CN113839040B - High-nickel ternary cathode material, preparation method thereof and lithium ion battery - Google Patents
High-nickel ternary cathode material, preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN113839040B CN113839040B CN202111015861.3A CN202111015861A CN113839040B CN 113839040 B CN113839040 B CN 113839040B CN 202111015861 A CN202111015861 A CN 202111015861A CN 113839040 B CN113839040 B CN 113839040B
- Authority
- CN
- China
- Prior art keywords
- equal
- cathode material
- coating layer
- ternary cathode
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a high-nickel ternary cathode material, a preparation method thereof and a lithium ion battery. The high-nickel ternary cathode material comprises: a ternary cathode material matrix with the chemical formula of LiNi X Mn Y Co 1‑X‑Y O 2 X is more than or equal to 0.6 and less than or equal to 0.90,0.05 and less than or equal to 0.15; the first coating layer is coated on the outer surface of the ternary cathode material substrate and is made of LiM Z O and M are transition metal elements; the second coating layer is coated on the outer surface of the first coating layer far away from the ternary cathode material matrix and is made of LiNi a Mn b Co c O 2 A is more than or equal to 0.3 and less than or equal to 0.5,0.2 and less than or equal to b is more than or equal to 0.4,0.2 and less than or equal to c is more than or equal to 0.4, and a + b + c =1. Based on the structure, the high-nickel ternary cathode material can effectively inhibit the corrosion of the electrolyte, and has better structural stability and higher capacity.
Description
Technical Field
The invention relates to the field of batteries, in particular to a high-nickel ternary cathode material, a preparation method thereof and a lithium ion battery.
Background
Among the many potentially commercially applicable lithium ion positive electrode materials, nickel-rich ternary positive electrode materials (NCM) have emerged from a large number of candidates due to their higher specific discharge capacity and low cost advantages. With the further commercial application of lithium ion batteries in the field of power batteries, conventional NCM cathode materials are sold in the marketThe increasing demand of people for the energy density of power batteries cannot be met gradually, and the improvement of the energy density of the NCM cathode material is urgent. According to the findings of previous researchers, the improvement of the cut-off voltage of the cathode material is a feasible scheme for improving the energy density of the lithium ion cathode material. However, liPF 6 Base electrolyte at high voltage (>4.3V) are extremely unstable and decompose to produce HF and induce a series of polarization reactions. The HF further erodes transition metal ions in the positive electrode material and causes irreversible phase change of the positive electrode material, which finally shows that the cycle stability of the positive electrode material is sharply reduced. In addition, although the specific capacity of the conventional high-nickel ternary cathode material is higher, the cycling stability and the thermal stability of the conventional high-nickel ternary cathode material are poorer due to the high oxidizability of nickel ions, so that the service life of a battery cell is shorter, and a great safety risk exists, so that the requirement of a power battery cannot be met.
Both surface modification and surface coating are effective means for suppressing side reactions between the electrode material and the organic electrolyte. In the field of surface coating, metal phosphide, metal oxide, fast ionic conductor, conductive polymer and the like as coating materials have been successfully applied to the anode material of the lithium ion battery, and the electrochemical performance of the electrode material is effectively improved. However, conventional coating methods or materials always suffer from inherent drawbacks, such as that metal oxides and metal phosphides as electrochemically inert substances do not contribute to the electrode kinetics at the material interface, and the conductive polymer/fast ion conductor each only positively contribute to a single aspect of electron transfer or ion transport. For example, the coating method is single, and most of the current commercial coatings are calcined after mechanical mixing, which causes the coating on the surface of the cycle to be easy to fall off, thereby causing the cycle performance of the material to be suddenly reduced at the later stage of the cycle. For example, many high-nickel ternary cathode materials are coated by a single layer or a single substance, and are easy to fall off at the later stage of cycle, thereby causing the cycle performance to be reduced.
In the field of surface modification, the stability of a crystal structure and the stability of a surface structure of a high-nickel ternary positive electrode material are improved mainly by doping and surface modification, so that the cycle retention rate of the high-nickel ternary positive electrode material in the cycle process of a lithium ion battery is improved. However, for the high-nickel ternary cathode material, after the precursor, the lithium hydroxide and the dopant are uniformly mixed and calcined at high temperature, the surface residual alkali (lithium hydroxide and lithium carbonate) is high, the higher the nickel content is, the higher the alkaline substance residue is, the residual alkali can cause unstable slurry in the subsequent cell preparation homogenate, the jelly phenomenon can occur in severe cases, and the residual alkali can cause adverse effects such as cell gas generation and the like. Therefore, the industry generally adopts a water washing mode to remove the residual alkaline substances on the surface. However, the water washing can erode the surface of the high-nickel ternary cathode material, and the stability of the surface structure is reduced. In addition, although the surface of the conventional high-nickel ternary cathode material is modified, the particles of the cathode material are easily damaged after a certain number of cycles, so that side reactions are quite large in the later cycle process, and the soft package battery cell has serious gas generation and has extremely bad influence on the cycle performance of the material.
In summary, the high-nickel ternary cathode material in the prior art has the problems of being incapable of effectively inhibiting the corrosion of the electrolyte, poor in structural stability, low in capacity and the like. Therefore, it is necessary to develop a new high nickel ternary cathode material to improve the above problems.
Disclosure of Invention
The invention mainly aims to provide a high-nickel ternary cathode material, a preparation method thereof and a lithium ion battery, and aims to solve the problems that the high-nickel ternary cathode material in the prior art can not effectively inhibit the corrosion of electrolyte, has poor structural stability, has low capacity and the like.
In order to achieve the above object, according to one aspect of the present invention, there is provided a high nickel ternary positive electrode material including: a ternary cathode material matrix with the chemical formula of LiNi X Mn Y Co 1-X-Y O 2 X is more than or equal to 0.6 and less than or equal to 0.90,0.05 and less than or equal to 0.15; the first coating layer is coated on the outer surface of the ternary cathode material substrate and is made of LiM Z O and M are transition metal elements, and Z is more than or equal to 0.1 and less than or equal to 1; the second coating layer is coated on the outer surface of the first coating layer far away from the ternary cathode material matrix and is made of LiNi a Mn b Co c O 2 A is more than or equal to 0.3 and less than or equal to 0.5,0.2 and less than or equal to b is more than or equal to 0.4,0.2 and less than or equal to c is more than or equal to 0.4, wherein a + b + c =1.
Further, the particle size of the high-nickel ternary cathode material is 10-11 μm; preferably, the thickness of the second cladding layer is 2 to 10nm.
Further, the material of the second coating layer is LiNi 1/3 Mn 1/3 Co 1/3 O 2 。
Further, the weight ratio of the first coating layer to the ternary cathode material matrix is 1 (500-3000); preferably, in the first cladding layer, M is one or more of Al, zr, si, ti, W, Y, mg, si, B, co, mn, V and P, more preferably one or more of Zr, W, V, al and Ti.
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for preparing the above high-nickel ternary positive electrode material, the method comprising: coating a first coating layer on the outer surface of a ternary cathode material substrate, wherein the ternary cathode material substrate is LiNi X Mn Y Co 1-X-Y O 2 X is more than or equal to 0.6 and less than or equal to 0.90,0.05 and less than or equal to 0.15; the first coating layer is LiM Z O and M are transition metals, and Z is more than or equal to 0.1 and less than or equal to 1; coating a second coating layer on the outer surface of the first coating layer, which is far away from the ternary cathode material substrate, so as to form the high-nickel ternary cathode material, wherein the second coating layer is LiNi a Mn b Co c O 2 A is more than or equal to 0.3 and less than or equal to 0.5,0.2 and less than or equal to b is more than or equal to 0.4,0.2 and less than or equal to c is more than or equal to 0.4, wherein a + b + c =1.
Further, mixing the ternary positive electrode material matrix, a lithium source, an M source and a chelating agent, sequentially carrying out sol-gel reaction and first oxidation sintering on the mixture, and coating a first coating layer, which is marked as LiNi, on the outer surface of the ternary positive electrode material matrix x Mn y Co 1-X-Y O 2 @LiM Z O; metal salt solution containing nickel, cobalt and manganese, precipitator, ammonia water and LiNi x Mn y Co 1-X-Y O 2 @LiM Z Mixing O for coprecipitation reaction, mixing the filtered precipitate with lithium hydroxide for second oxidizing sintering to form a layer on the outer surface of the first coating layerCoated with a second coating layer, denoted LiNi x Mn y Co 1-X-Y O 2 @LiM Z O@LiNi a Mn b Co c O 2 。
Further, in the coprecipitation reaction process, the reaction temperature is 40-50 ℃; the stirring speed is 600-800 rpm; the pH value of the reaction system is 10-11; the reaction time is 4-6 h; preferably, the molar ratio of nickel, cobalt and manganese elements in the metal salt solution is (0.3-5) to (0.2-0.4); preferably, the precipitant is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide or ammonium bicarbonate; preferably, the molar ratio of the total molar content of nickel, cobalt and manganese in the precipitant and the metal salt solution is (2-6) to (1-3).
Further, in the sol-gel reaction process, the reaction temperature is 40-50 ℃; the stirring speed is 500-800 rpm; the reaction time is 12-15 h; preferably, the chelating agent is one or more of citric acid, lactic acid, sodium citrate or ammonia water; preferably, the lithium source is one or more of lithium hydroxide, lithium carbonate, lithium oxalate, or lithium sulfate; preferably, the M source is one or more of oxides containing Al, zr, si, ti, W, Y, mg, si, B, co, mn, V and P, more preferably one or more of zirconia, tungsten oxide, vanadium oxide, alumina and titania; preferably, the molar ratio of the M source to the lithium source is (1-3) to (2-6).
Furthermore, in the first oxidation sintering process, the treatment temperature is 750-780 ℃, the treatment time is 8-12 h, and the oxygen volume concentration is more than or equal to 98 percent; preferably, in the second oxidation sintering process, the treatment temperature is 860-900 ℃, the treatment time is 10-12 h, and the oxygen volume concentration is more than or equal to 98%.
According to another aspect of the present invention, a lithium ion battery is provided, which includes a positive electrode material, wherein the positive electrode material is the above-mentioned high nickel ternary positive electrode material, or the high nickel ternary positive electrode material prepared by the above-mentioned preparation method.
Based on the double-layer cladding structure high-nickel ternary cathode material, the chemical erosion can be greatly inhibited, the surface impedance of the material can be reduced, and the defects and the structure of the material are fundamentally solvedAnd (5) problems are solved. Also, a low nickel ternary positive electrode material (LiNi) a Mn b Co c O 2 ) The high-nickel ternary positive electrode material has excellent structural stability in a circulation process, and can further isolate side reactions of electrolyte, unstable metal ions and the like in the battery, so that the problem of volume expansion of the battery material is effectively relieved, the service life of the battery material is prolonged, and the long circulation property of the battery is ensured. Meanwhile, liM Z And O is used as an intermediate coating layer, so that the contact area between the electrolyte and the cathode material can be further reduced, and the synergistic effect of the O, the matrix material and the second coating layer is better. Based on this, the coating layer of the double-layer coated high-nickel ternary cathode material is more difficult to fall off, and the high-nickel ternary cathode material has excellent performances of long service life and high safety, greatly improves the structural stability of the high-nickel ternary cathode material, and further can further reduce the generation of microcracks and the internal structural damage of the material. In addition, a low-nickel ternary positive electrode material (LiNi) a Mn b Co c O 2 ) As the second coating layer, the structural stability of the material is improved, the contact area between the material and the electrolyte is reduced, the conductivity of the material is not affected, and the capacity of the battery can be further improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows an XRD pattern of a high nickel ternary positive electrode material in one embodiment of the present invention.
Detailed Description
Interpretation of terms:
high-nickel ternary cathode material: the Ni content of the nickel-cobalt-manganese-lithium oxide occupies more than 60 percent of the total of Ni, co and Mn elements.
And (3) sintering: the experimental material is put into an experimental furnace and is placed for a period of time at a certain temperature and under a certain atmosphere.
Washing with water: mixing deionized water and the material to be washed according to a proportion, and then stirring to a certain degree.
Coating: the coating elements are theoretically present only on the surface of the material.
As described in the background of the invention section, the high-nickel ternary positive electrode material in the prior art has the problems of being unable to effectively inhibit the corrosion of the electrolyte, poor in structural stability, low in capacity and the like. In order to solve the problem, the invention provides a high-nickel ternary cathode material, which comprises the following components in parts by weight: a ternary cathode material matrix with the chemical formula of LiNi X Mn Y Co 1-X-Y O 2 X is more than or equal to 0.6 and less than or equal to 0.90,0.05 and less than or equal to 0.15; a first coating layer coated on the outer surface of the ternary cathode material matrix and made of LiM Z O and M are transition metal elements, and Z is more than or equal to 0.1 and less than or equal to 1; the second coating layer is coated on the outer surface of the first coating layer far away from the ternary cathode material matrix and is made of LiNi a Mn b Co c O 2 A is more than or equal to 0.3 and less than or equal to 0.5,0.2 and less than or equal to b is more than or equal to 0.4,0.2 and less than or equal to c is more than or equal to 0.4, wherein a + b + c =1.
Firstly, based on the double-layer cladding structure high-nickel ternary cathode material, the chemical erosion can be greatly inhibited, the surface impedance of the material can be reduced, and the defects and the structural problems of the material can be fundamentally solved. Second, low nickel ternary positive electrode materials (LiNi) a Mn b Co c O 2 ) The high-nickel ternary positive electrode material has excellent structural stability in a circulation process, and can further isolate side reactions of electrolyte, unstable metal ions and the like in the battery, so that the problem of volume expansion of the battery material is effectively solved, the service life of the battery material is prolonged, and the long circulation of the battery is ensured. Further, liM Z And the O is used as an intermediate coating layer, so that the contact area between the electrolyte and the cathode material can be further reduced, and the synergistic effect with the base material and the second coating layer is better. Based on the structure, the coating layer of the double-layer coated high-nickel ternary cathode material is less prone to falling off, the high-nickel ternary cathode material has excellent performances of long service life and high safety, the structural stability of the high-nickel ternary cathode material is greatly improved, and then the microcrack production of the material can be further reducedAnd internal structural damage. In addition, a low nickel ternary positive electrode material (LiNi) a Mn b Co c O 2 ) As the second coating layer, the structural stability of the material is improved, the contact area between the material and the electrolyte is reduced, the conductivity of the material is not affected, and the capacity of the battery can be further improved.
Note that LiNi used in the present application x Mn y Co 1-X-Y O 2 The material may be prepared by methods known in the art, and in some embodiments, the ternary cathode material matrix is prepared by a process comprising: and carrying out high-temperature oxidation sintering on the mixture of the nickel-cobalt-manganese hydroxide and the lithium hydroxide monohydrate to obtain the ternary cathode material matrix. The molar ratio of the lithium hydroxide monohydrate to the nickel-cobalt-manganese hydroxide is preferably (1-1.1): 1, the sintering temperature of the oxidation sintering is preferably 600-800 ℃, the time is 4-12 h, and the preferable atmosphere is required to be oxygen volume concentration more than or equal to 98%. And (3) carrying out double-roll crushing, ultracentrifugal grinding and crushing on the material obtained by the oxidation sintering, and then sieving by using a 300-400-mesh sieve to obtain the ternary cathode material matrix. By the preparation method, the appearance and the element proportion of the matrix material can be designed and controlled, so that the matrix material which is more suitable for the high-nickel ternary cathode material is obtained, and the electrical property of the cathode material is further improved.
In order to further balance the above excellent properties of the material, the particle size of the high nickel ternary positive electrode material is preferably 10 to 11 μm.
Preferably, the thickness of the second cladding layer is 2 to 10nm. Therefore, the side reaction of the electrolyte, metal ions and the like can be further isolated, and the long cycle performance of the battery can be further improved. More preferably, the second cladding layer is LiNi 1/3 Mn 1/3 Co 1/3 O 2 . Based on the material, the material not only can obtain higher stability and longer service life, but also has better conductivity and higher capacity.
Preferably, the weight ratio of the first coating layer to the ternary positive electrode material matrix is 1 (500-3000). More preferably, the firstIn the clad layer, M is one or more of Al, zr, si, ti, W, Y, mg, si, B, co, mn, V and P, more preferably one or more of Zr, W, V, al and Ti. Based on this, liM Z The intermediate coating layer is O, so that the intermediate coating layer has better adaptability with the base material and the second coating layer, and the stability and the conductivity of the material are better.
The invention also provides a preparation method of the high-nickel ternary cathode material, which comprises the following steps: coating a first coating layer on the outer surface of a ternary cathode material substrate, wherein the ternary cathode material substrate is LiNi X Mn Y Co 1-X-Y O 2 X is more than or equal to 0.6 and less than or equal to 0.90,0.05 and less than or equal to 0.15; the first coating layer is LiM Z O and M are transition metals, and Z is more than or equal to 0.1 and less than or equal to 1; coating a second coating layer on the outer surface of the first coating layer, which is far away from the ternary cathode material substrate, so as to form the high-nickel ternary cathode material, wherein the second coating layer is LiNi a Mn b Co c O 2 ，0.3≤a≤0.5，0.2≤b≤0.4，0.2≤c≤0.4。
Based on the above reasons, the high-nickel ternary cathode material with the double-layer coating structure is prepared, so that the chemical corrosion can be greatly inhibited, the surface impedance of the material can be reduced, and the defects and the structural problems of the material can be fundamentally solved. Low-nickel ternary positive electrode material (LiNi) a Mn b Co c O 2 ) The high-nickel ternary positive electrode material has excellent structural stability in a circulation process, and can further isolate the side reactions of electrolyte, unstable metal ions and the like in the battery, so that the problem of volume expansion of the battery material is effectively solved, the service life of the battery material is prolonged, and the long circulation property of the battery is ensured. Moreover, the double-layer coated high-nickel ternary cathode material has the excellent performances of long service life and high safety, and the structural stability of the high-nickel ternary cathode material is greatly improved, so that the generation of microcracks and the internal structural damage of the material can be further reduced. In addition, a low nickel ternary positive electrode material (LiNi) a Mn b Co c O 2 ) The coating layer can further improve the capacity of the battery. In addition thereto, by the preparation described aboveAccording to the method, the structure of the coated high-nickel ternary cathode material is not damaged, the coating thickness can be controlled according to different pre-coating amounts, the cost is low, and the coating method is simple and easy to implement.
Preferably, the preparation method comprises: mixing a ternary positive electrode material matrix, a lithium source, an M source and a chelating agent, and sequentially carrying out sol-gel reaction and first oxidation sintering on the mixture to coat a first coating layer, which is marked as LiNi, on the outer surface of the ternary positive electrode material matrix x Mn y Co 1-X-Y O 2 @LiM Z O; metal salt solution of nickel, cobalt and manganese, precipitant, ammonia water and LiNi x Mn y Co 1-X- Y O 2 @LiM Z Mixing O for coprecipitation reaction, mixing the filtered precipitate and lithium hydroxide for second oxidizing sintering to coat a second coating layer, namely LiNi, on the outer surface of the first coating layer x Mn y Co 1-X-Y O 2 @LiM Z O@LiNi a Mn b Co c O 2 . The chelating agent can effectively hold metal ions to facilitate the formation of a subsequent first coating substance on one hand, and can form a stable water-soluble complex to prevent other unnecessary precipitates or other substances from being generated on the other hand.
Mixing a lithium source, an M source and a chelating agent with a ternary cathode material matrix to perform a sol-gel reaction to form LiM on the matrix material Z OH precursor is first oxidized and sintered to form LiM Z The O coating layer can realize the uniform coating of the ternary anode material matrix, effectively reduces the contact area of the material and electrolyte, further reduces the side reaction on the surface of the material in the charge and discharge process, and improves the circulation stability of the anode material. Meanwhile, based on the operation, the thickness of the first coating layer is more suitable, the uniformity is better, and a better growth plane is further provided for the subsequent coating of the second coating layer on the basis of improving the stability of the material. In a preferred embodiment, the lithium source is one or more of lithium hydroxide, lithium carbonate, lithium hydroxide, or lithium sulfate; preferably, the M source is a source containing Al, zr, si, ti, W, Y, mg, siB, co, mn, V and P oxides, more preferably one or more of zirconia, tungsten oxide, vanadium oxide, alumina and titania.
In order to further improve the coating uniformity and stability of the first coating layer, preferably, the reaction temperature is 40-50 ℃ in the sol-gel reaction process; the stirring speed is 600-800 rpm; the reaction time is 12-15 h. Preferably, the chelating agent is one or more of citric acid, lactic acid, sodium citrate or ammonia water; preferably, the molar ratio of the M source to the lithium source is (1-3) to (2-6).
In a preferred embodiment, the LiM obtained by the sol-gel reaction described above is first obtained Z And (4) putting the OH precursor into a freeze dryer for freeze drying for 12-15 h. And then putting the dried material into an oxygen atmosphere furnace, setting the heating rate at 2 ℃/min, preserving the heat for 8-12 h at 750-780 ℃, and carrying out first oxidizing roasting under the atmosphere that the volume concentration of oxygen is more than or equal to 98%, and cooling the roasted material along with the furnace. Based on this, the bonding stability between the first coating layer and the base material is effectively improved, and the uniformity of the coating layer is improved. Grinding and sieving the material after the first oxidation sintering (300-400 meshes) to obtain LiNi x Mn y Co 1-X-Y O 2 @LiM Z O。
Preferably, the preparation method comprises: by mixing metal salt solution containing nickel, cobalt and manganese, precipitant, ammonia water and LiNi x Mn y Co 1-X-Y O 2 @LiM Z O mixing and carrying out coprecipitation reaction to form LiNi on the first coating layer a Mn b Co c (OH) 2 Adding lithium hydroxide into the precursor to perform second oxidation sintering to form LiNi a Mn b Co c O 2 And (4) coating. Based on coprecipitation reaction, a more uniform and compact low-nickel ternary coating layer can be formed on the first coating layer, the thickness of the second coating layer can be better controlled through the time of the coprecipitation reaction and the using amount of reactants, and the structural stability and the conductivity of the material can be better balanced.
In order to improve the stability and the high efficiency of the coprecipitation reaction and promote the structural performance and the conductive performance of the second coating layer to be better, the reaction temperature is preferably 40-50 ℃ in the coprecipitation reaction process; the stirring speed is 600-800 rpm; the pH value of the reaction system is 10-11; the reaction time is 4-6 h. Under the condition, the reaction stability is better, and the structural performance and the conductivity of the obtained material are better. Preferably, the molar ratio of nickel, cobalt and manganese elements in the metal salt solution is (0.3-0.5): (0.2-0.4): (0.2-0.4). Preferably, the precipitant is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide or ammonium bicarbonate; preferably, the molar ratio of the precipitant to the total metal molar weight of nickel, cobalt and manganese in the metal salt solution is (2-6) to (1-3). Based on this, the uniformity of the second cladding layer is better.
In a preferred embodiment, liNi is used x Mn y Co 1-X-Y O 2 @LiM Z Taking O as seed crystal and preparing LiNi with the concentration of 2-2.5 mol/L x Mn y Co 1-X-Y O 2 @LiM Z An aqueous solution of O; preparing a precipitator aqueous solution with the concentration of 4-4.5 mol/L; preparing a metal salt solution with the concentration of 1.5-2 mol/L. Reacting LiNi x Mn y Co 1-X-Y O 2 @LiM Z Adding the O aqueous solution into a reaction kettle, setting the temperature of the reaction kettle at 50-55 ℃, stirring at 600-800 rpm, and stirring for 30-35 min. And then, continuously adding a first part of precipitator aqueous solution and a first part of ammonia water solution into the reaction kettle to enable the pH value of the reaction system to be 10-11, and finally, simultaneously and continuously adding a metal salt solution, a second part of precipitator aqueous solution and a second part of ammonia water solution into the system to perform coprecipitation reaction, wherein the adding flow rate of the metal salt solution is 200-210 mL/h, the adding time is 4-6 h, and the reaction is carried out for 4-5 h under the condition. Based on this, the thickness of the second clad layer can be further effectively controlled within a more preferable range.
In a preferred embodiment, the mixed material after coprecipitation is sequentially subjected to suction filtration, washing and suction filtration to obtain LiNi a Mn b Co c (OH) 2 Putting the precursor into a vacuum drying ovenVacuum drying is carried out for 12-20 h. Therefore, the moisture in the material can be further promoted to be separated from the material, and the phenomenon that the excessive moisture is left in the material for a long time to cause the structural damage of the material is further avoided. Meanwhile, residual alkali can be further removed, and the electrochemical cycle performance of the material is further improved. And (3) putting the dried material into an oxygen atmosphere furnace, setting the heating rate at 2 ℃/min, the treatment temperature at 860-900 ℃, the treatment time at 10-12 h, and the oxygen volume concentration at more than or equal to 98 percent, so as to carry out second oxidizing roasting, and cooling the roasted material along with the furnace. Based on this, the bonding stability between the second cladding layer and the first cladding layer is effectively improved, and the uniformity of the cladding layer is improved. And grinding and sieving (400 meshes) the material after the second oxidizing roasting treatment to obtain the high-nickel ternary cathode material.
The invention also provides a lithium ion battery which comprises the cathode material, wherein the cathode material is the high-nickel ternary cathode material, or the high-nickel ternary cathode material prepared by the preparation method.
Preferably, the lithium ion battery is a button half battery, and the high-nickel ternary cathode material, SP, and PVDF are mixed according to a ratio of 92:4:4, preparing the button half cell, and adopting a metal lithium sheet as a negative electrode.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
(1) Uniformly mixing lithium hydroxide monohydrate and nickel-cobalt-manganese hydroxide according to a certain proportion, wherein the molar ratio of Li to Me (the molar content of total metal elements of nickel-cobalt-manganese) is 1.04:1;
(2) Putting the uniformly mixed materials into an oxygen atmosphere furnace, setting the heating rate to be 2 ℃/min, preserving the heat for 10h at 760 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the volume concentration of oxygen is more than or equal to 98%;
(3) Cooling, crushing the material by using a pair roller, ultracentrifugally grinding and crushing, and sieving by using a 400-mesh sieve to obtain the material marked as a ternary cathode material matrix (LiNi) 0.83 Mn 0.11 Co 0.06 O 2 )；
(4) Adding tungsten trioxide and lithium hydroxide into deionized water, wherein the weight ratio of tungsten trioxide: the molar ratio of lithium hydroxide is 1:2;
(5) Adding citric acid and the ternary cathode material matrix into the solution (4), and stirring for 12 hours;
(6) Putting the stirred solution into a freeze dryer for freeze drying for 12 hours;
(7) Placing the dried material into an oxygen atmosphere furnace for first oxidizing roasting, setting the heating rate to be 2 ℃/min, preserving the heat for 8 hours at 500 ℃, and cooling along with the furnace, wherein the atmosphere requirement is that the volume concentration of oxygen is more than or equal to 98%;
(8) Grinding and sieving the roasted material in the step (7) in sequence (400-mesh sieve), and marking the material as Li 1.04 Ni 0.83 Mn 0.11 Co 0.06 O 2 @Li 2 WO 4 . Wherein the weight ratio of the first coating layer to the base material is 1:1000, parts by weight;
(9) 4L of 4mol/L sodium hydroxide solution is prepared; preparing 4L of 1.5mol/L metal salt solution, wherein the molar ratio of nickel, cobalt and manganese elements is 1; configuration of 2mol/L Li 1.04 Ni 0.83 Mn 0.11 Co 0.06 O 2 @Li 2 WO 4 The molar ratio of the total metal molar content of nickel, cobalt and manganese in the metal salt solution to the precipitant is 1:2;
(10) Mixing Li in the step (9) 1.04 Ni 0.83 Mn 0.11 Co 0.06 O 2 @Li 2 WO 4 Adding the solution into a 5L reaction kettle, and simultaneously adding 100mL of ammonia water solution and the 4mol/L sodium hydroxide solution into the reaction kettle to enable the pH value of the system to be 11; setting the temperature of the reaction kettle to be 50 ℃, stirring at the speed of 600rpm, and stirring for 30min; then regulating the stirring speed of the reaction kettle to 800rpm, and continuously adding the 1.5mol/L metal salt solution, the ammonia water solution and the 4mol/L sodium hydroxide solution into the reaction kettle simultaneously to perform coprecipitation reaction; metal salt solution, ammonia water solution and the above 4mol/L sodium hydroxideThe adding flow rate of the solution is 200mL/h;
(11) After dropwise adding for 4h, stirring for 30min to age the slurry;
(12) Carrying out suction filtration and washing on the slurry solution after the reaction is finished;
(13) Putting the filtered material into a vacuum drying oven at 120 ℃ for vacuum drying for 12 hours;
(14) Uniformly mixing lithium hydroxide monohydrate and the dried material in the step (13), wherein the molar ratio of Li to Me (the molar content of nickel, cobalt and manganese total metal elements in the outermost layer) is 1:1;
(15) Putting the uniformly mixed material in the step (14) into an oxygen atmosphere furnace, setting the heating rate to be 2 ℃/min, preserving the heat for 12 hours at 980 ℃, and cooling along with the furnace, wherein the atmosphere is required to be that the volume concentration of oxygen is 98%;
(16) Sieving the roasted material by a 400-mesh sieve, and then packaging to obtain the double-layer coated Li 1.04 Ni 0.83 Mn 0.11 Co 0.06 O 2 @Li 2 WO 4 @LiNi 1/3 Mn 1/3 Co 1/3 O 2 . The particle size of the high-nickel ternary cathode material is 10 mu m; the second cladding layer thickness was 4nm.
Mixing the high-nickel ternary cathode material obtained by the preparation method, carbon black (SP) and polyvinylidene fluoride binder (PVDF) according to a weight ratio of 92:4:4, preparing the button half cell, and adopting a metal lithium sheet as a negative electrode.
The XRD pattern of the high-nickel ternary cathode material obtained by the preparation method is shown in figure 1.
Example 2
The only difference from example 1 is that: replacing tungsten trioxide with titanium dioxide, titanium dioxide: the molar ratio of lithium hydroxide is 2:3. wherein the weight ratio of the first coating layer to the base material is 2.
Example 3
The only difference from example 1 is that: replacing tungsten trioxide with aluminum oxide: the molar ratio of lithium hydroxide was 1:2. Wherein the weight ratio of the first coating layer to the base material is 1.
Example 4
The only difference from example 1 is that: replacing tungsten trioxide with zirconium dioxide, zirconium dioxide: the molar ratio of lithium hydroxide was 1:3. Wherein the weight ratio of the first coating layer to the base material is 1.
Example 5
The only difference from example 1 is that: replacing tungsten trioxide with vanadium oxide, vanadium oxide: the molar ratio of lithium hydroxide was 1:5. Wherein the weight ratio of the first coating layer to the base material is 1.
Example 6
The only difference from example 1 is that: the mol ratio of nickel, cobalt and manganese metals in the metal salt solution is respectively 4:4:2, the second coating layer is LiNi 0.4 Mn 0.4 Co 0.2 O 2 。
Example 7
The only difference from example 1 is that: the molar ratio of nickel, cobalt and manganese metals in the metal salt solution is respectively 5:4:1, the second coating layer is LiNi 0.5 Mn 0.4 Co 0.1 O 2 。
Example 8
The only difference from example 1 is that: in the coprecipitation reaction process, the reaction temperature is 40 ℃.
Example 9
The only difference from example 1 is that: the pH value of the reaction system is 10 in the coprecipitation reaction process.
Comparative example 1
The only difference from example 1 is that the second coating layer was not coated, and the material was denoted as Li 1.04 Ni 0.83 Mn 0.11 Co 0.06 O 2 @Li 2 WO 4 。
And (3) performance characterization:
the battery assembling method comprises the following steps: the positive pole piece is prepared by mixing the prepared material, conductive carbon black and a polyvinylidene fluoride (PVDF) adhesive according to the mass ratio of 90. The negative electrode adopts a metal lithium sheet, and the diaphragm is polypropyleneOlefin porous membrane, electrolyte lmol/L LiPF 6 (iv)/EC + DEC + DMC (EC: DEC: DMC =1. Initial specific capacity test conditions: testing at 0.1C, 2.7V-4.3V; multiplying power performance test conditions: 1C for 100 weeks; cycle performance test conditions: 0.1C, testing for 100 weeks at normal temperature; the results of the performance testing are shown in table 1 below.
TABLE 1
The present invention has been described in terms of the preferred embodiment, and it is not intended to be limited to the embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (19)
1. A high nickel ternary positive electrode material, comprising:
a ternary cathode material matrix with the chemical formula of LiNi X Mn Y Co 1-X-Y O 2 ，0.6≤X≤0.90，0.05≤Y≤0.15；
The first coating layer is coated on the outer surface of the ternary cathode material matrix and is made of Li 2 WO 4 ；
The second coating layer is coated on the outer surface of the first coating layer, which is far away from the ternary positive electrode material matrix, and is made of LiNi a Mn b Co c O 2 A is more than or equal to 0.3 and less than or equal to 0.5,0.2 and less than or equal to b is more than or equal to 0.4,0.2 and less than or equal to 0.4, and a + b + c =1.
2. The high-nickel ternary positive electrode material according to claim 1, wherein the particle size of the high-nickel ternary positive electrode material is 10 to 11 μm.
3. The high-nickel ternary positive electrode material according to claim 2, wherein the thickness of the second coating layer is 2 to 10nm.
4. The high-nickel ternary positive electrode material according to claim 1 or 2, wherein the material of the second coating layer is LiNi 1/3 Mn 1/3 Co 1/3 O 2 。
5. The high-nickel ternary cathode material as claimed in claim 1, wherein the weight ratio of the first coating layer to the ternary cathode material matrix is 1 (500 to 3000).
6. A method of making the high-nickel ternary positive electrode material of any of claims 1-5, comprising:
coating a first coating layer on the outer surface of a ternary cathode material substrate, wherein the ternary cathode material substrate is LiNi X Mn Y Co 1-X-Y O 2 X is more than or equal to 0.6 and less than or equal to 0.90,0.05 and less than or equal to 0.15; the first coating layer is Li 2 WO 4 ；
Coating a second coating layer on the outer surface of the first coating layer, which is far away from the ternary cathode material substrate, so as to form the high-nickel ternary cathode material, wherein the second coating layer is LiNi a Mn b Co c O 2 A is more than or equal to 0.3 and less than or equal to 0.5,0.2 and less than or equal to b is more than or equal to 0.4,0.2 and less than or equal to c is more than or equal to 0.4, wherein a + b + c =1.
7. The method of preparing a high-nickel ternary positive electrode material of claim 6, comprising:
mixing the ternary cathode material substrate, a lithium source, an M source and a chelating agent, sequentially carrying out sol-gel reaction and first oxidation sintering on the mixture, so as to coat the first coating layer on the outer surface of the ternary cathode material substrate, and marking the first coating layer as LiNi x Mn y Co 1-X-Y O 2 @ Li 2 WO 4 ；
Metal salt solution containing nickel, cobalt and manganese, precipitator, ammonia water and LiNi x Mn y Co 1-X-Y O 2 @ Li 2 WO 4 Mixing the two to perform a coprecipitation reaction, and then mixing the filtered precipitate with lithium hydroxide to perform a second oxide sintering to coat the second coating layer, which is marked as LiNi, on the outer surface of the first coating layer x Mn y Co 1-X-Y O 2 @ Li 2 WO 4 @ LiNi a Mn b Co c O 2 。
8. The preparation method of the high-nickel ternary cathode material according to claim 7, wherein the reaction temperature is 40 to 50 ℃ in the coprecipitation reaction process; the stirring speed is 600 to 800rpm; the pH value of the reaction system is 10 to 11; the reaction time is 4 to 6h.
9. The method for preparing the high-nickel ternary cathode material as claimed in claim 8, wherein the molar ratio of nickel, cobalt and manganese in the metal salt solution is (0.3 to 0.5): (0.2 to 0.4): 0.2 to 0.4).
10. The method of claim 8, wherein the precipitant is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, or ammonium bicarbonate.
11. The method of claim 8, wherein the molar ratio of the total molar content of nickel, cobalt, and manganese in the precipitant and the metal salt solution is (2~6): (1~3).
12. The method for preparing the high-nickel ternary cathode material according to claim 7, wherein the reaction temperature is 40-50 ℃ in the sol-gel reaction process; the stirring speed is 500 to 800rpm; the reaction time is 12 to 15h.
13. The method for preparing a high-nickel ternary cathode material according to claim 12, wherein the chelating agent is one or more of citric acid, lactic acid, sodium citrate or ammonia water.
14. The method of claim 12, wherein the lithium source is one or more of lithium hydroxide, lithium carbonate, lithium oxalate, or lithium sulfate.
15. The method of preparing a high-nickel ternary positive electrode material of claim 12, wherein the M source is tungsten oxide.
16. The method of claim 12, wherein the molar ratio of the M source to the lithium source is (1~3): (2~6).
17. The preparation method of the high-nickel ternary cathode material as claimed in claim 7, wherein in the first oxidation sintering process, the treatment temperature is 750 to 780 ℃, the treatment time is 8 to 12h, and the oxygen volume concentration is more than or equal to 98%.
18. The method for preparing the high-nickel ternary cathode material as claimed in claim 17, wherein the second oxidizing sintering process is carried out at 860 to 900 ℃ for 10 to 12h, and the oxygen volume concentration is greater than or equal to 98%.
19. A lithium ion battery comprises a positive electrode material, and is characterized in that the positive electrode material is the high-nickel ternary positive electrode material in any one of claims 1 to 5, or the high-nickel ternary positive electrode material prepared by the preparation method of the high-nickel ternary positive electrode material in any one of claims 6 to 18.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111015861.3A CN113839040B (en) | 2021-08-31 | 2021-08-31 | High-nickel ternary cathode material, preparation method thereof and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111015861.3A CN113839040B (en) | 2021-08-31 | 2021-08-31 | High-nickel ternary cathode material, preparation method thereof and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113839040A CN113839040A (en) | 2021-12-24 |
| CN113839040B true CN113839040B (en) | 2023-03-07 |
Family
ID=78961677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111015861.3A Active CN113839040B (en) | 2021-08-31 | 2021-08-31 | High-nickel ternary cathode material, preparation method thereof and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113839040B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115304107B (en) * | 2022-03-04 | 2023-12-05 | 深圳市德方创域新能源科技有限公司 | Lithium-rich nickel-containing ternary composite material and preparation method and application thereof |
| CN114725338A (en) * | 2022-03-17 | 2022-07-08 | 宁波容百新能源科技股份有限公司 | High-nickel multi-element positive electrode material, and preparation method and application thereof |
| CN115036493A (en) * | 2022-07-22 | 2022-09-09 | 宁波容百新能源科技股份有限公司 | Composite coating agent for positive electrode material, high-nickel single crystal positive electrode material and battery |
| CN117334883B (en) * | 2023-11-24 | 2024-02-02 | 广东省中科海钠科技有限责任公司 | Sodium-electricity positive electrode material and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108321366B (en) * | 2017-12-28 | 2020-07-17 | 合肥国轩高科动力能源有限公司 | Coating method for improving electrochemical performance of high-nickel ternary nickel-cobalt-manganese positive electrode material |
| CN109273701B (en) * | 2018-11-23 | 2022-03-18 | 中南大学 | High-nickel core-shell structure gradient nickel-cobalt-manganese ternary cathode material and preparation method thereof |
| CN109742336A (en) * | 2018-12-07 | 2019-05-10 | 北京理工大学 | A kind of surface layer coats the tertiary cathode material and preparation method of tungstate lithium and doping W |
| CN110061231A (en) * | 2019-05-17 | 2019-07-26 | 中伟新材料有限公司 | A kind of nickelic tertiary cathode material of modification and preparation method thereof |
| CN112349905B (en) * | 2019-08-06 | 2021-11-23 | 湖南杉杉新能源有限公司 | Double-coating modified lithium ion battery positive electrode material and preparation method thereof |
| CN112952049A (en) * | 2019-12-11 | 2021-06-11 | 深圳市贝特瑞纳米科技有限公司 | Method for repairing surface structure of high-nickel anode material, high-nickel anode material obtained by method and lithium ion battery |
-
2021
- 2021-08-31 CN CN202111015861.3A patent/CN113839040B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113839040A (en) | 2021-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109336193B (en) | Multi-element in-situ co-doped ternary material precursor and preparation method and application thereof | |
| CN113839040B (en) | High-nickel ternary cathode material, preparation method thereof and lithium ion battery | |
| CN111559763B (en) | Ternary high-nickel cubic precursor material and preparation method and application thereof | |
| CN115924993B (en) | Nickel-iron-manganese hydroxide and preparation method thereof | |
| CN110890535A (en) | Cathode material, preparation method thereof and application of cathode material in lithium ion battery | |
| EP4394976A1 (en) | Lithium-rich manganese-based positive electrode material, and preparation method therefor and use thereof | |
| CN113488634A (en) | Double-layer coated modified high-nickel cobalt-free single crystal ternary positive electrode material and preparation method thereof | |
| CN111725514A (en) | Modification method of high-nickel ternary cathode material of lithium ion battery | |
| CN109509875B (en) | High-rate single crystal lithium nickel cobalt manganese oxide cathode material and preparation method thereof | |
| WO2024046508A1 (en) | High-nickel ternary positive electrode material having cobalt gradient, preparation method therefor, and lithium ion battery | |
| CN112803023B (en) | Lanthanum-zirconium-codoped high-nickel ternary cathode material and preparation method and application thereof | |
| CN109841822A (en) | A kind of preparation method of the modified monocrystalline tertiary cathode material of lithium ion battery | |
| CN111180724A (en) | Preparation method of ternary single crystal cathode material | |
| WO2022089205A1 (en) | Doped high-nickel ternary material and preparation method therefor | |
| CN109659519A (en) | TiO2The ternary cathode material of lithium ion battery preparation method and product of nano fiber coated | |
| CN111600014B (en) | Modified high-specific-capacity high-nickel ternary cathode material and preparation method thereof | |
| CN111540890A (en) | Nickel cobalt lithium manganate ternary cathode material and preparation method thereof | |
| CN114497527A (en) | Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery | |
| CN115663134A (en) | Novel surface nano-coating and gradient doping integrated modified ultra-high nickel ternary cathode material and preparation method thereof | |
| CN115432748A (en) | Preparation method of nickel-manganese-based precursor and monocrystal layered positive electrode material of lithium/sodium ion battery | |
| CN117342630B (en) | Sodium ion positive electrode material, preparation method thereof, positive electrode plate and sodium battery | |
| CN113200571B (en) | Lithium transition metal oxide layered positive electrode material coated on surface of antimony compound and preparation method thereof | |
| CN114455647A (en) | Preparation method of surface confinement treatment full-concentration gradient quaternary high-nickel NCMA positive electrode material | |
| CN112952056B (en) | Lithium-rich manganese-based composite cathode material and preparation method and application thereof | |
| CN108807971B (en) | Lithium-rich manganese-based positive electrode material of lithium ion battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |