CN107706397B - Nickel-cobalt-manganese ternary composite electrode material modified by modified carbon nano tube and preparation method thereof - Google Patents
Nickel-cobalt-manganese ternary composite electrode material modified by modified carbon nano tube and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a nickel-cobalt-manganese ternary composite electrode material modified based on a modified nanotube, which is prepared from a modified carbon nanotube and a precursor; the modified carbon nano tube comprises one or two of a nitrogen modified carbon nano tube or a boron modified carbon nano tube; the modified carbon nano tube accounts for 1-10% of the mass of the composite electrode material; the precursor comprises lithium carbonate and nickel cobalt manganese, and the molar ratio of lithium element to nickel cobalt manganese in the lithium carbonate is 1.0-1.05: 1. The invention also provides a preparation method of the composite electrode material. The invention can solve the problems of low electronic conductivity, poor rate stability, poor high-voltage cycling stability and the like.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a preparation method of a nickel-cobalt-manganese ternary cathode material modified based on a modified nanotube.
Background
The ternary lithium ion battery anode material is a novel lithium ion battery anode material developed in recent years, and has the advantages of moderate cost, high capacity, high cycle stability and the like. Compared with lithium cobaltate materials, the ternary material has the advantages of reducing production cost, improving safety performance, having higher stability compared with lithium manganate materials, gradually showing the position in the anode material, and being a favorable competitor in the fields of electric vehicles and power batteries in the future.
Compared with lithium cobaltate, the ternary material also has some problems which need to be solved urgently, mainly comprise low electronic conductivity, poor rate stability, poor high-voltage cycle stability and the like, and the problems need to be solved for realizing large-scale production of the ternary material.
Disclosure of Invention
The invention aims to provide a nickel-cobalt-manganese ternary composite electrode material modified by a synthetic modified carbon nano tube and a preparation method thereof.
The invention adopts the following technical scheme:
a nickel-cobalt-manganese ternary composite electrode material modified by a modified nanotube is prepared from a modified carbon nanotube and a precursor; the modified carbon nano tube comprises one or two of a nitrogen modified carbon nano tube and a boron modified carbon nano tube; the modified carbon nano tube accounts for 1-10% of the mass of the composite electrode material; the precursor comprises lithium carbonate and nickel cobalt manganese, and the molar ratio of lithium element to nickel cobalt manganese in the lithium carbonate is 1.0-1.05: 1.
Furthermore, the modified carbon nano tube accounts for 1-5% of the mass of the composite electrode material.
More preferably, the modified carbon nano tube accounts for 5% of the mass of the composite electrode material.
Further, the nickel-cobalt-manganese ternary composite electrode material is α -NaFeO2A layered structure.
Further, the modified carbon nanotube is a nitrogen-modified carbon nanotube; the nitrogen source of the nitrogen modified carbon nano tube is melamine; the mass ratio of the nitrogen element in the melamine to the carbon nano tube is as follows: 0.04-0.06: 0.94-0.96.
Further, the modified carbon nanotube is a boron modified carbon nanotube; the boron source of the boron modified carbon nano tube is boric acid; the mass ratio of boron element to carbon nano tube in the boric acid is as follows: 0.04-0.06: 0.94-0.96.
Further, the modified carbon nanotube is a nitrogen-modified carbon nanotube and a boron-modified carbon nanotube; the nitrogen source of the nitrogen modified carbon nano tube is melamine; the boron source of the boron modified carbon nano tube is boric acid; the mass ratio of the nitrogen element in the melamine to the boron element in the boric acid to the carbon nano tube is as follows: 0.02-0.03: 0.94-0.96.
The preparation method of the nickel-cobalt-manganese ternary composite electrode material comprises the following steps:
(1) mixing carbon nano tubes, melamine and/or boric acid according to a mass ratio, carrying out ball milling to obtain a modified carbon nano tube precursor, and roasting the modified carbon nano tube precursor in a nitrogen atmosphere at the roasting temperature of 400-600 ℃ for 4-8h to obtain the modified carbon nano tubes;
(2) mixing lithium carbonate and nickel-cobalt-manganese material precursors in proportion, and adding the mixture into absolute ethyl alcohol for dispersion; preferably, the molar ratio of the lithium element to the nickel, cobalt and manganese in the lithium carbonate is 1.02: 1;
(3) weighing the modified carbon nanotubes according to the proportion of the modified carbon nanotubes in the anode material, placing the weighed modified carbon nanotubes in the ethanol obtained in the step (2), and fully dispersing and ball-milling to obtain a suspension;
(4) putting the suspension obtained in the step (3) in an oven to evaporate water to obtain a dry precursor;
(5) and (4) sintering the dried precursor in the step (4) in a nitrogen atmosphere box furnace at the sintering temperature of 700-900 ℃ for 12-24h to obtain the modified carbon nanotube modified nickel-cobalt-manganese ternary composite electrode material.
In the preparation method, the concentration of the ethanol in the step (2) is 99.5%.
In the preparation method, the ball milling time in the step (3) is 4-6 hours.
Preferably, the ball milling time in the step (3) is 4 hours.
In the preparation method, the drying condition in the step (4) is 60-80 ℃ and the time is 8-14 hours.
Preferably, the drying condition in the step (4) is a temperature of 70 ℃ for 12 hours.
Preferably, in the step (5), sintering is carried out in a box furnace in a nitrogen atmosphere, wherein the sintering temperature is 800 ℃, the sintering time is 12 hours, the heating rate is 3-8 ℃/min, and the preferred heating rate is 5 ℃/min.
In the preparation method, the molar ratio of the lithium element in the lithium carbonate in the step (2) to the nickel, cobalt and manganese is more than 1; preferably 1.01-1.05: 1.
In the preparation method, the content of nitrogen and boron in the composite electrode material in the step (3) is determined by the mass percentage of the modified carbon nanotube in the composite electrode material.
The invention has the beneficial effects that:
(1) compared with the existing synthesis method of the modified carbon nanotube, the synthesis process is more or less complicated, the reaction time is long, and even the use of strong acid is involved, so that the method is greatly limited in practical application. The modified carbon nano tube synthesized by the method takes melamine, boric acid and carbon nano tubes as raw materials, adopts ball milling and roasting methods, has simple synthesis process, greatly improves synthesis efficiency, has nontoxic and harmless raw materials, is green and environment-friendly, and is easy to realize industrialization.
(2) The electrode material is synthesized by a preparation method combining ball milling mixing and high-temperature sintering processes, the process is simple and convenient, the cost is low, and the method is suitable for large-scale production.
(3) The electrode material modified by the modified carbon nano tube can obviously improve the conductivity of the electrode material and improve the rate capability and the cycling stability of the electrode material.
(4) For those skilled in the art, although increasing the amount of the modified carbon nanotubes can increase the conductivity of the material and increase the electron transfer rate in the electrode material, the inventors found in the research process that too much modification of the modified carbon nanotubes can also impair the electrochemical performance to some extent, and therefore, the mass ratio of the modified carbon nanotubes (nitrogen and boron) in the composite electrode material is 1% to 10%, preferably 1% to 5%, and more preferably 5%.
(5) The modified carbon nano tube is one or the combination of two elements, and the doping of non-metal elements is mainly considered to increase the surface defects of the carbon nano tube, so that the conductivity of the electrode material can be improved, and the aim of improving the stability and the cycle performance of the material is fulfilled.
Detailed Description
The present invention will now be described and illustrated in detail by way of examples.
Comparative example 1
Weighing 9.22g of nickel-cobalt-manganese precursor and 3.8g of lithium carbonate, putting the nickel-cobalt-manganese precursor and the lithium carbonate into a ball milling tank, adding 50 ml of absolute ethyl alcohol, fully dispersing, ball milling for 4 hours to obtain a uniformly dispersed solution, and drying the solution in a 70 ℃ drying oven to obtain the dried nickel-cobalt-manganese composite electrode material precursor. Placing the precursor in a box furnace, calcining for 12 hours at 800 ℃, and heating at a rate of 5 ℃/min to obtain the unmodified nickel-cobalt-manganese electrode material, wherein the first discharge specific capacity reaches 120mAh/g under 1C discharge rate, and the capacity retention rate is 70% after 100 cycles.
Comparative example 2
9.22g of nickel-cobalt-manganese precursor and 3.8g of lithium carbonate are weighed and placed in a ball mill pot, 50 ml of absolute ethyl alcohol is added, and then 0.651g of carbon nano tubes are added into the suspension. And fully dispersing the solution, performing ball milling for 4 hours to obtain a uniformly dispersed solution, and drying the solution in a 70 ℃ drying oven to obtain a dried carbon nanotube modified nickel-cobalt-manganese composite electrode material precursor. And (3) placing the precursor in a box-type furnace, calcining at 800 ℃ for 12 hours in a nitrogen atmosphere, and heating at a rate of 5 ℃/min to prepare the modified nickel-cobalt-manganese composite electrode material with the carbon nano tube mass percentage of 5%. The composite electrode material is assembled into a button cell for charge and discharge tests, the first specific discharge capacity reaches 131mAh/g under the discharge rate of 1C, and the capacity retention rate is 78% after 100 cycles.
Example 1
Weighing 1g of carbon nano tube and 0.075g of melamine, putting the carbon nano tube and the melamine into a ball milling tank, carrying out ball milling for 4 hours, then placing the mixture into a box type furnace protected by nitrogen atmosphere, and roasting for 6 hours at 500 ℃ to obtain the nitrogen modified carbon nano tube. Then 9.22g of nickel-cobalt-manganese precursor and 3.8g of lithium carbonate are weighed and placed in a ball mill pot, 50 ml of absolute ethyl alcohol is added, and then 0.651g of nitrogen modified carbon nano-tube is added into the suspension. And fully dispersing the solution, performing ball milling for 4 hours to obtain a uniformly dispersed solution, and drying the solution in an oven at 70 ℃ for 12 hours to obtain a dried nitrogen-modified carbon nanotube-modified nickel-cobalt-manganese composite electrode material precursor. And (3) placing the precursor in a box-type furnace, calcining at 800 ℃ for 12 hours in a nitrogen atmosphere, and heating at a rate of 5 ℃/min to prepare the modified nickel-cobalt-manganese composite electrode material with the nitrogen-modified carbon nano tube mass percentage of 5%. The composite electrode material is assembled into a button cell for charge and discharge tests, the first specific discharge capacity reaches 140mAh/g under the discharge rate of 1C, and the capacity retention rate is 83% after 100 cycles.
Example 2
Weighing 1g of carbon nano tube and 0.06g of melamine, putting the carbon nano tube and the melamine into a ball milling tank, carrying out ball milling for 4 hours, then putting the mixture into a box type furnace protected by nitrogen atmosphere, and roasting for 4 hours at 400 ℃ to obtain the nitrogen modified carbon nano tube. Then 9.22g of nickel-cobalt-manganese precursor and 3.88g of lithium carbonate are weighed and placed in a ball mill pot, 50 ml of absolute ethyl alcohol is added, and then 0.131g of nitrogen modified carbon nano tube is added into the suspension. And fully dispersing the solution, performing ball milling for 5 hours to obtain a uniformly dispersed solution, and drying the solution in an oven at 60 ℃ for 14 hours to obtain a dry nitrogen-modified carbon nanotube-modified nickel-cobalt-manganese composite electrode material precursor. And (3) placing the precursor in a box-type furnace, calcining for 24 hours at 700 ℃ in the nitrogen atmosphere, and heating at the rate of 4 ℃/min to prepare the modified nickel-cobalt-manganese composite electrode material with the nitrogen-modified carbon nano tube mass percentage of 1%. The composite electrode material is assembled into a button cell for charge and discharge tests, the first discharge specific capacity reaches 139mAh/g under 1C discharge rate, and the capacity retention rate is 82% after 100 cycles.
Example 3
Weighing 1g of carbon nanotube and 0.2862g of boric acid, putting the carbon nanotube and the boric acid into a ball milling tank, ball milling for 4 hours, then placing the mixture into a box type furnace protected by nitrogen atmosphere, and roasting for 6 hours at 500 ℃ to obtain the boron modified carbon nanotube. Then 9.22g of nickel-cobalt-manganese precursor and 3.8g of lithium carbonate are weighed and placed in a ball mill, 50 ml of absolute ethyl alcohol is added, and then 0.651g of boron modified carbon nano tube is added into the suspension. And fully dispersing the solution, performing ball milling for 4 hours to obtain a uniformly dispersed solution, and drying the solution in a 70 ℃ drying oven to obtain a dried boron modified carbon nanotube modified nickel-cobalt-manganese composite electrode material precursor. And (3) placing the precursor in a box-type furnace, calcining at 800 ℃ for 12 hours in a nitrogen atmosphere, and heating at a rate of 5 ℃/min to prepare the modified nickel-cobalt-manganese composite electrode material with the boron modified carbon nanotube mass percentage of 5%. The composite electrode material is assembled into a button cell for charge and discharge tests, the first discharge specific capacity reaches 144mAh/g under the discharge rate of 1C, and the capacity retention rate is 85% after 100 cycles.
Example 4
Weighing 1g of carbon nanotube and 0.3429g of boric acid, putting the carbon nanotube and the boric acid into a ball milling tank, ball milling for 4 hours, then placing the mixture into a box type furnace protected by nitrogen atmosphere, and roasting for 8 hours at 600 ℃ to obtain the boron modified carbon nanotube. Then 9.22g of nickel-cobalt-manganese precursor and 3.73g of lithium carbonate are weighed and placed in a ball mill pot, 50 ml of absolute ethyl alcohol is added, and then 1.295g of boron modified carbon nano tube is added into the suspension. And fully dispersing the solution, performing ball milling for 6 hours to obtain a uniformly dispersed solution, and drying the solution in an oven at 80 ℃ for 8 hours to obtain a dried boron modified carbon nanotube modified nickel-cobalt-manganese composite electrode material precursor. And (3) placing the precursor in a box-type furnace, calcining at 900 ℃ for 18 hours in a nitrogen atmosphere, and heating at the rate of 6 ℃/min to prepare the modified nickel-cobalt-manganese composite electrode material with the boron modified carbon nano tube mass percentage of 10%. The composite electrode material is assembled into a button cell for charge and discharge tests, the first specific discharge capacity reaches 153mAh/g under the discharge rate of 1C, and the capacity retention rate is 86% after 100 cycles.
Example 5
Weighing 1g of carbon nano tube, 0.1431g of boric acid and 0.0375g of melamine, putting the carbon nano tube, 0.1431g of boric acid and 0.0375g of melamine into a ball milling tank, ball milling for 4 hours, then placing the mixture into a box type furnace protected by nitrogen atmosphere, and roasting for 6 hours at 500 ℃ to obtain the boron-nitrogen modified carbon nano tube. Then 9.22g of nickel-cobalt-manganese precursor and 3.8g of lithium carbonate are weighed and placed in a ball mill pot, 50 ml of absolute ethyl alcohol is added, and 0.3906g of boron-nitrogen modified carbon nano-tube is added into the suspension. And fully dispersing the solution, performing ball milling for 4 hours to obtain a uniformly dispersed solution, and drying the solution in a 70 ℃ drying oven to obtain a dry boron-nitrogen modified carbon nanotube modified nickel-cobalt-manganese composite electrode material precursor. And (3) placing the precursor in a box-type furnace, calcining at 800 ℃ for 12 hours in a nitrogen atmosphere, and heating at a rate of 5 ℃/min to prepare the modified nickel-cobalt-manganese composite electrode material with the boron-nitrogen modified carbon nano tube mass percentage of 3%. The composite electrode material is assembled into a button cell for charge and discharge tests, the first specific discharge capacity reaches 151mAh/g under the discharge rate of 1C, and the capacity retention rate is 89% after 100 cycles.
Example 6
Weighing 1g of carbon nano tube, 0.1431g of boric acid and 0.0375g of melamine, putting the carbon nano tube, 0.1431g of boric acid and 0.0375g of melamine into a ball milling tank, ball milling for 4 hours, then placing the mixture into a box type furnace protected by nitrogen atmosphere, and roasting for 6 hours at 500 ℃ to obtain the boron-nitrogen modified carbon nano tube. Then 9.22g of nickel-cobalt-manganese precursor and 3.8g of lithium carbonate are weighed and placed in a ball mill, 50 ml of absolute ethyl alcohol is added, and then 0.651g of boron-nitrogen modified carbon nano tube is added into the suspension. And fully dispersing the solution, performing ball milling for 4 hours to obtain a uniformly dispersed solution, and drying the solution in a 70 ℃ drying oven to obtain a dry boron-nitrogen modified carbon nanotube modified nickel-cobalt-manganese composite electrode material precursor. And (3) placing the precursor in a box-type furnace, calcining at 800 ℃ for 12 hours in a nitrogen atmosphere, and heating at a rate of 5 ℃/min to prepare the modified nickel-cobalt-manganese composite electrode material with the boron-nitrogen modified carbon nano tube mass percentage of 5%. The composite electrode material is assembled into a button cell for charge and discharge tests, the first discharge specific capacity reaches 165mAh/g under 1C discharge rate, and the capacity retention rate is 94% after 100 cycles.
Example 7
Weighing 1g of carbon nano tube, 0.1143g of boric acid and 0.0300g of melamine, putting the carbon nano tube, ball-milling the carbon nano tube in a ball-milling tank for 4 hours, then putting the mixture in a box-type furnace protected by nitrogen atmosphere, and roasting the mixture for 6 hours at 500 ℃ to obtain the boron-nitrogen modified carbon nano tube. Then 9.22g of nickel-cobalt-manganese precursor and 3.8g of lithium carbonate are weighed and placed in a ball mill, 50 ml of absolute ethyl alcohol is added, and then 0.651g of boron-nitrogen modified carbon nano tube is added into the suspension. And fully dispersing the solution, performing ball milling for 4 hours to obtain a uniformly dispersed solution, and drying the solution in a 70 ℃ drying oven to obtain a dry boron-nitrogen modified carbon nanotube modified nickel-cobalt-manganese composite electrode material precursor. And (3) placing the precursor in a box-type furnace, calcining at 800 ℃ for 12 hours in a nitrogen atmosphere, and heating at a rate of 5 ℃/min to prepare the modified nickel-cobalt-manganese composite electrode material with the boron-nitrogen modified carbon nano tube mass percentage of 5%. The composite electrode material is assembled into a button cell for charge and discharge tests, the first specific discharge capacity reaches 160mAh/g under the discharge rate of 1C, and the capacity retention rate is 94% after 100 cycles.
Example 8
Weighing 1g of carbon nano tube, 0.1431g of boric acid and 0.0375g of melamine, putting the carbon nano tube, 0.1431g of boric acid and 0.0375g of melamine into a ball milling tank, ball milling for 4 hours, then placing the mixture into a box type furnace protected by nitrogen atmosphere, and roasting for 6 hours at 500 ℃ to obtain the boron-nitrogen modified carbon nano tube. Then 9.22g of nickel-cobalt-manganese precursor and 3.8g of lithium carbonate are weighed and placed in a ball mill pot, 50 ml of absolute ethyl alcohol is added, and 1.0416g of boron-nitrogen modified carbon nano-tube is added into the suspension. And fully dispersing the solution, performing ball milling for 4 hours to obtain a uniformly dispersed solution, and drying the solution in a 70 ℃ drying oven to obtain a dry boron-nitrogen modified carbon nanotube modified nickel-cobalt-manganese composite electrode material precursor. And (3) placing the precursor in a box-type furnace, calcining at 800 ℃ for 12 hours in a nitrogen atmosphere, and heating at a rate of 5 ℃/min to prepare the modified nickel-cobalt-manganese composite electrode material with the boron-nitrogen modified carbon nano tube mass percentage of 8%. The composite electrode material is assembled into a button cell for charge and discharge tests, the first specific discharge capacity reaches 156mAh/g under 1C discharge rate, and after 100 cycles, the capacity retention rate is 91%.
Example 9
Weighing 1g of carbon nano tube, 0.1714g of boric acid and 0.0450g of melamine, putting the carbon nano tube, the boric acid and the melamine into a ball milling tank, carrying out ball milling for 4 hours, then putting the mixture into a box type furnace protected by nitrogen atmosphere, and roasting for 6 hours at 500 ℃ to obtain the boron-nitrogen modified carbon nano tube. Then 9.22g of nickel-cobalt-manganese precursor and 3.8g of lithium carbonate are weighed and placed in a ball mill, 50 ml of absolute ethyl alcohol is added, and then 0.651g of boron-nitrogen modified carbon nano tube is added into the suspension. And fully dispersing the solution, performing ball milling for 4 hours to obtain a uniformly dispersed solution, and drying the solution in a 70 ℃ drying oven to obtain a dry boron-nitrogen modified carbon nanotube modified nickel-cobalt-manganese composite electrode material precursor. And (3) placing the precursor in a box-type furnace, calcining at 800 ℃ for 12 hours in a nitrogen atmosphere, and heating at a rate of 5 ℃/min to prepare the modified nickel-cobalt-manganese composite electrode material with the boron-nitrogen modified carbon nano tube mass percentage of 5%. The composite electrode material is assembled into a button cell for charge and discharge tests, the first discharge specific capacity reaches 158mAh/g under the discharge rate of 1C, and the capacity retention rate is 93% after 100 cycles.
According to the experimental data, the composite electrode material prepared by using the boron-nitrogen modified carbon nano tube as the surface modification material through the process of combining surface modification and high-temperature sintering has excellent electrochemical performance; under the discharge rate of 1C, the first discharge specific capacity can reach 165mAh/g, and after 100 times of circulation, the capacity retention rate of the composite electrode material is 94%, which is obviously superior to that of an unmodified electrode material (comparative example 1) and an unmodified carbon nanotube modified electrode material (comparative example 2).
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, but not restrictive, and those skilled in the art can easily understand the spirit of the present invention from the above-mentioned embodiments and make various extensions and changes, but they are within the scope of the present invention without departing from the spirit of the present invention.
Claims (6)
1. A nickel-cobalt-manganese ternary composite electrode material modified by a modified nanotube is characterized by being prepared from a modified carbon nanotube and a precursor; the modified carbon nano tube accounts for 5% of the mass of the composite electrode material; the precursor comprises lithium carbonate and a nickel-cobalt-manganese material precursor, and the molar ratio of lithium element in the lithium carbonate to the nickel-cobalt-manganese material precursor is 1.0-1.05: 1;
the modified carbon nano tube is a nitrogen modified carbon nano tube and a boron modified carbon nano tube; the nitrogen source of the nitrogen modified carbon nano tube is melamine; the boron source of the boron modified carbon nano tube is boric acid; the mass ratio of the nitrogen element in the melamine to the boron element in the boric acid to the carbon nano tube is as follows: 0.02-0.03: 0.94-0.96;
the preparation method of the nickel-cobalt-manganese ternary composite electrode material comprises the following steps:
(1) mixing carbon nanotubes, melamine and boric acid according to a mass ratio, ball-milling, and then roasting in a nitrogen atmosphere at the roasting temperature of 400-600 ℃ for 4-8h to obtain modified carbon nanotubes;
(2) mixing lithium carbonate and nickel-cobalt-manganese material precursors in proportion, and adding the mixture into absolute ethyl alcohol for dispersion;
(3) weighing the modified carbon nanotubes according to the proportion of the modified carbon nanotubes in the anode material, placing the weighed modified carbon nanotubes in the ethanol obtained in the step (2), and fully dispersing and ball-milling to obtain a suspension;
(4) putting the suspension obtained in the step (3) in an oven to evaporate water to obtain a dry precursor;
(5) and (4) sintering the dried precursor in the step (4) in a nitrogen atmosphere box furnace at the sintering temperature of 700-900 ℃ for 12-24h to obtain the modified carbon nanotube modified nickel-cobalt-manganese ternary composite electrode material.
2. The nickel-cobalt-manganese ternary composite electrode material according to claim 1, wherein the nickel-cobalt-manganese ternary composite electrode material is α -NaFeO2A layered structure.
3. The nickel-cobalt-manganese ternary composite electrode material according to claim 1, wherein the concentration of ethanol in the step (2) is 99.5%.
4. The nickel-cobalt-manganese ternary composite electrode material according to claim 1, wherein the ball milling time in the step (3) is 4 to 6 hours.
5. The nickel-cobalt-manganese ternary composite electrode material according to claim 1, wherein the drying conditions in step (4) are a temperature of 60 to 80 ℃ and a time of 8 to 14 hours.
6. The nickel-cobalt-manganese ternary composite electrode material according to claim 1, wherein the molar ratio of the lithium element in the lithium carbonate to the nickel-cobalt-manganese material precursor in the step (2) is greater than 1.
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