CN106450217B - Method for modifying nickel cobalt lithium manganate ternary material - Google Patents
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Abstract
The invention provides a method for modifying a nickel cobalt lithium manganate ternary material, which comprises the following steps of carrying out vapor deposition on a nickel cobalt lithium manganate material under the conditions of a carbon source gas and a protective gas to obtain a carbon-coated modified nickel cobalt lithium manganate material. According to the invention, carbon is deposited on the surface of the nickel cobalt lithium manganate ternary material by a vapor deposition method, so that carbon coating is realized; the carbon coated by the nickel cobalt lithium manganate ternary material improves the first charge-discharge efficiency, improves the lithium ion diffusion coefficient and the electronic conductivity of the material, and improves the electrochemical performance of the NCM material. The modification method provided by the invention has the advantages of relatively simple equipment, few processes, controllable structure and higher battery capacity, cycle performance and rate capability of the material.
Description
Technical Field
The invention relates to the technical field of lithium ion battery electrode materials, relates to a method for modifying a nickel cobalt lithium manganate ternary material, and particularly relates to a method for carbon coating modification of a nickel cobalt lithium manganate ternary material.
Background
The lithium ion battery has the advantages of high working voltage, high specific energy, long cycle life, light weight, less white discharge, no memory effect, high cost performance and the like, has become a main selection object of rechargeable power supplies, portable electronic products and new energy vehicles in the fields of high-power electric vehicles, artificial satellites, aerospace and the like, and is an ideal new energy automobile energy storage and output power supply internationally recognized at present. Therefore, lithium ion batteries and related materials thereof become research hotspots of researchers. The anode material is one of the core parts of the lithium ion battery, determines the performance of the lithium ion battery, and the biggest bottleneck limiting the energy density, power density, cycle life and safety of the lithium ion power battery at present lies in the anode material technology.
At present, lithium ion battery anode materials are widely researched and applied to lithium cobaltate materials, lithium manganate materials, lithium iron phosphate materials, ternary materials and the like, wherein lithium cobaltate is the lithium ion battery anode material which is the earliest to realize industrial and commercial application, but cobalt is a rare resource, is expensive and has certain pollution to the environment, lithium nickelate has high theoretical specific capacity, is difficult to synthesize and poor in reproducibility of the materials, lithium manganate has rich resources and low price, but spinel lithium manganate has low capacity, the crystal structure is easy to generate Jahn-Teller effect, the capacity attenuation is fast, the cycle performance is poor, the performance performances of lithium cobaltate, lithium nickelate and lithium manganate are synthesized, and three transition metal elements of Ni, Co and Mn are combined to prepare lithium nickel cobalt manganese composite oxides, namely a nickel cobalt lithium manganate ternary material (NCM), namely a nickel cobalt lithium manganese ternary layered anode material, and the chemical formula of the lithium nickel cobalt manganese ternary layered anode material is L iNi1-x-yCoxMnyO2Including nickel-based ternary materials, or high nickel ternary materials (L iNi)1-x-yCoxMnyO2(1-x-y is more than or equal to 0.5)). due to the synergistic effect of the three elements of Ni, Co and Mn, L iCoO is synthesized2，LiNiO2And L iMnO2The three lithium ion battery anode materials have the advantages that the performance is better than that of any single-component anode material, and obvious synergistic effect exists. In the system, the electrochemical performance and the physical performance of the material are different along with the change of the proportion of the three transition metal elements, and the material has the characteristics of good thermal stability, high energy density, high specific capacity under high potential, low raw material cost and the like, and is considered to be one of the most promising positive materials of the lithium ion battery.
Although the lithium nickel cobalt manganese composite oxide ternary cathode material has the advantages. However, due to the cation mixed discharging effect and the change of the surface microstructure of the material in the first charging process, the first charging and discharging efficiency of the ternary material is not high; and the lithium ion diffusion coefficient and the electronic conductivity are low, so that the rate capability of the material is not ideal; the ternary material can generate strong side reaction with organic electrolyte in a wide voltage range, so that the impedance of the battery in the charging and discharging processes is increased, and the electrochemical performance of the material is reduced. The carbon coating modification of the ternary material is a great hot spot of the current research and can solve the problems. In the process of carbon coating by the traditional high-temperature cracking method, lithium nickelate in the ternary material is easy to reduce, so that the electrical property of the ternary material is influenced.
Therefore, how to obtain a better method for modifying the nickel cobalt lithium manganate ternary material to improve the electrical property thereof has become a problem to be solved urgently by various manufacturers and a front-line production research and development staff in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for modifying a nickel cobalt lithium manganate ternary material, and in particular, a method for carbon-coating and modifying a nickel cobalt lithium manganate ternary material.
The invention provides a method for modifying a nickel cobalt lithium manganate ternary material, which comprises the following steps:
A) and carrying out vapor deposition on the nickel cobalt lithium manganate material under the conditions of a carbon source gas and a protective gas to obtain the carbon-coated modified nickel cobalt lithium manganate material.
Preferably, the carbon source comprises one or more of an alkane, an alkene and an alkyne.
Preferably, the carbon source comprises one or more of methane, ethane, ethylene, propylene and acetylene;
the protective gas comprises one or more of carbon dioxide, nitrogen and an inert gas.
Preferably, the introduction rate of the carbon source gas is 20-100 m L/min.
Preferably, the introducing speed of the protective gas is 30-150 m L/min.
Preferably, the temperature of the vapor deposition is 500-1500 ℃;
the time of vapor deposition is 5-120 min;
the heating rate of the heating process of the vapor deposition is 5-30 ℃/min.
Preferably, the carbon coating amount of the carbon-coated modified nickel cobalt lithium manganate material is 3-10%.
Preferably, the vapor deposition method further comprises the step of introducing protective gas to remove air;
the protective gas is nitrogen and/or inert gas;
the introducing speed of the protective gas is 20-100 m L/min;
the introducing time of the protective gas is 10-120 min.
Preferably, the nickel cobalt lithium manganate material is a high-nickel ternary positive electrode material;
the chemical formula of the high-nickel ternary cathode material is shown as a formula (II),
LiNi1-x-yCoxMnyO2(II)；
wherein, (1-x-y) is not less than 0.5, x is more than 0, and y is more than 0.
The invention provides a lithium ion battery, and the anode comprises a modified nickel cobalt lithium manganate material prepared by any one of the technical schemes.
The invention provides a method for modifying a nickel cobalt lithium manganate ternary material, which comprises the following steps of carrying out vapor deposition on a nickel cobalt lithium manganate material under the conditions of a carbon source gas and a protective gas to obtain a carbon-coated modified nickel cobalt lithium manganate material. Compared with the prior art, the method has the advantages that carbon is deposited on the surface of the nickel cobalt lithium manganate ternary material through a vapor deposition method, so that carbon coating is realized; the ternary material of the nickel cobalt lithium manganate is coated with carbon, so that the mixed discharge of cations in a lithium layer is effectively reduced, the first charge-discharge efficiency is improved, and the lithium ion diffusion coefficient and the electronic conductivity of the material are improved; and the strong side reaction of the organic electrolyte and the electrode material is reduced, the impedance of the battery in the charging and discharging process is reduced, and the electrochemical performance of the NCM material is improved. The preparation method provided by the invention has the advantages of relatively simple equipment, less processes and controllable carbon structure, and the prepared carbon-coated modified nickel cobalt lithium manganate ternary material has higher battery capacity, cycle performance and rate capability. Experimental results show that the capacity of 1C of the lithium battery prepared from the carbon-coated modified nickel cobalt lithium manganate ternary material is 33.6, and after 50 times of circulation, the capacity can still reach 96.2%.
Drawings
FIG. 1 is a schematic flow chart of a device for preparing a carbon-coated lithium nickel cobalt manganese oxide ternary material by a vapor deposition method.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs analytical purity or purity conventional in the field of lithium ion batteries.
The invention provides a method for modifying a nickel cobalt lithium manganate ternary material, which comprises the following steps:
A) and carrying out vapor deposition on the nickel cobalt lithium manganate material under the conditions of a carbon source gas and a protective gas to obtain the carbon-coated modified nickel cobalt lithium manganate material.
The invention has no special limitation on the nickel cobalt lithium manganate material, and only needs to use NCM ternary material, namely nickel cobalt lithium manganate material, which is well known to those skilled in the art and used for manufacturing the lithium ion battery anode, wherein the chemical formula of the nickel cobalt lithium manganate material is shown as formula (I),
LiNi1-x-yCoxMnyO2(I)；
wherein x > 0, y > 0, 1 > 1-x-y > 0.
In order to improve the performance of the ternary material as the anode material, the nickel cobalt lithium manganate material is more preferably a high nickel cobalt lithium manganate ternary anode material (or nickel-rich nickel cobalt lithium manganate ternary material and nickel-based ternary material), the chemical formula of the high nickel cobalt lithium manganate ternary anode material is shown as a formula (II),
LiNi1-x-yCoxMnyO2(II)；
wherein, (1-x-y) is not less than 0.5, x is more than 0, and y is more than 0.
Furthermore, the value range of x is preferably 0.1-0.2, more preferably 0.12-0.18, and more preferably 0.14-0.16; the value range of y is preferably 0.1-0.3, more preferably 0.13-0.27, more preferably 0.16-0.24, and most preferably 0.19-0.21; the value range of 1-x-y is preferably 0.5-1-x-y-0.9, more preferably 0.6-1-x-y-0.9, and most preferably 0.7-1-x-y-0.8.
The invention has no special limitation on other conditions of the nickel cobalt lithium manganate material, and the conventional conditions of the NCM ternary material known by the technical personnel in the field can be selected by the technical personnel in the field according to the actual production condition, the composite condition and the product performance, and in order to further ensure the performance of the ternary composite material, the particle size of the nickel cobalt lithium manganate material is preferably 12-14 μm, more preferably 12.3-13.7 μm, and most preferably 12.5-13.5 μm.
The thickness of the carbon-coated layer is not particularly limited by the invention, and the carbon-coated layer can be coated with a conventional coating thickness well known to those skilled in the art, and the person skilled in the art can select the carbon-coated layer according to the actual production condition, the deposition condition and the product performance. The coating amount of the carbon coating is not particularly limited, and can be selected according to the actual production condition, the deposition condition and the product performance, and the carbon coating amount, namely the percentage content of the carbon in the modified nickel cobalt lithium manganate material, is preferably 3% -10%, more preferably 4% -9%, and most preferably 6% -7%, by adopting a vapor deposition technology and by controlling parameters.
According to the invention, the carbon-coated modified nickel cobalt lithium manganate material is adopted, so that the mixed discharge of cations in the lithium layer of the ternary material is effectively reduced, the first charge-discharge efficiency is improved, and the lithium ion diffusion coefficient and the electronic conductivity of the material are improved. And the organic electrolyte and the electrode material are reduced to generate strong side reaction, the impedance of the battery in the charging and discharging process is reduced, and the electrochemical performance of the material is improved.
The carbon source gas is not particularly limited, and may be a carbon source gas known to those skilled in the art, and those skilled in the art may select and adjust the carbon source gas according to actual production conditions, deposition conditions, and product properties, and the carbon source gas preferably includes one or more of alkane gas, alkene gas, and alkyne gas, more preferably includes one or more of methane, ethane, ethylene, propylene, and acetylene, more preferably methane, ethane, ethylene, propylene, or acetylene, and most preferably methane.
The protective gas is not particularly limited by the invention, and can be selected and adjusted by the protective gas known by the skilled in the art according to the actual production condition, the deposition condition and the product performance, the invention is used for improving the deposition effect, controlling the formation of the carbon structure and preventing the NCM ternary material from being reduced, the protective gas preferably comprises one or more of carbon dioxide, nitrogen and inert gas, more preferably carbon dioxide, nitrogen or argon, and most preferably carbon dioxide, the invention is not particularly limited by the introduction rate of the protective gas, and the skilled in the art can select and adjust according to the actual production condition, the deposition condition and the product performance, the invention is used for improving the deposition effect, controlling the formation of the carbon structure and preventing the NCM ternary material from being reduced, and the introduction rate of the protective gas is preferably 30-150 m L/min, more preferably 50-130 m L/min, more preferably 70-110 m L/min, and most preferably 80-100 m L/min.
The temperature of the vapor deposition is not particularly limited, and can be selected and adjusted according to the actual production condition, the deposition condition and the product performance, and can be selected and adjusted by the technical personnel in the field, in order to improve the deposition effect, control the formation of a carbon structure and prevent the reduction of the NCM ternary material, the temperature of the vapor deposition is preferably 500-1500 ℃, more preferably 700-1300 ℃, and most preferably 900-1100 ℃.
The time of the vapor deposition is not particularly limited, and a person skilled in the art can select and adjust the time according to the actual production condition, the deposition condition and the product performance, in order to improve the deposition effect, control the formation of the carbon structure and prevent the NCM ternary material from being reduced, the time of the vapor deposition is preferably 10-110 min, more preferably 30-90 min, more preferably 40-80 min and most preferably 50-70 min.
The specific conditions of the heating process of the vapor deposition are not particularly limited, and the heating process of the vapor deposition known by the skilled in the art can be selected and adjusted according to the actual production condition, the deposition condition and the product performance, the temperature rise rate of the heating process of the vapor deposition is preferably 5-30 ℃/min, more preferably 10-25 ℃/min, and most preferably 15-20 ℃/min, in order to improve the deposition effect, control the formation of a carbon structure and prevent the NCM ternary material from being reduced.
The gas is not particularly limited, protective gas well known to the skilled in the art can be used, the skilled in the art can select and adjust the gas according to the actual production condition, the deposition condition and the product performance, the gas is preferably nitrogen and/or inert gas, more preferably nitrogen and/or argon, and most preferably argon, the gas introduction rate is not particularly limited, the skilled in the art can select and adjust the gas according to the actual production condition, the deposition condition and the product performance, the gas introduction rate is preferably 20-100 m L/min, more preferably 30-90 m L/min, more preferably 40-80 m L/min, most preferably 50-70 m L/min, the gas introduction time is not particularly limited, the skilled in the art can select and adjust the gas according to the actual production condition, the deposition condition and the product performance, the gas introduction time is preferably 20-100 m L/min, more preferably 30-90 m L/min, more preferably 40-80 m L/min, most preferably 50-70 m L/min, the gas introduction time is preferably 30-10 min, and the gas introduction time is preferably 30-10 min, more preferably 30-10 min.
The invention also provides a lithium ion battery, and the positive electrode comprises the modified nickel cobalt lithium manganate material prepared by any one of the technical schemes.
The preparation method of the positive electrode is not particularly limited, and the conventional preparation method of the positive electrode of the NCM lithium ion battery, which is well known to those skilled in the art, is adopted.
The method adopts a simpler process, carries out carbon coating on the ternary material under the assistance of protective gas, particularly preferably carries out chemical vapor deposition by using carbon source gas and carbon dioxide as gas sources to carry out carbon coating on the ternary material, and leads the carbon layer to be coated on the surface of the ternary material smoothly without reacting with the ternary material by controlling the flow rate, the vapor deposition temperature and the holding time of the carbon dioxide and methane gas. The carbon dioxide is added, so that the carbon dioxide not only can play a role in catalyzing the surface of the ternary material, but also can inhibit the reduction of lithium nickelate in the ternary material in the carbon coating process, so that the coating of the carbon layer on the surface of the ternary material is realized, and the carbon dioxide is introduced to play a role in catalyzing the surface of the ternary material, so that the formation of the carbon layer is promoted.
The carbon-coated nickel cobalt lithium manganate ternary material prepared by the method effectively reduces mixed discharge of cations in a lithium layer, improves the first charge-discharge efficiency, and improves the lithium ion diffusion coefficient and the electronic conductivity of the material; and the strong side reaction of the organic electrolyte and the electrode material is reduced, the impedance of the battery in the charging and discharging process is reduced, and the electrochemical performance of the NCM material is improved. The preparation method provided by the invention has the advantages of relatively simple equipment, less processes and controllable carbon structure, and the prepared carbon-coated modified nickel cobalt lithium manganate ternary material has higher battery capacity, cycle performance and rate capability. Experimental results show that the capacity of 1C of the lithium battery prepared from the carbon-coated modified nickel cobalt lithium manganate ternary material is 33.6, and after 50 times of circulation, the capacity can still reach 96.2%.
For further illustration of the present invention, the following will describe in detail the method for modifying a nickel cobalt lithium manganate ternary material provided by the present invention with reference to the following examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed implementation and specific operation procedures are given, and are only for further illustration of the features and advantages of the present invention, but not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Weighing 5g of ternary materials, placing the ternary materials in a quartz boat 5, then placing the quartz boat in the middle of a quartz tube which is horizontally placed, and sending the quartz tube into a high-temperature area of a heating furnace.
The argon cylinder valve at 1 was opened to adjust the gas flow to 50m L/min and the gas was allowed to flow for 30min to exhaust the air in the quartz tube 6, then the argon cylinder valve at 1 was closed and carbon dioxide (CO) at 2 was opened2) Gas cylinder and methane (CH) at 34) The gas flow of the gas valve of the gas cylinder is adjusted to 50m L/min, and carbon dioxide and methane are simultaneously introduced into the quartz tube.
And opening the heating furnace 4, setting the heating speed to be 20 ℃/min, heating the quartz tube to 1000 ℃ from room temperature, and keeping the temperature at 1000 ℃ for 15min to crack methane, so that a carbon layer is generated and deposited on the surface of the ternary material.
And after the reaction is finished, stopping heating the quartz tube, closing gas valves of the carbon dioxide gas cylinder 2 and the methane gas cylinder 3, opening a gas valve of the argon gas cylinder 1, cooling the quartz tube and the sample inside to room temperature along with the furnace under the protection of argon gas, and taking out the quartz boat to obtain the required carbon-coated modified nickel cobalt lithium manganate ternary material.
The modified nickel cobalt lithium manganate ternary material obtained in the embodiment 1 of the invention is measured, and a weight gain method is adopted to obtain 5.17g of product, and the carbon coating amount can be calculated to be 3.4%.
Referring to fig. 1, fig. 1 is a schematic flow chart of an apparatus for preparing a carbon-coated nickel cobalt lithium manganate ternary material by a vapor deposition method according to the present invention. Wherein, 1 is an air valve of an argon gas cylinder, 2 is an air valve of a carbon dioxide gas cylinder, 3 is an air valve of a methane gas cylinder, 4 is a heating furnace, 5 is a quartz boat, and 6 is a quartz tube.
The button cell prepared from the modified lithium nickel cobalt manganese oxide ternary material obtained in the embodiment 1 of the invention and the conventional lithium nickel cobalt manganese oxide ternary material are subjected to electrical property measurement, a parallel comparison test is carried out, the result is shown in table 1, and table 1 is data for comparing the performance of the modified lithium nickel cobalt manganese oxide ternary material prepared in the embodiment of the invention and the conventional lithium nickel cobalt manganese oxide ternary material.
Example 2
Weighing 5g of ternary materials, placing the ternary materials in a quartz boat 5, then placing the quartz boat in the middle of a quartz tube which is horizontally placed, and sending the quartz tube into a high-temperature area of a heating furnace.
And opening the gas valve of the argon gas cylinder at the position 1, adjusting the gas flow to be 50m L/min, ventilating for 30min to exhaust the air in the quartz tube 6, then closing the gas valve of the argon gas cylinder at the position 1, opening the gas valves of the carbon dioxide gas cylinder at the position 2 and the methane gas cylinder at the position 3, respectively adjusting the gas flows to be 50m L/min and 80m L/min, and simultaneously introducing carbon dioxide and methane into the quartz tube.
And opening the heating furnace 4, setting the heating speed to be 25 ℃/min, heating the quartz tube to 1100 ℃ from room temperature, and keeping the temperature at 1100 ℃ for 20min to crack methane, so that a carbon layer is generated and deposited on the surface of the ternary material.
And after the reaction is finished, stopping heating the quartz tube, closing gas valves of the carbon dioxide gas cylinder 2 and the methane gas cylinder 3, opening a gas valve of the argon gas cylinder 1, cooling the quartz tube and the sample inside to room temperature along with the furnace under the protection of argon gas, and taking out the quartz boat to obtain the required carbon-coated modified nickel cobalt lithium manganate ternary material.
The modified nickel cobalt lithium manganate ternary material obtained in the embodiment 1 of the invention is measured, and a weight increasing method is adopted to obtain 5.43g of product, and the carbon coating amount can be calculated to be 8.6%.
The button cell prepared from the modified lithium nickel cobalt manganese oxide ternary material obtained in the embodiment 1 of the invention and the conventional lithium nickel cobalt manganese oxide ternary material are subjected to electrical property measurement, a parallel comparison test is carried out, the result is shown in table 1, and table 1 is data for comparing the performance of the modified lithium nickel cobalt manganese oxide ternary material prepared in the embodiment of the invention and the conventional lithium nickel cobalt manganese oxide ternary material.
Example 3
10g of ternary material is weighed and placed in a quartz boat 5, then the quartz boat is placed in the middle of a quartz tube which is horizontally placed, and the quartz tube is sent into a high-temperature area of a heating furnace.
And opening the gas valve of the argon gas cylinder at the position 1, adjusting the gas flow to be 50m L/min, ventilating for 40min to exhaust the air in the quartz tube 6, then closing the gas valve of the argon gas cylinder at the position 1, opening the gas valves of the carbon dioxide gas cylinder at the position 2 and the methane gas cylinder at the position 3, respectively adjusting the gas flows to be 60m L/min and 80m L/min, and simultaneously introducing carbon dioxide and methane into the quartz tube.
And opening the heating furnace, setting the heating speed at 25 ℃/min, heating the quartz tube to 1100 ℃ from room temperature, and keeping the temperature at 1100 ℃ for 20min to crack methane, so that a carbon layer is generated and deposited on the surface of the ternary material.
And after the reaction is finished, stopping heating the quartz tube, closing gas valves of the carbon dioxide gas cylinder 2 and the methane gas cylinder 3, opening a gas valve of the argon gas cylinder 1, cooling the quartz tube and the sample inside to room temperature along with the furnace under the protection of argon gas, and taking out the quartz boat to obtain the required carbon-coated modified nickel cobalt lithium manganate ternary material.
The modified nickel cobalt lithium manganate ternary material obtained in the embodiment 1 of the invention is measured, and a weight gain method is adopted to obtain 10.64g of product, and the carbon coating amount can be calculated to be 6.4%.
The button cell prepared from the modified nickel cobalt lithium manganate ternary material obtained in the embodiment 1 of the invention is subjected to electrical property measurement with the conventional nickel cobalt lithium manganate ternary material, and a parallel comparison test is carried out,
the anode is prepared by uniformly coating slurry on an aluminum foil with the thickness of 16 microns, wherein the mass ratio of the active material is 96%, the conductive agent SP (SP-L i, TIMIA L) is 2%, and the adhesive polyvinylidene fluoride (PVDF900, ARKEMA) is 2%, and the surface density is 0.164g/cm2The diameter of the round piece is 13mm, the negative electrode is a lithium piece (the diameter is 14mm, the thickness is 0.6mm), the diaphragm is a Celgard2320 diaphragm with the thickness of 16 microns, and the electrolyte contains 1 mol/L L iPF6And 5% by mass of a mixed solution of vinylene carbonate, diethyl carbonate and propylene carbonate (in a volume ratio of 3:3: 1). For comparison, a 2016 type button cell battery using a common conventional NCM ternary material as the positive electrode was also assembled. The cells were then tested for 0.2C capacity (1C ═ 35mA), rate (1C) and cycling performance (0.2C charge-discharge cycles).
The test results are shown in table 1, and table 1 shows the performance comparison data of the modified lithium nickel cobalt manganese oxide ternary material prepared in the embodiment of the invention and the conventional lithium nickel cobalt manganese oxide ternary material.
TABLE 1 comparative data of performance of modified lithium nickel cobalt manganese oxide ternary material prepared by the embodiment of the invention and conventional lithium nickel cobalt manganese oxide ternary material
As can be seen from table 1, the rate performance and cycle performance are improved after the NCM ternary material is coated with carbon. In addition, the capacity is slightly reduced with the increase of the carbon coating amount, but the rate capability and the cycle performance are improved.
The above detailed description of the method for modifying a carbon coating of a nickel cobalt lithium manganate ternary material provided by the present invention, and the specific examples applied herein to illustrate the principles and embodiments of the present invention, are only provided to help understand the method and the core concept of the present invention, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any device or system, and implementing any method in combination. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (4)
1. A method for modifying a nickel cobalt lithium manganate ternary material is characterized by comprising the following steps:
A) carrying out vapor deposition on a nickel cobalt lithium manganate material under the conditions of a carbon source gas and a protective gas to obtain a carbon-coated modified nickel cobalt lithium manganate material;
the carbon-coated modified nickel cobalt lithium manganate material is provided with a carbon coating layer;
a catalyst is not contained between the carbon coating layer of the carbon-coated modified nickel cobalt lithium manganate material and the nickel cobalt lithium manganate material;
the carbon source gas comprises one or more of an alkane, an alkene and an alkyne;
the introduction rate of the carbon source gas is 20-100 m L/min;
the protective gas comprises carbon dioxide, and can also comprise nitrogen and/or inert gas;
the introducing speed of the protective gas is 30-150 m L/min;
the temperature of the vapor deposition is 500-1500 ℃;
the time of vapor deposition is 5-120 min;
the heating rate of the heating process of the vapor deposition is 5-30 ℃/min;
before the vapor deposition, the method also comprises the step of introducing gas to remove air;
the gas comprises nitrogen and/or an inert gas;
the gas is introduced at a rate of 20-100 m L/min;
the gas is introduced for 10-120 min;
the carbon coating amount of the carbon-coated modified nickel cobalt lithium manganate material is 3-10%;
the protective gas comprises carbon dioxide, the carbon dioxide can play a role in catalyzing the surface of the ternary material and can inhibit lithium nickelate in the ternary material from being reduced in the carbon coating process, so that the carbon layer can be coated on the surface of the ternary material, and the carbon dioxide is introduced to play a role in catalyzing the surface of the ternary material and promote the formation of the carbon layer.
2. The modification method of claim 1, wherein the carbon source gas comprises one or more of methane, ethane, ethylene, propylene, and acetylene.
3. The modification method according to claim 1, wherein the lithium nickel cobalt manganese oxide material is a high nickel ternary positive electrode material;
the chemical formula of the high-nickel ternary cathode material is shown as a formula (II),
LiNi1-x-yCoxMnyO2（II）；
wherein, (1-x-y) is not less than 0.5, x is more than 0, and y is more than 0.
4. A lithium ion battery, characterized in that the positive electrode of the lithium ion battery comprises the modified nickel cobalt lithium manganate material prepared by the modification method of any one of claims 1 to 3.
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| CN108258226B (en) * | 2018-01-25 | 2020-04-07 | 深圳市德方纳米科技股份有限公司 | Carbon-coated ternary cathode material and preparation method thereof |
| CN108493406B (en) * | 2018-02-28 | 2020-09-15 | 中航锂电（洛阳）有限公司 | Application of high-nickel ternary cathode material as catalyst in preparation of carbon nanotube, cathode material and preparation method thereof, and lithium battery |
| CN108550810B (en) * | 2018-04-12 | 2020-06-12 | 合肥国轩高科动力能源有限公司 | Preparation method of cerium-doped and carbon-coated modified ternary positive electrode material |
| CN108598448A (en) * | 2018-06-27 | 2018-09-28 | 合肥工业大学 | A kind of three-dimensional structure carbon coating cobalt acid manganese nano-material and preparation method and application |
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| CN108963239B (en) * | 2018-08-14 | 2020-06-30 | 上海力信能源科技有限责任公司 | Preparation method of titanium dioxide coated nickel cobalt lithium manganate positive electrode material |
| CN110137483B (en) * | 2019-06-18 | 2022-03-22 | 贵州梅岭电源有限公司 | Nickel cobalt lithium manganate composite material and preparation method and application thereof |
| CN113044893A (en) * | 2021-03-12 | 2021-06-29 | 电子科技大学 | Method for carrying out carbon coating modification on high-nickel ternary material |
| CN113346081A (en) * | 2021-05-27 | 2021-09-03 | 南京市永信合智能科技有限公司 | Method for preparing carbon-coated ternary cathode nano material by alkyne oxidation |
| CN114988492B (en) * | 2022-05-31 | 2024-05-10 | 西安合升汇力新材料有限公司 | Nickel-rich ternary positive electrode material and preparation method and application thereof |
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