CN109817939B - Coated positive electrode material, and preparation method and application thereof - Google Patents
Coated positive electrode material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a coated positive electrode material, a preparation method and application thereof, wherein in the coated positive electrode material, the surface of positive electrode material particles is coated with a modified substance, the particles are bridged by the modified substance, and the modified substance is as follows: carbon nanotubes with modified inner surfaces. The method comprises the following steps: 1) dispersing positive electrode material particles, the carbon nano tubes with modified inner surfaces and an organic carbon source in a water-alcohol solution to obtain a suspension; 2) and carrying out microwave treatment on the obtained suspension in a certain atmosphere to obtain the coated positive electrode material. The battery adopting the coated anode material has excellent rate performance, high specific capacity and long cycle life. Moreover, the preparation method is simple and easy to operate, and the problem that the energy consumption is increased due to the fact that high-temperature sintering is needed for coating the carbon material in the prior art is solved.
Description
Technical Field
The invention relates to the technical field of new energy, relates to a positive electrode material, a preparation method and application thereof, and particularly relates to a coated positive electrode material, a preparation method thereof and application thereof in a positive electrode material of a lithium ion battery.
Background
In recent years, the rapid development of global new energy automobiles puts higher demands on the improvement of the energy density and the power density of a lithium ion battery. High nickel series positive electrode materials such as lithium nickel cobalt aluminate, lithium nickel cobalt manganese oxide, lithium nickel manganese oxide or lithium nickel cobalt oxide with high energy density have received wide attention. However, the main problems of the cathode material, especially the high-nickel ternary cathode material, are that the surface alkali content is too high, and the electrolyte is easily oxidized on the surface of the electrode to cause capacity loss. The properties of ternary materials are generally improved by means of coating, doping or surface modification, such as oxide coating, carbon material coating, fluoride coating, organic coating, lithium-containing salt coating, and the like. The surface of the anode material is modified with the carbon material, so that the reaction between the electrode material and electrolyte can be avoided, and the conductivity and other electrochemical properties of the electrode material can be improved.
CN 108199013a discloses a carbon-coated ternary material and a preparation method thereof, wherein the ternary material is combined with a carbon material by means of multiple ball milling to form the carbon-coated ternary material. The heat treatment process under the low-oxygen partial pressure atmosphere is avoided, the ternary material is prevented from being partially reduced, the electrochemical performance damage caused by the ternary material is avoided, the prepared carbon-coated ternary material has good electronic conductivity, the carbon coating can avoid the direct contact of the anode material and the electrolyte, and the rate capability, the cycle performance and the high-temperature storage performance of the anode material are improved. CN 109119628A discloses a co-doped modified high-nickel ternary positive electrode material and a preparation method thereof, and the chemical general formula is LiNixCoyMnzM1 aM2 bO2+d，M1Is one of alkali metal elements Li, Na or K; m2Is one of non-metal elements B, P, Si or S. The preparation method comprises mixing ternary precursor powder with lithium-containing compound and M1And compounds containing M2The compound is mixed at the temperature of 1 and is kept warm for a period of time, and the temperature is continuously raised to the temperature of 2 and kept warm, so that M and M' ions are uniformly diffused into the material, and the co-doped modified high-nickel ternary material is obtained. The high-nickel ternary material is codoped and modified to form Ni2+With Li+Low degree of mixed arrangement, increased interlayer spacing, stable structure, and excellent electrochemical activity, rate capability and cycling stability.
However, the above studies cannot solve the problems of storage property, electron conductivity, cycle stability and thermal stability of the positive electrode material.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to a coated cathode material, a method for preparing the same, and applications of the coated cathode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a coated cathode material, wherein a modified substance is coated on the surface of cathode material particles, the particles are bridged by the modified substance, and the modified substance is a carbon nanotube with a modified inner surface.
As a preferred technical solution of the coated cathode material of the present invention, the inner surface modified carbon nanotube is: the carbon nanotubes with metal oxides distributed on the inner surface are preferably ordered carbon nanotubes with metal oxides uniformly distributed on the inner surface.
Illustratively, the ordered carbon nanotubes having a metal oxide uniformly distributed on the inner surface can be prepared by the following method:
(1) dipping an anodic alumina template in a carbon-containing polymer solution, and after solid-liquid separation, sequentially cleaning, drying and thermally treating the template to obtain an ordered carbon nanotube containing the template;
(2) and (2) dropwise adding the sol containing the metal M element into the ordered carbon nano tube containing the template obtained in the step (1) for aging treatment, removing the template in the obtained product by using an alkaline solution after the aging treatment is finished, and then carrying out heat treatment to obtain the ordered carbon nano tube with the inner surface uniformly distributed with the metal oxide.
Preferably, in the carbon nanotube having the inner surface distributed with the metal oxide, the metal oxide is any one or a combination of at least two of oxides of Al, Mn, Ti, Ni, Co, Zr, Zn, Fe, Mg, Nb, V, Ru, W or Cr, and typical but non-limiting examples of the combination are: a combination of Al oxide and Ti oxide, Al oxide, Ni oxide, Mg oxide and Ti oxide, Co oxide, Fe oxide, V oxide and Cr oxide, Zr oxide, Zn oxide, W oxide and Cr oxide, and the like.
Preferably, in the carbon nanotube with metal oxide distributed on the inner surface, the mass percentage content of the metal oxide is 0.01% to 5%, for example, 0.01%, 0.03%, 0.05%, 0.1%, 0.15%, 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, or 5%, etc., preferably 0.1% to 3%.
Preferably, in the carbon nanotubes with the metal oxide distributed on the inner surface, the length-diameter ratio of the carbon nanotubes is (20-200):1, such as 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 100:1, 120:1, 130:1, 150:1, 170:1, 180:1 or 200: 1.
As a preferred technical solution of the coated cathode material of the present invention, a nanomaterial is further deposited on the outer surface of the inner surface-modified carbon nanotube, and the nanomaterial may include a nanopowder, a nanorod, a nanowire, a nanosheet, or a combination of any 2 or more morphologies.
Preferably, the mass ratio of the inner surface modified carbon nanotube to the nanomaterial is 100 (0.01-30), for example 100:0.01, 100:0.05, 100:0.1, 100:0.2, 100:0.3, 100:0.5, 100:0.8, 100:1, 100:3, 100:5, 100:10, 100:13, 100:15, 100:18, 100:20, 100:22, 100:24, 100:27, or 100:30, etc., preferably 100 (0.05-20), and more preferably 100 (0.05-0.5).
Preferably, the nanomaterial is a mixture of any one or at least two of nano cerium oxide, nano vanadium oxide, nano lanthanum oxide or nano molybdenum oxide, and the mixture is typically but not limited to: the nano-cerium oxide/nano-vanadium oxide mixture, the nano-cerium oxide/nano-lanthanum oxide/nano-molybdenum oxide mixture and the like. The nano cerium oxide or the nano molybdenum oxide is preferably any one or a mixture of the nano cerium oxide and the nano molybdenum oxide, and the nano cerium oxide is more preferably.
Preferably, the nanomaterial has a median particle size of 10nm to 150nm, such as 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 55nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 150nm, or the like, preferably 20nm to 100nm, and more preferably 35 nm.
Preferably, the positive electrode material is: any one or a mixture of at least two of lithium nickel cobalt aluminate, lithium nickel manganese oxide and lithium nickel cobalt oxide, preferably any one or a mixture of at least two of lithium nickel cobalt aluminate, lithium nickel cobalt aluminate and lithium nickel cobalt, and more preferably lithium nickel cobalt manganate.
Preferably, the positive electrode material is a high nickel positive electrode material, preferably a high nickel positive electrode material and/or a doped high nickel positive electrode material having a coating layer on the surface, more preferably a high nickel positive electrode material having a coating layer on the surface, and particularly preferably a high nickel positive electrode material having an oxide coating layer on the surface.
Preferably, in the high-nickel cathode material with the oxide coating layer on the surface, the composition of the oxide coating layer is as follows: any one or a mixture of at least two of cerium oxide, vanadium oxide, lanthanum oxide or molybdenum oxide, typical but non-limiting examples of which are: mixtures of cerium oxide and vanadium oxide, mixtures of cerium oxide and molybdenum oxide, mixtures of vanadium oxide, lanthanum oxide, or molybdenum oxide, and the like. Preferably, the metal oxide is cerium oxide or molybdenum oxide, or a mixture of both, and more preferably cerium oxide.
Preferably, in the high nickel cathode material having an oxide coating layer on the surface, the thickness of the oxide coating layer is 30nm to 200nm, such as 30nm, 40nm, 50nm, 60nm, 70nm, 85nm, 100nm, 120nm, 140nm, 160nm, 180nm or 200nm, and preferably 30nm to 100 nm. The proper thickness of the coating layer can improve the ionic conductivity, specific capacity and cycling stability of the cathode material.
Preferably, the doping element in the doped high nickel cathode material is any one or a mixture of at least two of sodium, aluminum, magnesium, titanium, vanadium or fluorine, and the mixture is typically but not limited to: mixtures of sodium and aluminum, mixtures of sodium and magnesium, mixtures of sodium and titanium, mixtures of aluminum, titanium and vanadium, and the like. Preferably any one or a mixture of at least two of aluminum, magnesium, titanium, or fluorine, and more preferably aluminum.
As a further preferable technical solution of the coated cathode material of the present invention, a nanomaterial is deposited on the outer surface of the inner surface modified carbon nanotube, the high nickel cathode material is a high nickel cathode material having an oxide coating layer on the surface, and the nanomaterial and the oxide coating layer have the same chemical composition.
In a second aspect, the present invention provides a method for preparing the coated cathode material according to the first aspect, the method comprising the steps of:
(1) dispersing the anode material, the inner surface modified carbon nano tube and the organic carbon source in a water-alcohol solution to obtain a suspension;
(2) and carrying out microwave treatment on the obtained suspension in a certain atmosphere to obtain the coated positive electrode material.
The dispersion in step (1) of the present invention is a uniform dispersion, and the dispersion is not limited to any vessel, and may be carried out, for example, in a reaction vessel.
In the method of the present invention, in the step (1), the mass ratio of the particles of the positive electrode material to the carbon nanotube material having the modified inner surface is 100 (0.01 to 10), for example, 100:0.01, 100:0.05, 100:0.1, 100:0.3, 100:0.5, 100:0.8, 100:1, 100:2.5, 100:5, 100:6, 100:7, 100:8, 100:9, or 100:10, preferably 100 (0.25 to 5), and more preferably 100: 0.2.
Preferably, in step (1), the cathode material is a high-nickel cathode material, preferably a high-nickel cathode material and/or a doped high-nickel cathode material with a coating layer on the surface, more preferably a high-nickel cathode material with a coating layer on the surface, and particularly preferably a high-nickel cathode material with an oxide coating layer on the surface.
Preferably, in step (1), the carbon nanotubes with metal oxides distributed on the inner surface are: the ordered carbon nanotube with metal oxide is distributed homogeneously in the inner surface.
Preferably, the dispersion in step (1) is any one of ultrasonic dispersion, mechanical stirring or spray dispersion or a mixture of at least two of the ultrasonic dispersion, the mechanical stirring and the spray dispersion.
Preferably, the method further comprises the step of depositing a nanomaterial on the outer surface of the inner surface-modified carbon nanotube before using the inner surface-modified carbon nanotube, wherein the deposition method comprises any one of vapor deposition, liquid deposition or electrochemical deposition or a mixture of at least two of the vapor deposition, the liquid deposition or the electrochemical deposition, and further preferably the liquid deposition.
Preferably, the hydroalcoholic solution of step (1) is: an aqueous solution of any one or a mixture of at least two of ethanol, methanol, ethylene glycol, glycerol or isopropanol.
Preferably, in the hydroalcoholic solution of step (1), the volume ratio of alcohol to water is (0.1-0.5: 1), such as 0.1:1, 0.2:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, or 0.5:1, etc.
Preferably, the organic carbon source in step (1) is any one or a combination of two or more of citric acid, sucrose, glucose, succinic acid, lactic acid and acetic acid.
Preferably, the mass concentration of the organic carbon source in the hydroalcoholic solution in the step (1) is 0.01% -3%, such as 0.01%, 0.05%, 0.1%, 0.3%, 0.6%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, etc.
Preferably, the mass ratio of the cathode material to the organic carbon source in the step (1) is (100: 800):1, such as 100:1, 200:1, 300:1, 400:1, 450:1, 500:1, 600:1, 700:1 or 800:1, etc.
Preferably, the certain atmosphere in step (2) is an air atmosphere or an oxygen atmosphere.
Preferably, the microwave power of the microwave treatment in step (2) is 500W-3000W, such as 500W, 600W, 750W, 850W, 1000W, 1100W, 1300W, 1500W, 1600W, 1800W, 2000W, 2200W, 2500W, 2750W or 3000W, etc.
Preferably, the microwave treatment time in step (2) is 10min-100min, such as 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min or 100 min.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) depositing cerium oxide with the median particle size of 10nm-200nm on the outer surface of an ordered carbon nanotube with metal oxide uniformly distributed on the inner surface to obtain a modified substance, wherein the mass ratio of the ordered carbon nanotube to the cerium oxide is 100 (0.01-30);
(2) adding a coated high-nickel anode material, a modified substance and an organic carbon source into a reaction kettle, wherein the mass ratio of the coated high-nickel anode material to the modified substance is 100 (0.01-10), and ultrasonically dispersing the modified substance between the coated high-nickel anode materials by taking a water-alcohol mixture as a solvent;
the coated high-nickel anode material comprises the following components: the surface of the high-nickel anode material is provided with a cerium oxide coating layer, and the thickness of the cerium oxide coating layer is 30nm-200 nm;
(3) and (3) treating the suspension obtained in the step (2) for 10min-100min by using microwaves with the power of 500W-3000W in the air atmosphere or the oxygen atmosphere to obtain the coated cathode material.
In a third aspect, the present invention provides a positive electrode comprising the coated positive electrode material according to the first aspect.
In a fourth aspect, the present invention provides a lithium ion battery comprising the coated cathode material according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the coated anode material is prepared by coating the anode material particles with the carbon nano tubes with modified inner surfaces and realizing bridging among the particles, so that the cycle stability, rate capability, storage capability, thermal stability and coulombic efficiency of the anode material can be improved, and a battery adopting the coated anode material has excellent rate capability, high specific capacity, long cycle life and thermal stability.
(2) The method is simple and easy to operate, solves the problem that the energy consumption is increased due to the fact that high-temperature sintering is needed for coating the carbon material in the prior art, and meanwhile, the high-power microwave treatment method is adopted to enable the grain boundary defect of the ternary material to be passivated after the organic carbon source is cracked, so that the electrochemical performance of the anode material is improved. The method of the invention has better industrial production and application prospect.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a coated cathode material, and a preparation method thereof comprises the following steps:
(1) depositing cerium oxide with the median particle size of 40nm on the outer surface of the ordered carbon nanotube with alumina uniformly distributed on the inner surface to obtain a modified substance, wherein the mass ratio of the ordered carbon nanotube to the cerium oxide is 100: 0.5;
in the ordered carbon nano tube with the alumina uniformly distributed on the inner surface, the mass percentage of the alumina is 0.1 percent, and the length-diameter ratio of the carbon nano tube is 20: 1;
(2) adding a coated high-nickel anode material, a modifying substance and citric acid into a reaction kettle, wherein the mass ratio of the coated high-nickel anode material to the modifying substance is 100:0.2, the mixture of water and ethanol is used as a solvent, the volume ratio of ethanol to water is 0.3:1, the mass concentration of citric acid in the alcohol water is 0.01%, and the mass ratio of the anode material to the citric acid is 100:1, and ultrasonically dispersing the modifying substance between the coated high-nickel anode materials; the coated high-nickel anode material comprises the following components: LiNi with cerium oxide coating layer on surface0.8Co0.1Mn0.1O2The thickness of the cerium oxide coating layer is 50 nm;
(3) and (3) treating the suspension obtained in the step (2) for 15min by using a microwave with the power of 1000W in an air atmosphere to obtain the coated cathode material.
The rate capability 10C/1C of the obtained material is 90%. The specific capacity under the charging and discharging conditions of 0.5C is 178mAh/g, and the capacity retention rate after 100 cycles is 98 percent.
Example 2
The embodiment provides a coated cathode material, and a preparation method thereof comprises the following steps:
(1) depositing molybdenum oxide with the median particle size of 100nm on the outer surface of an ordered carbon nanotube with zinc oxide uniformly distributed on the inner surface to obtain a modified substance, wherein the mass ratio of the ordered carbon nanotube to cerium oxide is 100: 1;
in the ordered carbon nano tube with the zinc oxide uniformly distributed on the inner surface, the mass percentage of the zinc oxide is 0.01 percent, and the length-diameter ratio of the carbon nano tube is 100: 1;
(2) adding a coated high-nickel anode material, a modified substance and sucrose into a reaction kettle, wherein the coated high-nickel anode material and the modified substance areThe mass ratio of the modified substance to the sucrose is 100:2, the mixture of water and ethanol is used as a solvent, the volume ratio of ethanol to water is 0.4:1, the mass concentration of the sucrose in the ethanol water is 0.05%, the mass ratio of the positive electrode material to the sucrose is 300:1, and the modified substance is sprayed and dispersed among the coated high-nickel positive electrode materials; the coated high-nickel anode material comprises the following components: LiNi with molybdenum oxide coating layer on surface0.83Co0.1Al0.07O2The thickness of the cerium oxide coating layer is 100 nm;
(3) and (3) treating the suspension obtained in the step (2) for 80min by using microwaves with the power of 500W in an oxygen atmosphere to obtain the coated cathode material.
The rate capability 10C/1C of the resulting material was 89%. The specific capacity under the charge-discharge condition of 0.5C is 180mAh/g, and the capacity retention rate after 100 cycles is 97%.
Example 3
The embodiment provides a coated cathode material, and a preparation method thereof comprises the following steps:
(1) depositing vanadium oxide with the median particle size of 150nm on the outer surface of an ordered carbon nanotube with chromium oxide uniformly distributed on the inner surface to obtain a modified substance, wherein the mass ratio of the ordered carbon nanotube to cerium oxide is 100: 0.05;
in the ordered carbon nano tube with the inner surface uniformly distributed with the chromium oxide, the mass percentage of the chromium oxide is 0.05 percent, the length-diameter ratio of the carbon nano tube is 300:1, and the mass ratio of the ordered carbon nano tube to the vanadium oxide is 100: 0.2;
(2) adding a coated high-nickel anode material, a modifying substance and succinic acid into a reaction kettle, wherein the mass ratio of the coated high-nickel anode material to the modifying substance is 100:5, the mixture of water and ethanol is used as a solvent, the volume ratio of ethanol to water is 0.3:1, the mass concentration of succinic acid in the alcohol water is 0.05%, and the mass ratio of the anode material to sucrose is 500:1, and mechanically stirring the modifying substance to disperse the modifying substance among the coated high-nickel anode materials; the coated high-nickel anode material comprises the following components: LiNi with vanadium oxide coating on surface0.85Co0.05Mn0.1O2The thickness of the vanadium oxide coating layer is 35 nm;
(3) and (3) treating the suspension obtained in the step (2) for 80min by using a microwave with the power of 500W in an air atmosphere to obtain the coated cathode material.
The rate capability 10C/1C of the obtained material is 92%. The specific capacity under the condition of 0.5C charge and discharge is 182mAh/g, and the capacity retention rate after 100 cycles is 97.5 percent.
Example 4
Except that the coating type high nickel anode material is replaced by the LiNi without the coating layer0.8Co0.1Mn0.1O2Otherwise, the other methods and conditions were the same as in example 1.
Example 5
The method and conditions were the same as in example 1 except that the coating layer of the coated high nickel positive electrode material was replaced with lanthanum oxide.
The rate capability 10C/1C of the obtained material is 85%. The specific capacity under the charge-discharge condition of 0.5C is 162mAh/g, and the capacity retention rate after 100 cycles is 90%.
Example 6
The procedure and conditions were the same as in example 2 except that the solvent in step (2) was adjusted to a mixed solution of alcohol and water in a volume ratio of 0.7: 1.
The rate capability 10C/1C of the resulting material was 86%. The specific capacity under the charge-discharge condition of 0.5C is 177mAh/g, and the capacity retention rate after 100 cycles is 94%.
Example 7
The method and conditions were the same as in example 1 except that the mass ratio of the ordered carbon nanotubes to the cerium oxide was 100: 15. The rate capability 10C/1C of the resulting material was 82%. The specific capacity under the charge-discharge condition of 0.5C is 165mAh/g, and the capacity retention rate after 100 cycles is 96%.
Example 8
Except that the microwave condition is changed into: the method and conditions were the same as in example 1 except that the microwave treatment was carried out at a power of 2000W for 30 min.
The rate capability 10C/1C of the resulting material was 91%. The specific capacity under the charge-discharge condition of 0.5C is 183mAh/g, and the capacity retention rate after 100 cycles is 98.5%.
Comparative example 1
The method and conditions were the same as in example 1 except that the modified substance in step (2) was replaced with a common carbon nanotube.
The rate capability 10C/1C of the resulting material was 75%. The specific capacity under the charge-discharge condition of 0.5C is 150mAh/g, and the capacity retention rate after 100 cycles is 78%.
Comparative example 2
The method and conditions were the same as in example 1 except that the modified substance in step (2) was replaced with the carbon nanotube having the modified outer surface.
The rate capability 10C/1C of the obtained material is 80%. The specific capacity under the charge-discharge condition of 0.5C is 161mAh/g, and the capacity retention rate after 100 cycles is 91%.
Comparative example 3
The method and conditions were the same as in example 1 except that the modified substance in step (2) was replaced with glucose and calcination was performed at 700 ℃ after microwave treatment. The rate capability 10C/1C of the resulting material was 76%. The specific capacity under the charge-discharge condition of 0.5C is 158mAh/g, and the capacity retention rate after 100 cycles is 79%.
Comparative example 4
The procedure and conditions were the same as in example 1 except that the microwave treatment was replaced with oven drying at the same temperature.
The rate capability 10C/1C of the resulting material was 77%. The specific capacity under the charge-discharge condition of 0.5C is 159mAh/g, and the capacity retention rate after 100 cycles is 81.5%.
It can be seen from the above comparative examples 1-4 that the use of ordinary carbon nanotubes, the use of ordinary carbon sources such as glucose, and the like, instead of the ordered carbon nanotubes with oxides distributed on the inner surface, which is used in the present application, in the ordinary carbon nanotubes, does not allow the formation of a three-dimensional conductive network distributed between particles of the positive electrode material and on the particle surface, and thus the purpose of improving the thermal stability, specific capacity, and rate capability of the positive electrode material is not achieved, and a good coating effect cannot be achieved. Compared with the prior art, the method has the advantages that the common drying oven drying treatment is adopted to replace the high-power microwave treatment, the anode material cannot be better prevented from being reduced like microwave pyrolysis, uniform coating cannot be realized, and the coating material cannot generate an efficient electron transmission medium, so that the purpose of passivating the crystal boundary defect of the ternary material cannot be achieved, the rate performance of the material is effectively improved, and the cycle performance of the material is improved.
The applicant states that the present invention is illustrated by the above examples to show the detailed method of the present invention, but the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must rely on the above detailed method to be carried out. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (36)
1. A coated anode material is characterized in that the surface of anode material particles is coated with a modified substance, the particles are bridged by the modified substance, the modified substance is a carbon nano tube with the modified inner surface,
the carbon nano tube with the modified inner surface is as follows: ordered carbon nanotubes with metal oxide uniformly distributed on the inner surface;
the ordered carbon nanotube with metal oxide uniformly distributed on the inner surface is prepared by the following method, and the method comprises the following steps:
(1) dipping an anodic alumina template in a carbon-containing polymer solution, and after solid-liquid separation, sequentially cleaning, drying and thermally treating the template to obtain an ordered carbon nanotube containing the template;
(2) dropwise adding a sol containing a metal M element into the ordered carbon nano tube containing the template obtained in the step (1) for aging treatment, removing the template in the obtained product by using an alkaline solution after the aging treatment is finished, and then carrying out heat treatment to obtain the ordered carbon nano tube with the inner surface uniformly distributed with metal oxides;
in the carbon nano tube with the modified inner surface, the mass percentage content of the metal oxide is 0.01-5%;
the cathode material is a high-nickel cathode material with an oxide coating layer on the surface, wherein the oxide coating layer comprises the following components: the thickness of the oxide coating layer is 30nm-200 nm.
2. The coated positive electrode material according to claim 1, wherein the metal oxide in the inner surface-modified carbon nanotube is any one or a combination of at least two of oxides of Al, Mn, Ti, Ni, Co, Zr, Zn, Fe, Mg, Nb, V, Ru, W, or Cr.
3. The coated cathode material according to claim 1, wherein the metal oxide is contained in the carbon nanotube having the modified inner surface in an amount of 0.1 to 3% by mass.
4. The coated positive electrode material according to claim 1, wherein the inner surface-modified carbon nanotube has an aspect ratio of (20-200): 1.
5. The coated cathode material according to claim 1, wherein the inner surface-modified carbon nanotubes further have a nanomaterial deposited on the outer surface thereof.
6. The coated cathode material according to claim 5, wherein the mass ratio of the inner surface-modified carbon nanotubes to the nanomaterial is 100 (0.01-30).
7. The coated cathode material according to claim 6, wherein the mass ratio of the inner surface-modified carbon nanotubes to the nanomaterial is 100 (0.05-20).
8. The coated cathode material according to claim 7, wherein the mass ratio of the inner surface-modified carbon nanotubes to the nanomaterial is 100 (0.05-0.5).
9. The coated cathode material according to claim 5, wherein the nanomaterial is any one of or a mixture of at least two of nano cerium oxide, nano vanadium oxide, nano lanthanum oxide, and nano molybdenum oxide.
10. The coated positive electrode material according to claim 9, wherein the nanomaterial is a mixture of one or both of nano cerium oxide and nano molybdenum oxide.
11. The coated positive electrode material according to claim 10, wherein the nanomaterial is a nano cerium oxide.
12. The coated positive electrode material of claim 5, wherein the nanomaterial has a median particle size of 10nm to 150 nm.
13. The coated positive electrode material of claim 12, wherein the nanomaterial has a median particle size of 20nm to 100 nm.
14. The coated positive electrode material of claim 13, wherein the nanomaterial has a median particle size of 35 nm.
15. The coated positive electrode material according to claim 1, wherein the composition of the oxide coating layer is cerium oxide.
16. The coated positive electrode material according to claim 1, wherein the thickness of the oxide coating layer in the high nickel positive electrode material having an oxide coating layer on the surface thereof is 30nm to 100 nm.
17. The coated cathode material according to claim 1, wherein a nanomaterial is deposited on the outer surface of the inner surface-modified carbon nanotube, the high-nickel cathode material has an oxide coating layer on the surface, and the nanomaterial and the oxide coating layer have the same chemical composition.
18. The method of preparing the coated positive electrode material according to claim 1, comprising the steps of:
(1) dispersing positive electrode material particles, the carbon nano tubes with modified inner surfaces and an organic carbon source in a water-alcohol solution to obtain a suspension;
(2) performing microwave treatment on the obtained suspension in a certain atmosphere to obtain a coated anode material;
in the step (1), the positive electrode material is a high-nickel positive electrode material with an oxide coating layer on the surface, and the oxide coating layer comprises the following components: any one or a mixture of two of cerium oxide or molybdenum oxide;
the certain atmosphere in the step (2) is air atmosphere or oxygen atmosphere.
19. The method of claim 18, wherein in step (1), the mass ratio of the positive electrode material particles to the inner surface-modified carbon nanotubes is 100 (0.01-10).
20. The method of claim 19, wherein in the step (1), the mass ratio of the positive electrode material particles to the inner surface-modified carbon nanotubes is 100 (0.25-5).
21. The method of claim 20, wherein in step (1), the mass ratio of the positive electrode material particles to the inner surface-modified carbon nanotubes is 100: 0.2.
22. The method of claim 18, wherein in step (1), the interior surface-modified carbon nanotubes are: the ordered carbon nanotube with metal oxide is distributed homogeneously in the inner surface.
23. The method of claim 18, wherein the dispersing in step (1) is any one of ultrasonic dispersing, mechanical stirring or spray dispersing or a mixture of at least two of the foregoing.
24. The method of claim 18, further comprising the step of depositing a nanomaterial on the outer surface of the inner surface-modified carbon nanotubes prior to their use, wherein the method of deposition comprises any one of vapor deposition, liquid deposition, or electrochemical deposition, or a mixture of at least two thereof.
25. The method of claim 24, wherein the deposition is liquid deposition or electrochemical deposition.
26. The method of claim 25, wherein the method of deposition is liquid phase deposition.
27. The method of claim 18, wherein the hydroalcoholic solution of step (1) is: an aqueous solution of any one or a mixture of at least two of ethanol, methanol, ethylene glycol, glycerol or isopropanol.
28. The method of claim 18, wherein the hydroalcoholic solution of step (1) has a volume ratio of alcohol to water of (0.1-0.5) to 1.
29. The method of claim 18, wherein the organic carbon source in step (1) is any one of citric acid, sucrose, glucose, succinic acid, lactic acid or acetic acid or a combination of at least two thereof.
30. The method of claim 18, wherein the organic carbon source of step (1) has a mass concentration of 0.01% to 3% in the hydroalcoholic solution.
31. The method as claimed in claim 18, wherein the mass ratio of the cathode material to the organic carbon source in the step (1) is (100): 800): 1.
32. The method of claim 18, wherein the microwave power of the microwave treatment of step (2) is 500W to 3000W.
33. The method of claim 18, wherein the microwave treatment of step (2) is performed for a time period of 10min to 100 min.
34. The method of claim 18, wherein the method comprises the steps of:
(1) depositing cerium oxide with the median particle size of 10nm-200nm on the outer surface of an ordered carbon nanotube with metal oxide uniformly distributed on the inner surface to obtain a modified substance, wherein the mass ratio of the ordered carbon nanotube to the cerium oxide is 100 (0.01-30);
(2) adding a coated high-nickel anode material, a modified substance and an organic carbon source into a reaction kettle, wherein the mass ratio of the coated high-nickel anode material to the modified substance is 100 (0.01-10), and ultrasonically dispersing the modified substance between the coated high-nickel anode materials by taking a water-alcohol mixture as a solvent;
the coated high-nickel anode material comprises the following components: the surface of the high-nickel anode material is provided with a cerium oxide coating layer, and the thickness of the cerium oxide coating layer is 30nm-200 nm;
(3) and (3) treating the suspension obtained in the step (2) for 10min-100min by using microwaves with the power of 500W-3000W in the air atmosphere or the oxygen atmosphere to obtain the coated cathode material.
35. A positive electrode comprising the coated positive electrode material according to any one of claims 1 to 17.
36. A lithium ion battery comprising the coated positive electrode material according to any one of claims 1 to 17.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105336927A (en) * | 2015-09-28 | 2016-02-17 | 深圳市贝特瑞新能源材料股份有限公司 | Modified super-hydrophobic material-coated lithium ion battery high-nickel cathode material and preparation method thereof |
| CN105390700A (en) * | 2015-11-16 | 2016-03-09 | 哈尔滨工业大学 | Method for modifying positive electrode of lithium ion battery by adding metal oxide/carbon composite material |
| CN107845786A (en) * | 2017-09-27 | 2018-03-27 | 中国科学院过程工程研究所 | A kind of hud typed positive electrode, its preparation method and the purposes in lithium ion battery of composite cladding |
| CN108281622A (en) * | 2017-12-19 | 2018-07-13 | 湖南艾华集团股份有限公司 | A kind of preparation method of the porous composite negative pole material of transition metal oxide/carbon nanotube |
-
2019
- 2019-02-15 CN CN201910118072.9A patent/CN109817939B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105336927A (en) * | 2015-09-28 | 2016-02-17 | 深圳市贝特瑞新能源材料股份有限公司 | Modified super-hydrophobic material-coated lithium ion battery high-nickel cathode material and preparation method thereof |
| CN105390700A (en) * | 2015-11-16 | 2016-03-09 | 哈尔滨工业大学 | Method for modifying positive electrode of lithium ion battery by adding metal oxide/carbon composite material |
| CN107845786A (en) * | 2017-09-27 | 2018-03-27 | 中国科学院过程工程研究所 | A kind of hud typed positive electrode, its preparation method and the purposes in lithium ion battery of composite cladding |
| CN108281622A (en) * | 2017-12-19 | 2018-07-13 | 湖南艾华集团股份有限公司 | A kind of preparation method of the porous composite negative pole material of transition metal oxide/carbon nanotube |
Non-Patent Citations (1)
| Title |
|---|
| "Microwave synthesis of Li3V2(PO4)3/C as positive-electrode materials for rechargeable lithium batteries";Xi Yupeng et al.;《Journal of Alloys and Compounds》;20141213;第628卷;第396-400页 * |
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