CN114335487A - Preparation method and application of cobalt phosphide/carbon composite electrode material - Google Patents
Preparation method and application of cobalt phosphide/carbon composite electrode material Download PDFInfo
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- CN114335487A CN114335487A CN202210021131.2A CN202210021131A CN114335487A CN 114335487 A CN114335487 A CN 114335487A CN 202210021131 A CN202210021131 A CN 202210021131A CN 114335487 A CN114335487 A CN 114335487A
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- 239000002131 composite material Substances 0.000 title claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000007772 electrode material Substances 0.000 title claims abstract description 28
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 27
- 239000010941 cobalt Substances 0.000 title claims abstract description 27
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 7
- 239000008103 glucose Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910003003 Li-S Inorganic materials 0.000 claims abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000011780 sodium chloride Substances 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 238000005486 sulfidation Methods 0.000 claims 1
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000004321 preservation Methods 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 229910021392 nanocarbon Inorganic materials 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a preparation method and application of a cobalt phosphide/carbon composite electrode material. The preparation method comprises the following steps: mixing NaCl, glucose, thiourea and cobalt acetate, putting the mixture into a polytetrafluoroethylene lining reaction kettle, putting the reaction kettle into an oven, reacting at 160 ℃, and then carbonizing the obtained precursor at 800 ℃, phosphorizing at 300 ℃ and vulcanizing at 155 ℃ to finally obtain the required cobalt phosphide/carbon composite electrode material; the prepared cobalt phosphide/carbon composite electrode material has the advantages of stable structure, excellent electrochemical performance, good cycle performance, high specific capacitance and the like, and is very suitable for being applied to Li-S batteries as an electrode material.
Description
Technical Field
The invention belongs to the technical field of new energy electronic materials, and relates to a preparation method and application of a cobalt phosphide/carbon composite electrode material.
Background
In the face of the current situation of conventional energy exhaustion and ecological environment pollution, a lithium-sulfur battery (Li-S battery) has become a hot spot of the current world research, is rich in elemental sulfur reserve as an active substance, is pollution-free and environment-friendly, and is used as an important constituent material of the Li-S battery. However, the existing Li-S battery still has the defects of poor rate performance and short cycle life, and the shuttle effect and the volume expansion generated in the charging and discharging process are also seriously controlledAbout the development of Li-S batteries. Preparing a composite material with a cobalt phosphide nanorod structure supported by a porous carbon skeleton by using Jiangjitao through low-temperature phosphating, and then changing the concentration of a cobalt nitrate solution to prepare composite materials with different CoP loading amounts, wherein when the concentration of the cobalt nitrate solution is 0.15mol L-1Then, the lithium storage performance of the prepared composite material (CoP/C-0.15) is optimal, and the lithium storage performance is 1000mA g-1The specific capacity can be maintained at 292mAh g after 1000 cycles of circulation under the current density-1At 5000mA g-1The specific capacity under the current density can still reach 152mAh g-1(JiangJetao carbon composite cobalt phosphide material preparation and its lithium (sodium) storage performance research [ D]Black dragon river: university of harbourine engineering, 2018).
Chinese patent document CN111517298A discloses an amorphous cobalt phosphide/nano carbon composite material, comprising the following steps: (1) dissolving soluble cobalt salt in a mixed solution of ethanol and water, adding a nano carbon material and concentrated ammonia water (the ammonia content is 25-28 wt%), stirring and mixing uniformly at room temperature, and performing ultrasonic dispersion to obtain a dispersion solution I; wherein the nano carbon material is more than one of graphene oxide, reduced graphene oxide and carbon nano tubes; the mass ratio of the cobalt salt to the nano carbon material is 1: 0.5-5; (2) sealing the dispersion liquid I, and then heating and stirring in an oil bath to obtain a dispersion liquid II; wherein the oil bath temperature is 80-120 ℃; the heating and stirring time is 6 to 12 hours; (3) pouring the dispersion liquid II into a sealed hydrothermal reaction kettle for hydrothermal reaction, naturally cooling to room temperature after the reaction is finished, performing centrifugal separation, washing the obtained solid with water and ethanol, and freeze-drying to obtain a precursor; wherein the temperature of the hydrothermal reaction is 120-220 ℃; the time of the hydrothermal reaction is 8-24 h; (4) annealing the precursor and hypophosphite at high temperature in a protective gas atmosphere to obtain an amorphous cobalt phosphide/nano-carbon composite material; wherein the high-temperature annealing temperature is 300-600 ℃; the high-temperature annealing time is 1-3 h; the mass ratio of the precursor to the hypophosphite is 1: 5-1: 50.
Disclosure of Invention
Aiming at the prior art, the invention provides a preparation method and application of a new preparation method of a cobalt phosphide/carbon composite electrode material.
The technical scheme of the invention is as follows:
according to the invention, the preparation method of the cobalt phosphide/carbon composite electrode material comprises the following steps:
(1) weighing 12 g of NaCl, 2 g of glucose, 1 g of thiourea and 0.4 g of cobalt acetate by using an electronic balance, weighing 50 ml of deionized water by using a measuring cylinder, adding the deionized water into a beaker, fully dissolving the deionized water, putting the beaker into a stainless steel reaction kettle, putting the reaction kettle into an oven, and setting the temperature to be 160 DEG CoAnd C, the time is 6 hours, and the dried product is alternately centrifugally washed three times by deionized water and absolute ethyl alcohol. Put in 60oC, drying in an oven for 12 hours to obtain a precursor;
(2) carbonizing the precursor obtained in the step (1) at 800 ℃, wherein the heating speed is 2 ℃ for min-1Keeping the temperature at 800 ℃ for 2 h;
(3) adding the product obtained in the step (2) into a beaker containing deionized water, then placing the beaker on a magnetic stirrer to stir for 8 hours, centrifuging the obtained mixed solution through a centrifuge, pouring out supernatant, alternately centrifuging and washing the obtained product for three times by using the deionized water and absolute ethyl alcohol, and drying the obtained product for 12 hours at the temperature of 60 ℃;
(4) and (3) mixing the product obtained in the step (3) and sodium hypophosphite in a mass ratio of 1:10 phosphorizing at 300 deg.C, and heating at 2 deg.C for 2 min-1Keeping the temperature at 300 ℃ for 2 h;
(5) carrying sulfur on the phosphatized product obtained in the step (4) and elemental sulfur at 155 ℃ according to the mass ratio of 4:6, and heating the mixture for 2 ℃ min-1Keeping the temperature at 155 ℃ for 12 hours to obtain the cobalt phosphide/carbon composite electrode material;
according to the present invention, it is preferred that glucose in step (1) be commercially available as a carbon source.
According to the present invention, it is preferred that the hydrothermal reaction time in step (1) is 6 hours.
According to the present invention, it is preferable that the carbonization temperature in the step (2) is 800 ℃.
According to the present invention, it is preferable that the mass ratio of the carbon material to the sodium hypophosphite in the step (4) is 1: 10.
according to the present invention, it is preferred that the phosphating temperature in step (4) is 300 ℃.
According to the present invention, it is preferable that the mass ratio of the carbon material to the elemental sulfur in the step (5) is 4: 6.
According to the present invention, it is preferred that the vulcanization temperature in the step (5) is 155 ℃ and the vulcanization time is 12 hours.
Drawings
FIG. 1 is a scanning electron microscope image of a cobalt phosphide/carbon composite electrode material prepared in example 1 of the present invention.
FIG. 2 is a constant current charge-discharge diagram of the cobalt phosphide/carbon composite electrode material prepared in example 1 of the present invention.
FIG. 3 is an electrochemical impedance diagram of the cobalt phosphide/carbon composite electrode material prepared in inventive example 1.
Detailed Description
The present invention will be further described with reference to the following embodiments and drawings, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
12 g of NaCl, 2 g of glucose, 1 g of thiourea and 0.4 g of cobalt acetate are weighed by an electronic balance, 50 ml of deionized water is weighed by a measuring cylinder and added into a beaker, and the mixture is stirred by a glass rod and is subjected to ultrasonic oscillation until the mixture is completely dissolved. Pouring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven, setting the temperature at 160 ℃, reacting for 6 hours, cooling to room temperature after the reaction kettle reaches the set temperature, and carefully taking the reaction kettle out. The product was washed three times with deionized water and absolute ethanol by alternate centrifugation. Then the mixture is put into an oven at 60 ℃ for drying for 12 h.
Putting a precursor obtained by high-temperature hydrothermal reaction into an open-type vacuum atmosphere tubular electric furnace, firstly exhausting and vacuumizing, then filling argon into the tubular furnace, carbonizing at 800 ℃, and raising the temperature for 2 ℃ for min-1The heat preservation temperature is 800 DEG CAnd (5) warming for 2 h.
Sequentially centrifugally washing with deionized water and anhydrous ethanol for three times, using anhydrous ethanol for the last time, and adding 60oAnd C, drying in an oven for 12 hours.
Weighing the product after washing and sodium hypophosphite according to the mass ratio of 1:10, putting the product into a vacuum atmosphere tubular electric furnace, putting a crucible containing the sodium hypophosphite into an upper air inlet, putting a crucible containing a sample into a lower air inlet, filling argon into the tubular furnace, carrying out phosphorization at 300 ℃, and raising the temperature for 2 ℃ for min-1The heat preservation temperature is 300 ℃, and the heat preservation time is 2 hours.
And (3) mixing the phosphated product and elemental sulfur in a mass ratio of 4: weighing 6 proportions respectively, grinding the two materials, placing into a vacuum tubular electric furnace, heating to 155 deg.C under nitrogen atmosphere, and heating at 2 deg.C for 2 min-1And keeping the temperature at 155 ℃ for 2 hours to obtain the cobalt phosphide/carbon composite electrode material.
Assembling the obtained electrode material into a button cell, wherein the electrolyte adopts LiFL6The capacity of the battery was measured at various current densities of 0.1 to 3C, and at a current density of 0.5C, the battery capacity was about 580 mAh g-1Frequency range of electrochemical impedance test 0.01 Hz-105 Hz。
Example 2:
12 g of NaCl, 2 g of glucose, 1 g of thiourea and 0.4 g of cobalt acetate are weighed by an electronic balance, 50 ml of deionized water is weighed by a measuring cylinder and added into a beaker, and the mixture is stirred by a glass rod and is subjected to ultrasonic oscillation until the mixture is completely dissolved. Pouring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven, setting the temperature at 160 ℃, reacting for 6 hours, cooling to room temperature after the reaction kettle reaches the set temperature, and carefully taking the reaction kettle out. The product was washed three times with deionized water and absolute ethanol by alternate centrifugation. Then the mixture is put into an oven at 60 ℃ for drying for 12 h.
Putting a precursor obtained by high-temperature hydrothermal into an open-type vacuum atmosphere tubular electric furnace, firstly exhausting and vacuumizing, then filling argon into the tubular furnace, carbonizing at 700 ℃, and raising the temperature for 2 ℃ for min-1The heat preservation temperature is 700 ℃, and the heat preservation time is 2 hours.
Sequentially centrifugally washing with deionized water and anhydrous ethanol for three times, using anhydrous ethanol for the last time, and adding 60oAnd C, drying in an oven for 12 hours.
Weighing the product after washing and sodium hypophosphite according to the mass ratio of 1:10, putting the product into a vacuum atmosphere tubular electric furnace, putting a crucible containing the sodium hypophosphite into an upper air inlet, putting a crucible containing a sample into a lower air inlet, filling argon into the tubular furnace, carrying out phosphorization at 300 ℃, and raising the temperature for 2 ℃ for min-1The heat preservation temperature is 300 ℃, and the heat preservation time is 2 hours.
And (3) mixing the phosphated product and elemental sulfur in a mass ratio of 4: weighing 6 proportions respectively, grinding the two materials, placing into a vacuum tubular electric furnace, heating to 155 deg.C under nitrogen atmosphere, and heating at 2 deg.C for 2 min-1And keeping the temperature at 155 ℃ for 2 hours to obtain the cobalt phosphide/carbon composite electrode material.
Assembling the obtained electrode material into a button cell, wherein the electrolyte adopts LiFL6The capacity of the battery was measured at various current densities of 0.1 to 3C, and at a current density of 0.5C, the battery capacity was about 400 mAh g-1Frequency range of electrochemical impedance test 0.01 Hz-105 Hz。
Example 3:
12 g of NaCl, 2 g of glucose, 1 g of thiourea and 0.4 g of cobalt acetate are weighed by an electronic balance, 50 ml of deionized water is weighed by a measuring cylinder and added into a beaker, and the mixture is stirred by a glass rod and is subjected to ultrasonic oscillation until the mixture is completely dissolved. Pouring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven, setting the temperature at 160 ℃, reacting for 12 hours, cooling to room temperature after the reaction kettle reaches the set temperature, and carefully taking the reaction kettle out. The product was washed three times with deionized water and absolute ethanol by alternate centrifugation. Then the mixture is put into an oven at 60 ℃ for drying for 12 h.
Putting a precursor obtained by high-temperature hydrothermal reaction into an open-type vacuum atmosphere tubular electric furnace, firstly exhausting and vacuumizing, then filling argon into the tubular furnace, carbonizing at 800 ℃, and raising the temperature for 2 ℃ for min-1The heat preservation temperature is 800 ℃, and the heat preservation time is 2 hours.
Sequentially using deionized water andwashing with anhydrous ethanol by alternate centrifugation for three times, using anhydrous ethanol for the last time, and adding 60oAnd C, drying in an oven for 12 hours.
Weighing the product after washing and sodium hypophosphite according to the mass ratio of 1:10, putting the product into a vacuum atmosphere tubular electric furnace, putting a crucible containing the sodium hypophosphite into an upper air inlet, putting a crucible containing a sample into a lower air inlet, filling argon into the tubular furnace, carrying out phosphorization at 300 ℃, and raising the temperature for 2 ℃ for min-1The heat preservation temperature is 300 ℃, and the heat preservation time is 2 hours.
And (3) mixing the phosphated product and elemental sulfur in a mass ratio of 4: weighing 6 proportions respectively, grinding the two materials, placing into a vacuum tubular electric furnace, heating to 155 deg.C under nitrogen atmosphere, and heating at 2 deg.C for 2 min-1And keeping the temperature at 155 ℃ for 2 hours to obtain the cobalt phosphide/carbon composite electrode material.
Assembling the obtained electrode material into a button cell, wherein the electrolyte adopts LiFL6The capacity of the battery was measured at various current densities of 0.1 to 3C, and at a current density of 0.5C, the battery capacity was about 580 mAh g-1However, the rate performance of the battery is not superior to that of the battery under 6h of hydrothermal reaction, and the frequency range of electrochemical impedance test is 0.01 Hz-105 Hz。
Claims (7)
1. A preparation method of a cobalt phosphide/carbon composite electrode material comprises the following steps:
(1) weighing 12 g of NaCl, 2 g of glucose, 1 g of thiourea and 0.4 g of cobalt acetate by using an electronic balance, weighing 50 ml of deionized water by using a measuring cylinder, adding the deionized water into a beaker, fully dissolving the deionized water, putting the beaker into a stainless steel reaction kettle, putting the reaction kettle into an oven, and setting the temperature to be 160 DEG CoC, time 6h, alternately centrifuging and washing the dried product for three times by using deionized water and absolute ethyl alcohol; put in 60oC, drying in an oven for 12 hours to obtain a precursor;
(2) carbonizing the precursor obtained in the step (1) at 800 ℃, wherein the heating speed is 2 ℃ for min-1Keeping the temperature at 800 ℃ for 2 h;
(3) adding the product obtained in the step (2) into a beaker containing deionized water, then placing the beaker on a magnetic stirrer to stir for 8 hours, centrifuging the obtained mixed solution through a centrifuge, pouring out supernatant, alternately centrifuging and washing the obtained product for three times by using the deionized water and absolute ethyl alcohol, and drying the obtained product for 12 hours at the temperature of 60 ℃;
(4) and (3) mixing the product obtained in the step (3) and sodium hypophosphite in a mass ratio of 1:10 phosphorizing at 300 deg.C, and heating at 2 deg.C for 2 min-1Keeping the temperature at 300 ℃ for 2 h;
(5) carrying sulfur on the phosphatized product obtained in the step (4) and elemental sulfur at 155 ℃ according to the mass ratio of 4:6, and heating the mixture for 2 ℃ min-1And keeping the temperature at 155 ℃ for 12 hours to obtain the cobalt phosphide/carbon composite electrode material.
2. The method for preparing a cobalt phosphide/carbon composite electrode material as set forth in claim 1, wherein the reaction time in step (1) is 6 hours.
3. The method for preparing a cobalt phosphide/carbon composite electrode material according to claim 1, wherein the hydrothermal reaction temperature in step (1) is 160 ℃.
4. The method for preparing a cobalt phosphide/carbon composite electrode material according to claim 1, wherein the carbonization temperature in the step (2) is 800 ℃.
5. The method for preparing a cobalt phosphide/carbon composite electrode material according to claim 1, wherein the phosphating temperature in step (4) is 300 ℃.
6. The method for preparing a cobalt phosphide/carbon composite electrode material according to claim 1, wherein the sulfidation temperature in step (5) is 155 ℃.
7. The application of the cobalt phosphide/carbon composite electrode material can be used as an electrode material of a Li-S battery.
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