvement of the structural components and crystals of the precursor of the nickel-rich ternary cathode material, so that the production cost of the precursor of the nickel-rich ternary cathode material is greatly increased, and the uniformity and stability of the nickel-rich ternary cathode material are not well controlled. The method has low requirement on the precursor of the nickel-rich ternary cathode material, can reduce the manufacturing cost of the nickel-rich ternary cathode material, simultaneously ensures that the preparation of the nickel-rich ternary cathode material is easy to control, has good quality stability and greatly improves the consistency of the material.
According to an embodiment of the present invention, a ratio of the amount of the metal element in the first nanometal compound to the total amount of the ternary element in the nickel-rich ternary cathode material precursor may be 0.1% to 2%, such as 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, and 2%, wherein the ternary elements are nickel, cobalt, and manganese, respectively, or the ternary elements are nickel, cobalt, and aluminum, respectively. Therefore, the ratio of the amount of the metal element in the first nano metal compound to the total amount of the ternary element in the precursor of the nickel-rich ternary cathode material is set in the range, so that the structural stability, the cycle performance and the thermal stability of the final nickel-rich ternary cathode material are improved.
According to an embodiment of the present invention, the first nanometal compound may include at least one of a metal oxide, a metal fluoride, a metal chloride, a metal phosphate, and a metal hydroxide, wherein the metal element includes at least one of Mg, Al, Zr, Mo, Ti, V, Fe, Na, K, Ca, Nb, Mn. Therefore, the nickel-rich ternary cathode material can be modified by utilizing the metal elements, so that the structural stability, the cycle performance and the thermal stability of the nickel-rich ternary cathode material are improved.
According to an embodiment of the present invention, the lithium source powder may include at least one of lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, and lithium acetate. Therefore, the lithium source powder can be used for reacting with the nickel-rich ternary cathode material precursor to form a nickel-rich ternary cathode material primary product. Taking lithium hydroxide monohydrate as an example, the equation of the reaction between the nickel-rich ternary cathode material precursor and lithium hydroxide monohydrate is as follows: 4NixCoyM(1-x-y)(OH)2+4LiOH·H2O+O2→4LiNixCoyM(1-x-y)O2+10H2O。
According to an embodiment of the present invention, the ratio of the amount of the substance of the lithium element in the lithium source powder to the total amount of the substance of the ternary element in the nickel-rich ternary cathode material precursor may be 1.01 to 1.2, such as 1.01, 1.04, 1.06, 1.08, 1.10, 1.12, 1.15, 1.18, 1.2, wherein the ternary elements are a nickel element, a cobalt element, and a manganese element, respectively, or the ternary elements are a nickel element, a cobalt element, and an aluminum element, respectively. That is, the amount of lithium species in the lithium source powder is 1% to 20% more than the total amount of ternary species in the nickel-rich ternary positive electrode material precursor. Therefore, the lithium source powder can be fully reacted with the nickel-rich ternary cathode material precursor, the excessive part of the lithium source powder is not excessive, and the raw material is saved.
S200: mixing the first powder with a first coating agent to obtain a first coating material
According to an embodiment of the present invention, in this step, the first powder is mixed with the first coating agent to obtain the first coating material. According to some embodiments of the present invention, the first capping agent may be an aqueous solution of a halogen compound, the second capping agent in S400 is a second nanometal compound, and the content of the halogen compound is 2.5% to 10%, such as 2.5%, 5%, 7.5%, 10%, based on the total mass of the aqueous solution of the halogen compound. The inventors have intensively studied and found that when the content of the halogen compound is higher or lower than the above range, the chemical stability of the final nickel-rich ternary cathode material is not favorably improved significantly. According to the invention, the first powder is coated by using the halogen compound aqueous solution with the solute content within the range, and then the second sintering treatment is carried out, so that a modified shell layer for coating the first powder can be formed, the chemical stability of the final nickel-rich ternary cathode material can be improved, the material is protected from acid corrosion of electrolyte, the thermal stability and the electrical cycle performance of the material are improved, the thickness of the modified shell layer formed by sintering treatment is thinner, the diffusion of lithium ions in the charging and discharging process can not be blocked, and the specific discharge capacity of the material is effectively improved.
According to an embodiment of the present invention, when the first coating agent is an aqueous solution of a halogen compound, the temperature at which the first powder and the aqueous solution of the halogen compound are mixed may be 25 to 55 ℃, such as 25 ℃, 30 ℃, 40 ℃, 50 ℃, 55 ℃, and the mixing temperature is a constant temperature, the mixing speed may be 15 to 50rpm, such as 15rpm, 20rpm, 30rpm, 40rpm, 50rpm, and the mixing time may be 15 to 60min, such as 15min, 20min, 30min, 40min, 50min, and 60 min. Therefore, the aqueous solution of the halogen compound can be well coated on the outer surface of the first powder by mixing under the conditions, so that the subsequent second sintering treatment is facilitated, and a modified shell layer coated on the first powder is formed.
According to the embodiment of the invention, when the first coating agent is an aqueous solution of a halogen compound, the first powder and the aqueous solution of the halogen compound are mixed under the above conditions, and then the first coating material is obtained through filtering and drying.
According to an embodiment of the present invention, the halogen compound may include at least one of boric acid, hydrobromic acid, boron oxide, nickel fluoride, lithium fluoride, aluminum fluoride, sodium hypochlorite. Therefore, the modified shell layer formed by the halogen compound can improve the chemical stability of the final nickel-rich material, protect the material from acid corrosion of electrolyte, and improve the thermal stability and the electrical cycle performance of the material.
According to other embodiments of the present invention, the first coating agent may be a second nano metal compound, and then the second coating agent in S400 is an aqueous solution of a halogen compound, and the ratio of the amount of the metal element in the second nano metal compound to the total amount of the ternary element in the nickel-rich ternary cathode material precursor may be 0.1% to 1.7%, such as 0.1%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, and 1.7%, where the ternary elements are nickel, cobalt, and manganese, respectively, or the ternary elements are nickel, cobalt, and aluminum, respectively. The inventors have intensively studied and found that when the ratio of the amount of the metal element in the second nano metal compound to the total amount of the ternary element in the precursor of the nickel-rich ternary cathode material is higher or lower than the above range, the final nickel-rich ternary cathode material is not favorable for remarkably improving the electrical property, rate capability and cycle performance. According to the invention, the first powder is coated by using the second nano metal compound with the material quantity ratio within the range to obtain the first coating material, and then the first coating material is subjected to second sintering treatment to form a modified shell layer for coating the first powder, so that the capability of the final nickel-rich ternary cathode material for resisting corrosion of hydrofluoric acid can be improved, the dissolution of metal ions in the material is prevented, the surface impedance of the material is reduced, the circulation stability is improved, the structural stability of the material under high voltage is improved, the thickness of the modified shell layer formed by sintering treatment is thinner, the diffusion of lithium ions in the charging and discharging process can not be blocked, and the specific discharge capacity of the material is effectively improved.
According to an embodiment of the present invention, when the first coating agent is a second nano metal compound, mixing the first powder and the second nano metal compound includes: firstly, premixing the first powder and the second nano metal compound, and then mixing at a high speed, wherein the premixing time can be 15-30min, such as 15min, 20min, 25min, and 30min, the high-speed mixing speed can be 500-1000rpm, such as 500rpm, 600rpm, 700rpm, 800rpm, 900rpm, and 1000rpm, and the high-speed mixing time can be 15-30min, such as 15min, 20min, 25min, and 30 min. Therefore, the second nano metal compound can be well coated on the outer surface of the first powder by mixing under the conditions, so that the subsequent second sintering treatment is facilitated, and a modified shell layer coated on the first powder is formed. Moreover, the inventor finds that premixing the first powder and the second nano metal compound before high-speed mixing is beneficial to improving the electrical property, rate capability and cycle performance of the final nickel-rich ternary cathode material.
According to an embodiment of the present invention, the second nano-metal compound may include at least one of metal oxide, metal fluoride, metal chloride, metal phosphate, and metal hydroxide, wherein the metal element includes at least one of Mg, Al, Zr, Mo, Ti, V, Fe, Na, K, Ca, Nb, Mn. Therefore, the modified shell layer formed by the nano metal compound can improve the electrical property, rate capability and cycle performance of the final nickel-rich ternary cathode material.
S300: performing second sintering treatment on the first coating material to form a first modified shell layer coating the first powder so as to obtain second powder
According to an embodiment of the present invention, in this step, the first coating material is subjected to a second sintering process to form a first modified shell layer coating the first powder, so as to obtain a second powder. According to some embodiments of the present invention, when the first coating agent is an aqueous solution of a halogen compound, the temperature of the second sintering treatment may be 200-450 ℃, such as 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, the time of the second sintering treatment may be 1.5-5h, such as 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, and the second sintering treatment is performed in an oxygen atmosphere. Thus, the second sintering treatment is performed under the above conditions, so that the halogen compound can be infiltrated or adsorbed into the first powder, and a first modified shell layer having a uniform and dense thickness can be obtained.
According to other embodiments of the present invention, when the first capping agent is the second nano metal compound, the temperature of the second sintering process may be 450-. Therefore, the second sintering treatment is carried out under the conditions, so that the second nano metal compound can be well adsorbed on the first powder, and a first modified shell layer with uniform thickness and compactness is obtained.
S400: mixing the second powder with a second coating agent to obtain a second coating material
According to an embodiment of the present invention, in this step, the second powder is mixed with a second coating agent to obtain a second coating material. According to some embodiments of the present invention, when the first coating agent in S200 is an aqueous solution of a halogen compound, the second coating agent in this step is a second nano-metal compound, and mixing the second powder with the second nano-metal compound includes: firstly, premixing the second powder and the second nano metal compound, and then, carrying out high-speed mixing, wherein the premixing time can be 15-30min, the high-speed mixing rotation speed can be 500-1000rpm, and the high-speed mixing time can be 15-30 min. Therefore, the second nano metal compound can be well coated on the outer surface of the second powder by mixing under the conditions to form a second coating material, so that the subsequent third sintering treatment is facilitated, and a modified shell layer coated on the second powder is formed.
The specific material of the second nano-metal compound and the amount of the second nano-metal compound (i.e. the ratio of the amount of the metal element in the second nano-metal compound to the total amount of the ternary element in the nickel-rich ternary cathode material precursor) have been described in detail above, and are not repeated herein.
According to other embodiments of the present invention, when the first capping agent in S200 is the second nano metal compound, the second capping agent in this step is an aqueous solution of a halogen compound, the temperature at which the second powder and the aqueous solution of the halogen compound are mixed may be 25 to 55 ℃, the mixing temperature is a constant temperature, the rotation speed of the mixing may be 15 to 50rpm, and the mixing time may be 15 to 60 min. Therefore, the aqueous solution of the halogen compound can be well coated on the outer surface of the second powder by mixing under the conditions, so that the subsequent third sintering treatment is facilitated, and a modified shell layer coated on the second powder is formed. The second coating material is obtained by mixing the second powder with an aqueous solution of a halogen compound, and then filtering and drying the mixture.
The specific materials of the halogen compound and the solute content of the aqueous solution of the halogen compound have been described in detail above, and are not described herein again.
S500: carrying out third sintering treatment on the second coating material to form a second modified shell layer coating the second powder so as to obtain the nickel-rich ternary cathode material
According to the embodiment of the invention, in the step, the second coating material is subjected to a third sintering treatment to form a second modified shell layer coating the second powder, so as to obtain the nickel-rich ternary cathode material. According to some embodiments of the present invention, when the first capping agent is an aqueous solution of a halogen compound and the second capping agent is a second nano-metal compound, the temperature of the third sintering process may be 450-. Thus, the third sintering treatment is performed under the above conditions, so that the second nano metal compound can be adsorbed on the second powder, and a second modified shell layer with uniform and dense thickness can be obtained.
According to other embodiments of the present invention, when the first coating agent is the second nano-metal compound and the second coating agent is an aqueous solution of a halogen compound, the temperature of the third sintering process may be 200-450 ℃, the time of the third sintering process may be 1.5-5h, and the third sintering process is performed in an oxygen atmosphere. Thus, the halogen compound can be impregnated into or adsorbed on the second powder by performing the third sintering treatment under the above-described conditions, and a second modified shell layer having a uniform and dense thickness can be obtained.
According to the embodiment of the invention, the powder obtained by the third sintering treatment is sieved to obtain the final nickel-rich ternary cathode material.
According to the embodiment of the invention, the finally obtained nickel-rich ternary cathode material has two modified shell layers, when the first coating agent is an aqueous solution of a halogen compound and the second coating agent is a second nano metal compound, the first modified shell layer is formed by coating a first powder body with the aqueous solution of the halogen compound and performing second sintering treatment, and the second modified shell layer is formed by coating a second powder body with the second nano metal compound and performing third sintering treatment; when the first coating agent is a second nano metal compound and the second coating agent is an aqueous solution of a halogen compound, the first modified shell layer is formed by coating the first powder with the second nano metal compound and performing second sintering treatment, and the second modified shell layer is formed by coating the second powder with the aqueous solution of the halogen compound and performing third sintering treatment. The modified shell layer formed by the aqueous solution of the halogen compound is arranged in the nickel-rich ternary positive electrode material, so that the chemical stability of the final nickel-rich ternary positive electrode material can be improved, the material is protected from acid corrosion of an electrolyte, the thermal stability and the electrical cycle performance of the material are improved, the modified shell layer formed by the second nano metal compound is arranged in the nickel-rich ternary positive electrode material, the capability of the final nickel-rich ternary positive electrode material in resisting corrosion of hydrofluoric acid can be improved, the metal ions in the material are prevented from being dissolved, the surface impedance of the material is reduced, the cycle stability is improved, and the structural stability of the material under high voltage is improved.
According to the embodiment of the invention, since the sintering temperature of the second nano metal compound is higher than that of the halogen compound, the second nano metal compound is coated first, and the volatilization of the halogen element in the halogen compound can be reduced.
According to the embodiment of the invention, in order to further improve the performance of the nickel-rich ternary cathode material, surface modification treatment (for example, three times) can be performed for multiple times, however, the cost is increased as the number of times of surface modification treatment is increased.
In conclusion, in the process of forming the primary nickel-rich ternary cathode material, metal element doping modification is synchronously performed to obtain first powder, and then surface modification (namely, coating and sintering) is performed on the first powder twice to form two modified shell layers on the surface of the first powder, so that the cycle performance of the material is greatly improved under the condition that the nickel-rich ternary cathode material is ensured to have higher energy density, and meanwhile, the safety and stability of the material are greatly improved. In addition, the method also has the advantages of simple process, high process operability, easy industrial production and implementation and the like.
In another aspect of the invention, a nickel-rich ternary cathode material is provided. According to an embodiment of the present invention, the nickel-rich ternary cathode material is prepared using the method described above. Therefore, the nickel-rich ternary cathode material has the advantages of high energy density, long cycle life, stable structure, good cycle performance, high safety performance and the like, and the practicability of the nickel-rich ternary cathode material is greatly improved.
According to an embodiment of the present invention, the nickel-rich ternary positive electrode material has two modified shell layers, wherein one modified shell layer is composed of a halogen compound, and the other modified shell layer is composed of a second nanometal compound, and the coating relationship of the two modified shell layers is not particularly limited, for example, the inner modified shell layer is composed of a halogen compound, and the outer modified shell layer is composed of a second nanometal compound, or the inner modified shell layer is composed of a second nanometal compound, and the outer modified shell layer is composed of a halogen compound. Therefore, the nickel-rich ternary cathode material can obtain good cycle performance, rate capability, chemical stability and safety performance.
In another aspect of the present invention, a lithium ion battery is provided. According to an embodiment of the invention, the lithium ion battery comprises a positive electrode sheet comprising the nickel-rich ternary positive electrode material described above. Thus, the lithium ion battery has all the characteristics and advantages of the nickel-rich ternary cathode material described above, and the description thereof is omitted. In general, the lithium ion battery has the advantages of high energy density, good cycle performance, long cycle life, high safety performance and the like.
The invention will now be illustrated by means of specific examples, which are provided for illustration only and should not be construed as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications.
Example 1
The preparation process of the nickel-rich ternary cathode material is as follows:
(1) preparing first powder. First, 67.95g of polymorphic Ni were weighed0.83Co0.11Mn0.06(OH)2And 0.1853g of nano molybdenum oxide (the ratio of the amount of the molybdenum element to the total amount of the nickel, cobalt and manganese elements is 0.16%), and mixing Ni0.83Co0.11Mn0.06(OH)2Mixing with nanometer molybdenum oxide by hand shaking for 15 min. Subsequently, 32.083g of lithium hydroxide monohydrate powder (the ratio of the amount of the substance of lithium to the total amount of the substances of nickel, cobalt and manganese is 1.04, namely the amount of the substance of lithium is 4% in excess of the total amount of the substances of nickel, cobalt and manganese) was weighed, and added to the mixture of the former two powders, and the mixture was hand-shaken and mixed for 15min, and then high-speed mixed in a high-speed mixer at a rotation speed of 700rpm for 45min, so as to obtain a mixed powder. Then, sintering is carried out for 16h under the condition of pure oxygen atmosphere and 750 ℃, and the first powder is obtained by crushing and sieving (such as 350 meshes).
(2) And mixing the first powder with a first coating agent to obtain a first coating material. The first coating agent is boric acid, the mass concentration of the boric acid is 2.5%, the first powder is added into the boric acid, the mixture is stirred for 45min at the temperature of 35 ℃ and the rotating speed of 25rpm, and the first coating material is obtained by filtering and drying.
(3) And sintering the first coating material to form a first modified shell layer coating the first powder, and obtaining second powder. Sintering the first coating material for 2.5h under the condition of pure oxygen atmosphere and 300 ℃, and sieving (such as 350 meshes) to obtain second powder.
(4) And mixing the second powder with a second coating agent to obtain a second coating material. The second coating agent is nano-zirconia, the mass of the nano-zirconia is 0.4523g (the ratio of the amount of the zirconium element to the total amount of the nickel, cobalt and manganese elements is 0.5%), the nano-zirconia is added into the second powder, the mixture is mixed by hand shaking for 15min, the mixture is mixed in a high-speed mixer at the high speed of 1000rpm for 15min, and the second coating material is obtained.
(5) And sintering the second coating material to form a second modified shell layer coating the second powder, so as to obtain the nickel-rich ternary cathode material. And sintering the second coating material for 2.5h under the conditions of pure oxygen atmosphere and 650 ℃, and sieving (such as 350 meshes) to obtain the nickel-rich ternary cathode material.
Example 2
The preparation process of the nickel-rich ternary cathode material in this example is substantially the same as that of example 1, except that in step (1), 65.78g of polycrystalline Ni is weighed0.83Co0.11Mn0.06(OH)2And 0.4424g of nano zirconia (the ratio of the amount of the substance of zirconium element to the total amount of the substances of nickel, cobalt and manganese is 0.5%), and mixing Ni0.83Co0.11Mn0.06(OH)2Hand-shaking with nanometer zirconia for 15 min. Subsequently, 33.45g of lithium hydroxide monohydrate powder (the ratio of the amount of the substance of lithium to the total amount of the substances of nickel, cobalt and manganese is 1.12, that is, the amount of the substance of lithium is 12% in excess of the total amount of the substances of nickel, cobalt and manganese) was weighed, and added to the mixture of the former two powders, and the mixture was hand-shaken and mixed for 15min, and then high-speed mixed in a high-speed mixer at 1000rpm for 15min, so as to obtain a mixed powder. Then, sintering is carried out for 20h under the condition of pure oxygen atmosphere and 720 ℃, and the first powder is obtained by crushing and sieving (such as 350 meshes).
Example 3
The preparation process of the nickel-rich ternary cathode material in this example is substantially the same as that in example 2, except that in step (2), the mass concentration of boric acid is 5%, and in step (4), the mass of nano zirconia is 1.3569g (the ratio of the amount of the zirconium element to the total amount of the nickel, cobalt and manganese elements is 1.55%).
Example 4
The preparation process of the nickel-rich ternary cathode material in this example is substantially the same as that in example 3, except that in step (1), the mass of the nano-zirconia is 0.8812g (the ratio of the amount of the zirconium element to the total amount of the nickel, cobalt and manganese elements is 1.006%), the high-speed mixing time is 10min, in step (2), the first coating agent is sodium hypochlorite, the mass concentration of the sodium hypochlorite is 2.5%, and in step (4), the mass of the nano-zirconia is 1.4896g (the ratio of the amount of the zirconium element to the total amount of the nickel, cobalt and manganese elements is 1.7%).
Example 5
The preparation process of the nickel-rich ternary cathode material in this example is substantially the same as that in example 2, except that in step (2), the mass concentration of boric acid is 10%.
Example 6
The preparation process of the nickel-rich ternary cathode material in this example is substantially the same as that in example 2, except that in step (2), the mass concentration of boric acid is 11%.
Example 7
The preparation process of the nickel-rich ternary cathode material in this example is substantially the same as that in example 2, except that in step (2), the mass concentration of boric acid is 2%.
Example 8
The preparation process of the nickel-rich ternary cathode material in this example is substantially the same as that in example 2, except that, in the step (4), the mass of the nano zirconia is 1.7524g (the ratio of the amount of the zirconium element to the total amount of the nickel, cobalt and manganese elements is 2%).
Example 9
The preparation process of the nickel-rich ternary cathode material in this example is substantially the same as that in example 2, except that, in the step (4), the mass of the nano zirconia is 0.0701g (the ratio of the amount of the zirconium element to the total amount of the nickel, cobalt and manganese elements is 0.08%).
Example 10
The preparation process of the nickel-rich ternary cathode material in this example is substantially the same as that in example 2, except that in step (1), the mass of the nano zirconia is 1.84g (the ratio of the amount of the zirconium element to the total amount of the nickel, cobalt and manganese elements is 2.1%).
Example 11
The preparation process of the nickel-rich ternary cathode material in this example is substantially the same as that in example 2, except that the sintering temperature in step (3) is 500 ℃, and the sintering temperature in step (5) is 800 ℃.
Example 12
The process for preparing the nickel-rich ternary cathode material of this example is substantially the same as that of example 2, except that lithium hydroxide monohydrate powder was added to Ni in step (1)0.83Co0.11Mn0.06(OH)2After mixing with the nano zirconia, the mixture was directly subjected to high-speed mixing without hand mixing.
Comparative example 1
The preparation process of the nickel-rich ternary cathode material in the comparative example is basically the same as that in example 2, except that after the first powder is obtained in step (1), the subsequent steps are not performed, that is, the first powder obtained in step (1) is the final nickel-rich ternary cathode material, and the nickel-rich ternary cathode material does not have a modified shell layer.
Comparative example 2
The preparation process of the nickel-rich ternary cathode material in the comparative example is basically the same as that in example 2, except that after the second powder is obtained in step (3), the subsequent steps are not performed, that is, the second powder obtained in step (3) is the final nickel-rich ternary cathode material, and the nickel-rich ternary cathode material has a modified shell layer formed by halogen compounds.
Comparative example 3
The preparation process of the nickel-rich ternary cathode material in the comparative example is basically the same as that in the example 2, except that the step (4) and the step (5) are directly performed without performing the step (2) and the step (3) after the first powder is obtained in the step (1), namely the first powder is mixed with the nano zirconia to obtain a coating material, and the coating material is sintered to obtain the final nickel-rich ternary cathode material, wherein the nickel-rich ternary cathode material is provided with a modified shell layer formed by the nano zirconia.
Performance testing
1. XRD (X-ray diffraction) tests were carried out on the nickel-rich ternary positive electrode materials obtained in examples 1 to 12 and comparative examples 1 to 3, respectively, and I of the materials was calculated003/I104The peak intensity ratio, the value of the lattice parameter c/a is calculated.
2. The nickel-rich ternary cathode materials obtained in examples 1 to 12 and comparative examples 1 to 3 were mixed with a conductive agent acetylene black and a binder PVDF (8% solid content) according to a mass ratio of 90: 5: 5, uniformly mixing, then blending into slurry with solid content of 48% and moderate viscosity by using NMP (N-methyl-pyrrolidone), uniformly coating the slurry on an aluminum foil, drying in vacuum at 80 ℃ for 8h, and rolling and cutting into a circular pole piece with the diameter of 14 mm. 6 pole pieces with similar quality are respectively selected from the pole pieces made of the materials of each example or comparative example, and are dried for 12 hours in vacuum. In the glove box, the pole piece is used as a positive pole piece, the metal lithium piece is used as a negative pole, the ceramic diaphragm is used, the electrolyte adopts the special electrolyte of the nickel-rich ternary positive pole material, the 2032 button cell is assembled, 6 cells are assembled in each embodiment or comparative example, and finally the measured data is the average value of the data obtained by the 6 cells. The blue CT2001 battery tester is used for carrying out charge and discharge tests, the test temperature is constant at 25 ℃, the electrochemical test voltage range is 3-4.3V, the multiplying power tests are carried out at 0.1C, 0.2C, 0.5C, 1C and 2C, and the cycle test is carried out at 1C for 100-cycle charge and discharge performances.
The test results are shown in table 1.
TABLE 1
In addition, I003/I104The higher the peak intensity ratio, the lower the lithium and nickel mixed-out degree in the material, and the more beneficial to the migration of lithium ions in the charging and discharging process. The higher the value of c/a, the better the layered structure of the material, and the more favorable the deintercalation of lithium ions.
The cycle retention rates of the batteries obtained in examples 1-12 and comparative examples 1-3, which are obtained by charging and discharging for 100 weeks at the magnifications of 0.1C, 0.2C, 0.5C and 2C, respectively, have the same trend as the cycle retention rate measured by charging and discharging for 100 weeks at the magnification of 1C, namely, the cycle retention rates of examples 1-5 are higher than those of examples 6-12, and the cycle retention rates of examples 1-12 are higher than those of comparative examples 1-3.
In the description of the present invention, the terms "upper", "lower", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of describing the present invention but do not require that the present invention must be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
In the description herein, references to the description of "one embodiment," "another embodiment," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction. In addition, it should be noted that the terms "first" and "second" in this specification are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (13)
1. A method for preparing a nickel-rich ternary cathode material, comprising:
(1) mixing a nickel-rich ternary positive electrode material precursor, a first nano metal compound and lithium source powder, and performing first sintering treatment to obtain first powder;
(2) mixing the first powder with a first coating agent to obtain a first coating material;
(3) performing second sintering treatment on the first coating material to form a first modified shell layer for coating the first powder so as to obtain second powder;
(4) mixing the second powder with a second coating agent to obtain a second coating material;
(5) performing third sintering treatment on the second coating material to form a second modified shell layer coating the second powder to obtain the nickel-rich ternary cathode material,
the first coating agent is an aqueous solution of a halogen compound, the second coating agent is a second nano metal compound, or the first coating agent is a second nano metal compound, and the second coating agent is an aqueous solution of a halogen compound.
2. The method according to claim 1, wherein the halogen compound is contained in an amount of 2.5 to 10% based on the total mass of the aqueous solution of the halogen compound.
3. The method according to claim 1, wherein the ratio of the amount of the metal element in the second nanometal compound to the total amount of the ternary element in the nickel-rich ternary cathode material precursor is 0.1% to 1.7%, wherein the ternary elements are nickel, cobalt and manganese, or the ternary elements are nickel, cobalt and aluminum, respectively.
4. The method of claim 1, wherein mixing the nickel-rich ternary positive electrode material precursor, the first nanometal compound, and the lithium source powder in step (1) comprises:
premixing the nickel-rich ternary cathode material precursor, the first nano metal compound and the lithium source powder for 5-30min,
mixing the premixed powder at a high speed, wherein the rotating speed of the high-speed mixing is 500-1500rpm, and the time of the high-speed mixing is 15-60 min;
optionally, the temperature of the first sintering treatment is 750-950 ℃, and the time of the first sintering treatment is 10-25 h.
5. The method according to claim 1, wherein the ratio of the amount of the metal element in the first nanometal compound to the total amount of the ternary element in the nickel-rich ternary cathode material precursor is 0.1% to 2%, wherein the ternary elements are nickel, cobalt and manganese, respectively, or the ternary elements are nickel, cobalt and aluminum, respectively.
6. The method according to claim 1, wherein a ratio of an amount of a substance of a lithium element in the lithium source powder to a total amount of a ternary element in the nickel-rich ternary cathode material precursor is 1.01 to 1.2, wherein the ternary elements are a nickel element, a cobalt element, and a manganese element, respectively, or the ternary elements are a nickel element, a cobalt element, and an aluminum element, respectively.
7. The method according to claim 1, wherein the first powder is mixed with the aqueous solution of the halogen compound, or the second powder is mixed with the aqueous solution of the halogen compound,
wherein the mixing temperature is 25-55 ℃, the mixing speed is 15-50rpm, and the mixing time is 15-60 min.
8. The method as claimed in claim 1, wherein the first coating agent is an aqueous solution of the halogen compound, the temperature of the second sintering treatment is 200-450 ℃, the time of the second sintering treatment is 1.5-5h,
or the second coating agent is the aqueous solution of the halogen compound, the temperature of the third sintering treatment is 200-450 ℃, and the time of the third sintering treatment is 1.5-5 h.
9. The method of claim 1, wherein the first powder is mixed with the second nano-metal compound, or the second powder is mixed with the second nano-metal compound,
wherein the mixing comprises premixing and high-speed mixing in sequence, the premixing time is 15-30min, the high-speed mixing rotation speed is 500-1000rpm, and the high-speed mixing time is 15-30 min.
10. The method as claimed in claim 1, wherein the first coating agent is the second nano-metal compound, the temperature of the second sintering treatment is 450 ℃ and 750 ℃, the time of the second sintering treatment is 2.5-5h,
or, the second coating agent is the second nano metal compound, the temperature of the third sintering treatment is 450-750 ℃, and the time of the third sintering treatment is 2.5-5 h.
11. The method of claim 1, wherein the nickel-rich ternary positive electrode material precursor comprises at least one of nickel cobalt manganese hydroxide and nickel cobalt aluminum hydroxide;
optionally, the first nanometal compound and the second nanometal compound are each independently at least one selected from the group consisting of metal oxides, metal fluorides, metal chlorides, metal phosphates, and metal hydroxides, wherein the metal element includes at least one of Mg, Al, Zr, Mo, Ti, V, Fe, Na, K, Ca, Nb, Mn;
optionally, the halogen compound comprises at least one of boric acid, hydrobromic acid, boron oxide, nickel fluoride, lithium fluoride, aluminum fluoride, sodium hypochlorite;
optionally, the lithium source powder includes at least one of lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, and lithium acetate.
12. A nickel-rich ternary positive electrode material, characterized in that it is prepared by the method according to any one of claims 1 to 11.
13. A lithium ion battery comprising a positive electrode sheet comprising the nickel-rich ternary positive electrode material of claim 12.
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