CN114804068B - Hard carbon negative electrode material, preparation method thereof and battery containing hard carbon negative electrode material - Google Patents
Hard carbon negative electrode material, preparation method thereof and battery containing hard carbon negative electrode material Download PDFInfo
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of battery materials. The invention provides a hard carbon cathode material and a preparation method thereof, wherein a carbon source is subjected to high-temperature pretreatment in a protective atmosphere to obtain low-purity hard carbon powder; carrying out acid purification on the low-purity hard carbon powder in an acid solution, and then sequentially washing and drying to obtain acid-purified hard carbon powder; carrying out heat treatment on the acid purified hard carbon powder and an organic carbon source to obtain a single-layer coated hard carbon material; and carrying out chemical vapor deposition on the single-layer coated hard carbon material in a vapor carbon source, and then screening to obtain the hard carbon cathode material. The invention also provides a battery comprising the hard carbon anode material. The method solves the problems of large specific surface area and low first coulombic efficiency of the hard carbon cathode material through high-temperature graphitization pretreatment, acid purification and multilayer carbon coating. The battery prepared by the hard carbon negative electrode material has the initial coulombic efficiency of more than 70 percent and the capacity retention rate of more than 94 percent after 100 cycles.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a hard carbon negative electrode material, a preparation method thereof and a battery containing the hard carbon negative electrode material.
Background
The hard carbon is non-graphitizable amorphous carbon, has larger interlayer spacing than the graphite cathode, has good rapid charge and discharge performance, and particularly has excellent low-temperature charge and discharge performance. At present, the precursor for preparing the hard carbon is mainly a high molecular polymer, the wide application of the precursor in the field of lithium ion batteries is limited due to the high cost of the high molecular polymer, and the high molecular polymer generates air holes in the pyrolysis process, so that the specific surface area of the hard carbon is high, the hard carbon is easy to absorb moisture and oxygen, the side reactions are more, the first coulombic efficiency is low, and the service life is short.
In order to solve the problems of high specific surface area and low coulombic efficiency for the first time of hard carbon, a CVD carbon coating method is adopted in patent CN111952565A to modify the surface of the hard carbon, but the specific surface area of a carbon layer coated by the method cannot be obviously reduced, and the carbon layer is difficult to ensure that pores in the hard carbon are uniformly filled. In patent CN108110232B, an electrophoresis process (containing a Li source in a solution) is adopted to process a hard carbon negative electrode material, and a layer of SEI film is formed on the surface of the hard carbon negative electrode material to reduce the occurrence of side reactions during the first charge and discharge process, but the thickness and uniformity of the SEI film formed by the method are difficult to control, and the occurrence of side reactions during the first charge and discharge cannot be well avoided; and redundant lithium sources in the hard carbon material after the electrophoresis treatment are difficult to completely remove, and the stability is not good when slurry is prepared, so that the subsequent processing is not facilitated.
Therefore, the research and development of the hard carbon cathode material which has low cost, reduces the specific surface area of hard carbon, improves the first coulombic efficiency and the cycle stability have important economic value and significance.
Disclosure of Invention
The invention aims to provide a hard carbon negative electrode material, a preparation method thereof and a battery containing the hard carbon negative electrode material aiming at the defects of the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a hard carbon negative electrode material, which comprises the following steps:
1) Carrying out high-temperature pretreatment on a carbon source in a protective atmosphere to obtain low-purity hard carbon powder;
2) Carrying out acid purification on the low-purity hard carbon powder in an acid solution, and then sequentially washing and drying to obtain acid-purified hard carbon powder;
3) Carrying out heat treatment on the acid purified hard carbon powder and an organic carbon source to obtain a single-layer coated hard carbon material;
4) And carrying out chemical vapor deposition on the single-layer coated hard carbon material in a vapor carbon source, and then screening to obtain the hard carbon cathode material.
Preferably, the high-temperature pretreatment in the step 1) is carried out at 1500-2200 ℃ for 8-20 h.
Preferably, the protective atmosphere in the step 1) is nitrogen or argon; the carbon source is waste tires.
Preferably, the acid solution in the step 2) contains one or more of hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid; the mass fraction of the low-purity hard carbon powder in the acid solution is 15-50%.
Preferably, the temperature of the acid purification in the step 2) is 45-90 ℃, and the time is 4-12 h; the drying temperature is 70-90 ℃.
Preferably, the organic carbon source in the step 3) comprises one or more of asphalt, phenolic resin, sucrose and polyethylene glycol; the mass ratio of the acid-purified hard carbon powder to the organic carbon source is 100-11; the temperature of the heat treatment is 950-1500 ℃, and the time is 2-8 h.
Preferably, the gas-phase carbon source in the step 4) comprises one or more of methane, acetylene and ethylene; the temperature of the chemical vapor deposition is 700-1200 ℃, and the time is 3-6 h; the chemical vapor deposition is carried out under a protective atmosphere.
The invention also provides the hard carbon negative electrode material prepared by the preparation method, wherein the median particle diameter D50 of the hard carbon negative electrode material is 5-12 mu m, and the specific surface area is less than or equal to 15m 2 (iv) g; tap density is more than or equal to 0.75g/cm 3 (ii) a The first reversible specific capacity is more than or equal to 530mAh/g, and the first coulombic efficiency is more than or equal to 71 percent.
The invention also provides a battery containing the hard carbon negative electrode material, which comprises the negative electrode material, a lithium sheet and electrolyte; the negative electrode material comprises a hard carbon negative electrode material, polyvinylidene fluoride and SuperP, wherein the mass ratio of the hard carbon negative electrode material to the polyvinylidene fluoride to the SuperP is 90-94.
Preferably, the electrolyte contains LiPF 6 Ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, the LiPF 6 The concentration of (A) is 0.8-1.2 mol/L; the volume ratio of the ethylene carbonate to the dimethyl carbonate to the methyl ethyl carbonate is 0.8-1.2.
The beneficial effects of the invention include the following:
1) The invention takes the waste tires as the carbon source to prepare the hard carbon cathode material of the lithium ion battery, not only provides a low-cost raw material for the production of the hard carbon material, but also provides an effective way for recycling the waste tires.
2) The method solves the problems of large specific surface area and low coulombic efficiency of the hard carbon cathode material for the first time through high-temperature graphitization pretreatment, acid purification and multilayer carbon coating. The reversible capacity of the battery prepared by the hard carbon negative electrode material exceeds 530mAh/g, the first coulombic efficiency is more than 70%, and the capacity retention rate is more than 94% after 100 cycles.
Detailed Description
The invention provides a preparation method of a hard carbon negative electrode material, which comprises the following steps:
1) Carrying out high-temperature pretreatment on a carbon source in a protective atmosphere to obtain low-purity hard carbon powder;
2) Carrying out acid purification on the low-purity hard carbon powder in an acid solution, and then sequentially washing and drying to obtain acid-purified hard carbon powder;
3) Carrying out heat treatment on the acid purified hard carbon powder and an organic carbon source to obtain a single-layer coated hard carbon material;
4) And carrying out chemical vapor deposition on the single-layer coated hard carbon material in a vapor carbon source, and then screening to obtain the hard carbon cathode material.
In the invention, the temperature of the high-temperature pretreatment in the step 1) is preferably 1500-2200 ℃, more preferably 1600-2000 ℃, and more preferably 1800-1900 ℃; the time of the high-temperature pretreatment is preferably 8 to 20 hours, more preferably 10 to 18 hours, and still more preferably 12 to 16 hours.
In the invention, the protective atmosphere in the step 1) is preferably nitrogen or argon; the carbon source is preferably waste tires; the carbon source is subjected to high-temperature pretreatment after crushing, demagnetizing and screening; and cooling the high-temperature pretreatment product to obtain low-purity hard carbon powder.
The high-temperature pretreatment of the invention can remove most of impurities which are easy to crack and volatilize and the like in the carbon source, improve the graphitization degree of the hard carbon material and reduce the specific surface area of the hard carbon material.
In the invention, the acid solution in the step 2) preferably contains one or more of hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid; the acid solution is further preferably a mixed solution of concentrated hydrochloric acid and concentrated nitric acid or hydrofluoric acid; the volume ratio of the concentrated hydrochloric acid to the concentrated nitric acid is preferably 3; the mass concentration of the concentrated hydrochloric acid is preferably 36 to 38%, and more preferably 37%; the mass concentration of the concentrated nitric acid is preferably 65 to 70 percent, and more preferably 66 to 69 percent; the mass concentration of the hydrofluoric acid is preferably 40-60%, and more preferably 50%; the mass concentration of the sulfuric acid is preferably 70 to 98 percent, and more preferably 75 to 90 percent; the mass fraction of the low-purity hard carbon powder in the acid solution is preferably 15 to 50%, more preferably 20 to 45%, and still more preferably 25 to 40%.
In the invention, the temperature for purifying the acid in the step 2) is preferably 45-90 ℃, more preferably 50-85 ℃, and more preferably 55-75 ℃; the time for purifying the acid is preferably 4 to 12 hours, more preferably 6 to 10 hours, and even more preferably 8 to 9 hours; the number of acid purification is preferably 1 to 4 times, and more preferably 2 to 3 times; the drying temperature is preferably 70 to 90 ℃, more preferably 75 to 85 ℃, and still more preferably 80 ℃.
In the invention, the organic carbon source in the step 3) preferably comprises one or more of asphalt, phenolic resin, sucrose and polyethylene glycol; the mass ratio of the acid-purified hard carbon powder to the organic carbon source is preferably 100; the temperature of the heat treatment is preferably 950 to 1500 ℃, more preferably 1000 to 1400 ℃, and even more preferably 1100 to 1300 ℃; the time for the heat treatment is preferably 2 to 8 hours, more preferably 3 to 7 hours, and still more preferably 4 to 6 hours.
In the present invention, the heat treatment of step 3) is preferably performed under an inert atmosphere; after the heat treatment is finished, sequentially cooling, crushing and sieving to obtain a single-layer coated hard carbon material; the single-layer coated hard carbon material is coated in a solid phase.
In the invention, the gas-phase carbon source in the step 4) preferably contains one or more of methane, acetylene and ethylene; the mass ratio of the gas-phase carbon source to the single-layer coated hard carbon material is preferably 2 to 5, more preferably 3 to 4.
In the invention, the temperature of the chemical vapor deposition in the step 4) is preferably 700-1200 ℃, more preferably 800-1000 ℃, and more preferably 850-950 ℃; the time of the chemical vapor deposition is preferably 3 to 6 hours, and more preferably 4 to 5 hours; the chemical vapor deposition is preferably carried out under a protective atmosphere.
The chemical vapor deposition is vapor coating.
The invention also provides the hard carbon cathode material prepared by the preparation method.
In the present invention, the hard carbon negative electrode material has a median particle diameter D50 of 5 to 12 μm, preferably 6 to 11 μm, and more preferably 7 to 10 μm; the specific surface area of the hard carbon negative electrode material is less than or equal to 15m 2 G, preferably ≤ 14m 2 (ii)/g; tap density is more than or equal to 0.75g/cm 3 Preferably ≥ 0.8g/cm 3 (ii) a The first reversible specific capacity is more than or equal to 530mAhPer gram, preferably more than or equal to 550mAh/g; the first coulombic efficiency is more than or equal to 71 percent, preferably more than or equal to 73 percent.
The invention also provides a battery containing the hard carbon cathode material, wherein the battery contains the cathode material, a lithium sheet and electrolyte; the negative electrode material comprises a hard carbon negative electrode material, polyvinylidene fluoride and Super P; the mass ratio of the hard carbon negative electrode material, the polyvinylidene fluoride and the Super P is preferably from 90 to 94.
In the present invention, the electrolyte contains LiPF 6 Ethylene Carbonate (EC), dimethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC), the LiPF 6 The concentration of (B) is preferably 0.8 to 1.2mol/L, and more preferably 1mol/L; the volume ratio of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate is preferably 0.8-1.2.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1) Taking 20kg of waste tire samples, carrying out mechanical crushing, screening and demagnetizing procedures to obtain waste tire particles with the median particle size D50 of 10-20 mu m, transferring the waste tire particles into a graphitization furnace, carrying out pretreatment for 10h at 2000 ℃ under the protection of nitrogen, and naturally cooling the samples after the pretreatment to obtain the low-purity hard carbon powder.
2) Adding low-purity hard carbon powder into newly-prepared aqua regia (the aqua regia is a mixed solution of concentrated hydrochloric acid and concentrated nitric acid with the volume ratio of 3; the mass concentration of concentrated hydrochloric acid is 37 percent, the mass concentration of concentrated nitric acid is 66 percent), the mass fraction of low-purity hard carbon powder in aqua regia is 25 percent, the hard carbon powder is stirred and acid-purified for 8 hours at 80 ℃, the hard carbon powder after the aqua regia is acid-washed is washed to be neutral by deionized water, the hard carbon powder is dried in an oven at 85 ℃, a dried product is added into hydrofluoric acid with the mass concentration of 50 percent, the mass fraction of the hard carbon powder in the hydrofluoric acid is 25 percent, the hard carbon powder is stirred and acid-purified for 2 hours at 80 ℃, the hard carbon powder is washed to be neutral by deionized water, and the hard carbon powder is dried in the oven at 85 ℃ to obtain the acid-purified hard carbon powder.
3) Uniformly mixing 2000g of acid purified hard carbon powder and 170g of asphalt, putting the mixture into a box furnace, carrying out heat treatment for 4 hours at 1050 ℃ under the protection of nitrogen, cooling, grinding and sieving to obtain a solid-phase carbon-coated hard carbon material;
4) Adding 1000g of solid-phase carbon-coated hard carbon material into a CVD (chemical vapor deposition) furnace, taking nitrogen as protective gas, taking acetylene as a gas-phase carbon source, taking the flow of acetylene at 1.0L/min, taking the mass ratio of acetylene to the solid-phase carbon-coated hard carbon material as 3.5, carrying out chemical vapor deposition for 3h at 800 ℃, cooling and screening after the chemical vapor deposition is finished, and thus obtaining the hard carbon cathode material.
The hard carbon negative electrode material of example 1 had a median particle diameter D50 of 6 to 10 μm and a specific surface area of 14.5m 2 (g) tap density of 0.8g/cm 3 。
Example 2
The pretreatment temperature in step 1) of example 1 was changed from 2000 ℃ to 2200 ℃ under the same conditions as in example 1.
The hard carbon negative electrode material of example 2 had a median particle diameter D50 of 8 to 12 μm and a specific surface area of 14.8m 2 (ii)/g, tap density 0.78g/cm 3 。
Example 3
The pretreatment temperature in step 1) of example 1 was changed from 2000 ℃ to 1500 ℃, and the other conditions were the same as in example 1.
The hard carbon negative electrode material of example 3 had a median particle diameter D50 of 6 to 9 μm and a specific surface area of 14.6m 2 (ii)/g, tap density 0.77g/cm 3 。
Example 4
The acid purification temperatures in both steps of step 2) of example 1 were changed from 80 ℃ to 60 ℃ and the other conditions were the same as in example 1.
The hard carbon negative electrode material of example 4 had a median particle diameter D50 of 6 to 10 μm and a specific surface area of 14.4m 2 The tap density is 0.8g/cm 3 。
Example 5
The amount of pitch added in step 3) of example 1 was changed from 170g to 220g, and the other conditions were the same as in example 1.
Median particle diameter of hard carbon negative electrode material of example 5D50 is 8-10 μm, and the specific surface area is 14.3m 2 (ii)/g, tap density 0.82g/cm 3 。
Example 6
The amount of the asphalt added in step 3) of example 1 was changed from 170g to 100g, and the other conditions were the same as in example 1.
The hard carbon negative electrode material of example 6 had a median particle diameter D50 of 7 to 9 μm and a specific surface area of 14.2m 2 (g) tap density of 0.79g/cm 3 。
Example 7
The acetylene in step 4) of example 1 was changed to methane, and the chemical vapor deposition temperature was changed from 800 ℃ to 1100 ℃, under the same conditions as in example 1.
The hard carbon negative electrode material of example 7 had a median particle diameter D50 of 8 to 11 μm and a specific surface area of 14.1m 2 (ii)/g, tap density 0.81g/cm 3 。
Example 8
1) Taking 20kg of waste tire samples, mechanically crushing, screening and demagnetizing to obtain waste tire particles with the median particle size D50 of 10-20 microns, transferring the waste tire particles into a graphitization furnace, pretreating at 1800 ℃ for 15 hours under the protection of nitrogen, and naturally cooling the samples after pretreatment to obtain the low-purity hard carbon powder.
2) Adding low-purity hard carbon powder into newly-prepared aqua regia (the aqua regia is a mixed solution of concentrated hydrochloric acid and concentrated nitric acid with the volume ratio of 3; the mass concentration of concentrated hydrochloric acid is 37 percent, the mass concentration of concentrated nitric acid is 66 percent), the mass fraction of low-purity hard carbon powder in aqua regia is 35 percent, the hard carbon powder is stirred and acid-purified for 7 hours at 55 ℃, the hard carbon powder after the aqua regia is acid-washed is washed to be neutral by deionized water, the hard carbon powder is dried in an oven at 75 ℃, a dried product is added into hydrofluoric acid with the mass concentration of 55 percent, the mass fraction of the hard carbon powder in the hydrofluoric acid is 35 percent, the hard carbon powder is stirred and acid-purified for 2 hours at 70 ℃, the hard carbon powder is washed to be neutral by deionized water, and the hard carbon powder is dried in the oven at 75 ℃ to obtain the acid-purified hard carbon powder.
3) Uniformly mixing 2000g of acid purified hard carbon powder and 140g of cane sugar, putting the mixture into a box furnace, carrying out heat treatment for 6 hours at 1350 ℃ under the protection of nitrogen, cooling, grinding and sieving to obtain a solid-phase carbon-coated hard carbon material;
4) Adding 1000g of solid-phase carbon-coated hard carbon material into a CVD (chemical vapor deposition) furnace, taking nitrogen as a protective gas, taking a gas-phase carbon source as ethylene, taking the flow of the ethylene as 1.0L/min, taking the mass ratio of the ethylene to the solid-phase carbon-coated hard carbon material as 4.5, carrying out chemical vapor deposition for 5h at 1000 ℃, cooling and screening after the chemical vapor deposition is finished, and thus obtaining the hard carbon negative electrode material.
The hard carbon negative electrode material of example 8 had a median particle diameter D50 of 7 to 10 μm and a specific surface area of 14m 2 The tap density is 0.8g/cm 3 。
Comparative example 1
The pretreatment step of step 1) in example 1 was omitted, and the other conditions were the same as in example 1.
Comparative example 2
The two acid purification steps of step 2) in example 1 were omitted and the other conditions were the same as in example 1.
Comparative example 3
The chemical vapor deposition step of step 4) in example 1 was omitted, and the other conditions were the same as in example 1.
Comparative example 4
The step of solid-phase carbon coating by heat treatment in step 3) in example 1 was omitted, and the other conditions were the same as in example 1.
The hard carbon anode materials of examples 1 to 8 and comparative examples 1 to 4 were used to prepare CR2032 type batteries for electrochemical performance testing. The method comprises the following specific steps: and (2) mixing the following components in percentage by mass: 4:4, adding the hard carbon negative electrode material, PVDF and SuperP into a sealed bottle, adding a proper amount of N-methyl pyrrolidone (the solid content is 33%) to enable the slurry to be in a viscous state, dispersing for 5min in a high-speed slurry dispersing machine at the rotating speed of 2000rpm to obtain uniform slurry, coating the slurry on an aluminum foil, drying in vacuum (the vacuum degree is-0.09 mPa) for 6h at 100 ℃, and rolling to obtain the pole piece. The cathode material uses a lithium sheet, and the electrolyte is LiPF with 1mol/L 6 Solution, solute EC, DMC and EMC in a volume ratio of 1. And (3) taking the polypropylene fiber as a diaphragm, and assembling the button cell in an inert atmosphere glove box. The charge-discharge voltage range of the cycle performance test is 0.005-2.0V, the nominal capacity is 750mAh/g, the activation is carried out by cycling for 3 weeks at the current density of 0.1C, and then the cycle is 10At 0 weeks, the results are shown in table 1 below.
Table 1 performance test results for batteries made with different hard carbon negative electrode materials
As can be seen from table 1, the battery prepared from the hard carbon negative electrode material of the present invention has good first reversible specific capacity, high first coulombic efficiency and cycle retention rate, and changing any one step in the preparation method of the present invention will cause the first coulombic efficiency and cycle retention rate to decrease, and after the pretreatment step and the two-step acid purification step of the present invention are omitted in comparative examples 1 and 2, the first reversible specific capacity, the first coulombic efficiency and the cycle stability are significantly decreased, and the single-layer coating side reactions of comparative examples 3 and 4 are large in extent, and the first coulombic efficiency and the cycle stability are poor.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (8)
1. A preparation method of a hard carbon negative electrode material is characterized by comprising the following steps:
1) Carrying out high-temperature pretreatment on a carbon source in a protective atmosphere to obtain low-purity hard carbon powder;
2) Carrying out acid purification on the low-purity hard carbon powder in an acid solution, and then sequentially washing and drying to obtain acid-purified hard carbon powder;
3) Carrying out heat treatment on the acid purified hard carbon powder and an organic carbon source to obtain a single-layer coated hard carbon material;
4) Carrying out chemical vapor deposition on the single-layer coated hard carbon material in a vapor carbon source and then screening to obtain a hard carbon cathode material;
the temperature of the high-temperature pretreatment in the step 1) is 2000-2200 ℃, and the time is 8-20h; the carbon source is waste tires;
the organic carbon source in the step 3) comprises one or more of asphalt, phenolic resin and polyethylene glycol; the mass ratio of the acid-purified hard carbon powder to the organic carbon source is 100 to 5-11; the temperature of the heat treatment is 950-1500 ℃, and the time is 2-8h.
2. The method according to claim 1, wherein the protective atmosphere in step 1) is nitrogen or argon.
3. The method according to claim 2, wherein the acid solution of step 2) contains one or more of hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid; the mass fraction of the low-purity hard carbon powder in the acid solution is 15-50%.
4. The preparation method according to claim 3, wherein the temperature for purifying the acid in the step 2) is 45 to 90 ℃ and the time is 4 to 12h; the drying temperature is 70 to 90 ℃.
5. The method according to claim 4, wherein the gas phase carbon source in step 4) comprises one or more of methane, acetylene and ethylene; the temperature of the chemical vapor deposition is 700-1200 ℃, and the time is 3-6 h; the chemical vapor deposition is carried out under a protective atmosphere.
6. The hard carbon negative electrode material prepared by the preparation method of any one of claims 1 to 5, wherein the median particle diameter D50 of the hard carbon negative electrode material is 5 to 12 μm, and the specific surface area is less than or equal to 15m 2 (iv) g; tap density is more than or equal to 0.75g/cm 3 (ii) a The first reversible specific capacity is more than or equal to 530mAh/g, and the first coulombic efficiency is more than or equal to 71 percent.
7. A battery comprising the hard carbon anode material of claim 6, wherein the battery comprises an anode material, a lithium sheet, and an electrolyte; the negative electrode material comprises a hard carbon negative electrode material, polyvinylidene fluoride and Super P, wherein the mass ratio of the hard carbon negative electrode material to the Super P is 90-94: 3-5.
8. The battery of claim 7, wherein the electrolyte comprises LiPF 6 Ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, the LiPF 6 The concentration of (b) is 0.8 to 1.2mol/L; the volume ratio of the ethylene carbonate to the dimethyl carbonate to the ethyl methyl carbonate is 0.8 to 1.2, and is 0.8 to 1.2.
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