CN117954613A - Carbon-coated cobalt-copper bimetallic phosphide composite nano material and preparation method and application thereof - Google Patents
Carbon-coated cobalt-copper bimetallic phosphide composite nano material and preparation method and application thereof Download PDFInfo
- Publication number
- CN117954613A CN117954613A CN202410274423.6A CN202410274423A CN117954613A CN 117954613 A CN117954613 A CN 117954613A CN 202410274423 A CN202410274423 A CN 202410274423A CN 117954613 A CN117954613 A CN 117954613A
- Authority
- CN
- China
- Prior art keywords
- copper
- carbon
- zif
- cocu
- cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 33
- 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 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920001690 polydopamine Polymers 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 15
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000006228 supernatant Substances 0.000 claims description 32
- 229910001415 sodium ion Inorganic materials 0.000 claims description 11
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 abstract description 6
- 239000010941 cobalt Substances 0.000 abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 239000010949 copper Substances 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 41
- 238000005303 weighing Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 6
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- -1 dimethyl imidazole cobalt copper Chemical compound 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a carbon-coated cobalt-copper bimetallic phosphide composite nano material and a preparation method and application thereof, wherein the method comprises the steps of uniformly mixing cobalt nitrate, copper nitrate, cetyltrimethylammonium bromide and 2-methylimidazole in deionized water, standing, washing a precipitate, and drying to obtain CoCu-ZIF; dispersing the CoCu-ZIF into methanol, adjusting the pH to 8.5, adding dopamine hydrochloride, stirring for 22-26 hours, washing the precipitate, and drying to obtain the polydopamine coated CoCu-ZIF; calcining the polydopamine coated CoCu-ZIF and red phosphorus in an anaerobic environment to obtain the carbon coated cobalt-copper bimetallic phosphide composite nanomaterial. The structural stability and electrochemical performance of the cobalt phosphide are improved through the introduction of the second metal copper and the coating of the carbon material, so that higher specific capacity, longer cycle life and better charge and discharge performance are realized.
Description
Technical Field
The invention belongs to the field of preparation of battery cathode materials, and particularly relates to a carbon-coated cobalt-copper bimetallic phosphide composite nanomaterial as well as a preparation method and application thereof.
Background
To alleviate the environmental problems associated with fossil fuels, lithium Ion Battery (LIBs) energy storage devices have been widely used in the field of portable electronic devices and the like. However, the progress of the application is severely limited due to the excessive cost and shortage of lithium resources. Thus, in this case, sodium Ion Batteries (SIBs) are the current hot spot direction due to the high natural abundance of sodium. However, due to the excessive radius of sodium ionsResulting in slow ion diffusion kinetics and severe volume changes of the active material, which seriously hamper the practical application of sodium ion batteries. Thus, the search for new, suitable electrode materials is highly desirable for a wide range of practical applications in the future.
Transition metal phosphide (such as FeP, snP, coP, ni 2 P) is a promising negative electrode material of a rechargeable battery, and is particularly suitable as a conversion type negative electrode material due to low oxidation-reduction potential and higher theoretical specific capacity. Among them, cobalt phosphide (CoP) has a unique NiAs-type crystal structure and has a high theoretical specific capacity, and is a typical representative of transition metal phosphides. However, coP is used as a negative electrode material, and problems such as inherent poor conductivity and volume change are frequently encountered in the conversion reaction process of a battery, which causes easy structural damage and continuous formation and rupture of a solid electrolyte interface film (SEI), so that the electrolyte is exhausted, resulting in degradation of coulombic efficiency and cycle stability.
In China patent application number 202310824079.9, named as a preparation method of a tin phosphide/MXene composite material and application of the composite material in a sodium ion battery, stannous chloride molten salt method is adopted to etch MXene, metal tin particles are reduced in situ, the metal tin particles are limited between MXene sheets, then deionized water is used for washing to remove redundant salt, and finally the obtained product and red phosphorus are subjected to hydrothermal treatment in ethylenediamine solution to obtain the tin phosphide/MXene composite material. The problems that exist are: the individual metal phosphides are poor in conductivity, which in turn results in low battery capacity. The sheet of MXene material does not very well buffer the volume expansion caused by sodium ions during migration.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a carbon-coated cobalt-copper bimetallic phosphide composite nano material, a preparation method and application thereof, and the structural stability and electrochemical performance of cobalt phosphide are improved through the introduction of second metal copper and the coating of carbon materials, so that higher specific capacity, longer cycle life and better charge-discharge performance are realized.
The invention is realized by the following technical scheme:
A preparation method of a carbon-coated cobalt-copper bimetallic phosphide composite nanomaterial comprises the following steps:
S1, uniformly mixing cobalt nitrate, copper nitrate, cetyltrimethylammonium bromide and 2-methylimidazole in deionized water, wherein the molar ratio of the cobalt nitrate to the copper nitrate to the 2-methylimidazole is (1.7-1.9): (0.1-0.3): (20-40), standing to obtain a mixed system a, washing and drying the precipitate in the mixed system a to obtain the CoCu-ZIF;
S2, dispersing the CoCu-ZIF into methanol, adjusting the pH of the obtained dispersion to 8.5, adding dopamine hydrochloride, stirring and reacting for 22-26 hours, wherein the mass ratio of the CoCu-ZIF to the dopamine hydrochloride is 100: (30-50) obtaining a mixed system b, washing and drying the precipitate in the mixed system b to obtain the polydopamine coated CoCu-ZIF;
S3, coating the polydopamine coated CoCu-ZIF and red phosphorus according to the following formula (2-1): and (3) calcining the mixture in an oxygen-free environment according to the mass ratio of 1 to obtain the carbon-coated cobalt-copper bimetallic phosphide composite nanomaterial.
Preferably, the ratio of cetyltrimethylammonium bromide to 2-methylimidazole as described in S1 is (10-20) mg: (20-40) mmol.
Preferably, S1 is prepared by dissolving cobalt nitrate, copper nitrate and cetyltrimethylammonium bromide in deionized water, wherein the ratio of the copper nitrate to the deionized water is (0.1-0.3) mmol:20mL to form solution A; according to (20-40) mmol:200mL, 2-methylimidazole is dissolved in deionized water to form a solution B, and the solution B and the solution A are stirred uniformly.
Preferably, the standing as described in S1 is carried out for 22-26 hours.
Preferably, S1 centrifuging the mixed system a at 8000-10000r/min for 3-5min, pouring out the supernatant, centrifuging and washing the precipitate with 30-50mL of ethanol for 2-3 times each time, pouring out the supernatant, and drying at 65-75 ℃ for 22-26h to obtain CoCu-ZIF;
S2, centrifuging the mixed system b at 8000-10000r/min for 3-5min, pouring out the supernatant, centrifuging and washing the precipitate with 30-50mL of ethanol for 2-3 times each time, pouring out the supernatant, and drying at 65-75 ℃ for 22-26h to obtain the polydopamine coated CoCu-ZIF.
Preferably, S2 is dispersed in 30mL of methanol per 100mg of CoCu-ZIF, and Tris-HCl is added to adjust the pH of the resulting dispersion to 8.5.
Preferably, S3 is calcined after grinding polydopamine coated CoCu-ZIF and red phosphorus into powder.
Further, the calcination in S3 is carried out at 600-700 ℃ for 2-3 hours.
A carbon-coated cobalt-copper bimetallic phosphide composite nanomaterial obtained by the method of preparing a carbon-coated cobalt-copper bimetallic phosphide composite nanomaterial as described in any one of the above.
The application of the carbon-coated cobalt-copper bimetallic phosphide composite nano material in sodium ion batteries.
Compared with the prior art, the invention has the following beneficial technical effects:
The invention provides a preparation method of a carbon-coated cobalt-copper bimetal phosphide composite nano material, which comprises the steps of firstly preparing a CoCu-ZIF by a sedimentation method, then coating a carbon material on the surface of the ZIF, discarding a multi-step phosphating method of the traditional method, and obtaining the carbon-coated copper-doped cobalt phosphide composite nano electrode material by one-step phosphating/carbonizing. Firstly, copper ions have better conductivity, so that compared with single cobalt phosphide, the copper ions are introduced to improve the overall conductivity of the material, enhance the electron conductivity of the electrode, and help to improve the intercalation/deintercalation kinetics of sodium ions.
Drawings
FIG. 1 is an X-ray photoelectron spectroscopy (XPS) chart of the CoCuP@C electrode material prepared in example 1.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the CoCuP@C electrode material prepared in example 1.
Fig. 3 is a graph of the cycling performance of the cocup@c electrode material prepared in example 1 in a sodium ion battery.
Detailed Description
The invention will be further described by way of embodiments, which are intended to be illustrative rather than limiting.
The invention relates to a preparation method of a carbon-coated cobalt-copper bimetallic phosphide (namely copper-doped cobalt phosphide, coCuP@C) composite nano material, which comprises the following steps:
Cobalt nitrate hexahydrate (1.7-1.9 mmol), copper nitrate trihydrate (0.1-0.3 mmol) and CTAB (cetyl trimethylammonium bromide, 10-20 mg) are dissolved in 20mL deionized water and stirred uniformly to form solution A; 2-methylimidazole (20-40 mmol) was dissolved in 200mL of deionized water to form solution B, and then the solution B and solution A were stirred well.
After standing for 22-26h, centrifuging the obtained purple solution at 8000-10000r/min for 3-5min, pouring out supernatant, centrifuging and washing the precipitate with 30-50mL of ethanol for 2-3 times each time, and pouring out supernatant.
Drying in a drying oven at 65-75 ℃ for 22-26h to obtain CoCu-ZIF (dimethyl imidazole cobalt copper), weighing 100mg, dispersing into 30mL of methanol, adding buffer solution Tris-HCL to adjust pH=8.5, then adding dopamine hydrochloride (30-50 mg), stirring for reacting for 22-26h, centrifuging the obtained black solution at 8000-10000r/min for 3-5min, pouring out the supernatant, centrifuging and washing the precipitate with 30-50mL of ethanol for 2-3 times each time, pouring out the supernatant, and drying in a drying oven at 65-75 ℃ for 22-26h to obtain polydopamine coated dimethyl imidazole cobalt copper, namely CoCu-ZIF@PDA.
Weighing 50mg of CoCu-ZIF@PDA and red phosphorus, grinding into powder, and placing in a tube furnace, wherein the mass ratio of the CoCu-ZIF@PDA to the red phosphorus is (2-1): 1, namely 25-50mg of red phosphorus, and calcining for 2-3 hours at 600-700 ℃ under a protective atmosphere (argon or nitrogen) to obtain the CoCuP@C nanomaterial, which can be used as a negative electrode material of a sodium ion battery.
Example 1:
1.8mmol of cobalt nitrate hexahydrate, 0.2mmol of copper nitrate trihydrate and 15mg of CTAB are dissolved in 20mL of deionized water and stirred uniformly to form solution A; 20mmol of 2-methylimidazole was dissolved in 200mL of deionized water to form solution B, and then solution B was added to solution A and stirred well.
After standing for 24 hours, the resulting purple solution was centrifuged at 10000r/min for 3min, the supernatant was decanted, and then the precipitate was washed 3 times with 50mL of ethanol each time by centrifugation, and the supernatant was decanted.
Drying in a 70 ℃ oven for 24 hours to obtain CoCu-ZIF, weighing 100mg to disperse into 30mL of methanol, adding Tris-HCl to adjust pH=8.5, adding 40mg of dopamine hydrochloride to stir and react for 24 hours, centrifuging the obtained black solution at 10000r/min for 3 minutes, pouring out the supernatant, centrifugally washing the precipitate with 50mL of ethanol for 3 times each time, pouring out the supernatant, and drying in a 70 ℃ oven for 24 hours to obtain CoCu-ZIF@PDA.
Weighing 50mg of CoCu-ZIF@PDA and 50mg of red phosphorus, grinding into powder, placing into a tube furnace, and calcining for 2 hours at 600 ℃ under argon to obtain the CoCuP@C nanomaterial.
Referring to FIG. 1, FIG. 1 is an X-ray photoelectron spectroscopy (XPS) chart of the CoCuP@C electrode material prepared in example 1, and the existence of orbital peaks of Cu, co and P indicates the successful preparation of bimetallic phosphide.
Referring to fig. 2, fig. 2 is a Scanning Electron Microscope (SEM) image of the cocup@c electrode material prepared in example 1. It can be seen that the cocup@c electrode material is formed by a free stack of less than five hundred nanoparticles.
Referring to fig. 3, fig. 3 is a graph showing the cycle performance of the cocup@c electrode material prepared in example 1 at a current density of 1Ag -1 as a negative electrode material for a sodium ion battery. The reversible specific capacity of the electrode tends to be stable after 10 cycles, and the discharge capacity is maintained within the range of 420-470mAh g -1 from 10 cycles to 500 cycles. The electrode material was shown to have excellent cycling stability, and the right coulombic efficiency plot maintained around 100% further demonstrated its excellent stability. And the CoCuP@C nano material still has 464mAh g -1 discharge specific capacity after 500 circles of circulation, which proves that the CoCuP@C nano material obtained by the invention has higher capacity.
Example 2:
1.7mmol of cobalt nitrate hexahydrate, 0.2mmol of copper nitrate trihydrate and 15mg of CTAB are dissolved in 20mL of deionized water and stirred uniformly to form solution A; 20mmol of 2-methylimidazole was dissolved in 200mL of deionized water to form solution B, and then solution B was added to solution A and stirred well.
After standing for 25h, the resulting purple solution was centrifuged at 9000r/min for 4min, the supernatant was decanted, after which the pellet was washed 2 times with 50mL of ethanol each time by centrifugation, and the supernatant was decanted.
Drying in a 70 ℃ oven for 24 hours to obtain CoCu-ZIF, weighing 100mg to disperse into 30mL of methanol, adding Tris-HCl to adjust pH=8.5, adding 40mg of dopamine hydrochloride to stir and react for 24 hours, centrifuging the obtained black solution for 5 minutes at 8000r/min, pouring out the supernatant, centrifugally washing the precipitate with 50mL of ethanol for 2 times each time, pouring out the supernatant, and drying in a 70 ℃ oven for 24 hours to obtain CoCu-ZIF@PDA.
Weighing 50mg of CoCu-ZIF@PDA and 50mg of red phosphorus, grinding into powder, placing into a tube furnace, and calcining for 2 hours at 700 ℃ under the protection of nitrogen to obtain the CoCuP@C nanomaterial.
Example 3:
1.9mmol of cobalt nitrate hexahydrate, 0.1mmol of copper nitrate trihydrate and 10mg of CTAB are dissolved in 20mL of deionized water and stirred uniformly to form solution A; 20mmol of 2-methylimidazole was dissolved in 200mL of deionized water to form solution B, and then solution B was added to solution A and stirred well.
After standing for 26 hours, the resulting purple solution was centrifuged at 8000r/min for 5min, the supernatant was decanted, and then washed 3 times with 50mL of ethanol each time, and the supernatant was decanted.
Drying in a 70 ℃ oven for 24 hours to obtain CoCu-ZIF, weighing 100mg to disperse into 30mL of methanol, adding Tris-HCl to adjust pH=8.5, adding 40mg of dopamine hydrochloride to stir and react for 26 hours, centrifuging the obtained black solution at 9000r/min for 5 minutes, pouring out the supernatant, centrifugally washing the precipitate with 40mL of ethanol for 3 times each time, pouring out the supernatant, and drying in a 70 ℃ oven for 24 hours to obtain CoCu-ZIF@PDA.
Weighing 50mgCoCu-ZIF@PDA and 25mg of red phosphorus, grinding into powder, placing into a tube furnace, and calcining for 3 hours at 600 ℃ under argon to obtain the CoCuP@C nanomaterial.
Example 4:
1.8mmol of cobalt nitrate hexahydrate, 0.2mmol of copper nitrate trihydrate and 15mg of CTAB are dissolved in 20mL of deionized water and stirred uniformly to form solution A; 40mmol of 2-methylimidazole was dissolved in 200mL of deionized water to form solution B, and then solution B was added to solution A and stirred well.
After standing for 24 hours, the resulting purple solution was centrifuged at 9000r/min for 5min, the supernatant was decanted, and then washed 3 times with 30mL of ethanol each time, and the supernatant was decanted.
Drying in a 70 ℃ oven for 24 hours to obtain CoCu-ZIF, weighing 100mg to disperse into 30mL of methanol, adding Tris-HCl to adjust pH=8.5, adding 40mg of dopamine hydrochloride to stir and react for 24 hours, centrifuging the obtained black solution at 10000r/min for 5 minutes, pouring out the supernatant, centrifugally washing the precipitate with 40mL of ethanol for 2 times each time, pouring out the supernatant, and drying in a 70 ℃ oven for 24 hours to obtain CoCu-ZIF@PDA.
Weighing 50mgCoCu-ZIF@PDA and 25mg of red phosphorus, grinding into powder, placing into a tube furnace, and calcining for 3 hours at 600 ℃ under argon to obtain the CoCuP@C nanomaterial.
Example 5:
1.8mmol of cobalt nitrate hexahydrate, 0.2mmol of copper nitrate trihydrate and 20mg of CTAB are dissolved in 20mL of deionized water and stirred uniformly to form solution A; 40mmol of 2-methylimidazole was dissolved in 200mL of deionized water to form solution B, and then solution B was added to solution A and stirred well.
After standing for 24 hours, the resulting purple solution was centrifuged at 8000r/min for 5min, the supernatant was decanted, and then washed 3 times with 40mL of ethanol each time, and the supernatant was decanted.
Drying in a 70 ℃ oven for 24 hours to obtain CoCu-ZIF, weighing 100mg to disperse into 30mL of methanol, adding Tris-HCl to adjust pH=8.5, adding 40mg of dopamine hydrochloride to stir and react for 24 hours, centrifuging the obtained black solution at 9000r/min for 4 minutes, pouring out the supernatant, centrifugally washing the precipitate with 50mL of ethanol for 3 times each time, pouring out the supernatant, and drying in a 70 ℃ oven for 25 hours to obtain CoCu-ZIF@PDA.
Weighing 50mgCoCu-ZIF@PDA and 25mg of red phosphorus, grinding into powder, placing into a tube furnace, and calcining for 3 hours at 600 ℃ under the protection of argon or nitrogen to obtain the CoCuP@C nanomaterial.
Claims (10)
1. The preparation method of the carbon-coated cobalt-copper bimetallic phosphide composite nanomaterial is characterized by comprising the following steps of:
S1, uniformly mixing cobalt nitrate, copper nitrate, cetyltrimethylammonium bromide and 2-methylimidazole in deionized water, wherein the molar ratio of the cobalt nitrate to the copper nitrate to the 2-methylimidazole is (1.7-1.9): (0.1-0.3): (20-40), standing to obtain a mixed system a, washing and drying the precipitate in the mixed system a to obtain the CoCu-ZIF;
S2, dispersing the CoCu-ZIF into methanol, adjusting the pH of the obtained dispersion to 8.5, adding dopamine hydrochloride, stirring and reacting for 22-26 hours, wherein the mass ratio of the CoCu-ZIF to the dopamine hydrochloride is 100: (30-50) obtaining a mixed system b, washing and drying the precipitate in the mixed system b to obtain the polydopamine coated CoCu-ZIF;
S3, coating the polydopamine coated CoCu-ZIF and red phosphorus according to the following formula (2-1): and (3) calcining the mixture in an oxygen-free environment according to the mass ratio of 1 to obtain the carbon-coated cobalt-copper bimetallic phosphide composite nanomaterial.
2. The method for preparing the carbon-coated cobalt-copper bimetal phosphide composite nanomaterial according to claim 1, wherein the ratio of cetyl trimethylammonium bromide to 2-methylimidazole in S1 is (10-20) mg: (20-40) mmol.
3. The method for preparing the carbon-coated cobalt-copper bimetallic phosphide composite nanomaterial according to claim 1, wherein S1 is prepared by dissolving cobalt nitrate, copper nitrate and cetyltrimethylammonium bromide in deionized water, and the ratio of copper nitrate to deionized water is (0.1-0.3) mmol:20mL to form solution A; according to (20-40) mmol:200mL, 2-methylimidazole is dissolved in deionized water to form a solution B, and the solution B and the solution A are stirred uniformly.
4. The method for preparing a carbon-coated cobalt-copper bimetal phosphide composite nanomaterial according to claim 1, wherein the standing of S1 is performed for 22-26 hours.
5. The method for preparing the carbon-coated cobalt-copper bimetal phosphide composite nanomaterial according to claim 1, wherein S1 is characterized in that a mixed system a is centrifuged for 3-5min at 8000-10000r/min, supernatant is poured off, then the precipitate is centrifugally washed 2-3 times with 30-50mL of ethanol each time, finally the supernatant is poured off, and the mixture is dried at 65-75 ℃ for 22-26h to obtain CoCu-ZIF;
S2, centrifuging the mixed system b at 8000-10000r/min for 3-5min, pouring out the supernatant, centrifuging and washing the precipitate with 30-50mL of ethanol for 2-3 times each time, pouring out the supernatant, and drying at 65-75 ℃ for 22-26h to obtain the polydopamine coated CoCu-ZIF.
6. The method for preparing a carbon-coated cobalt-copper bimetal phosphide composite nanomaterial according to claim 1, wherein S2 is prepared by dispersing each 100mg of CoCu-ZIF in 30mL of methanol, and adding Tris-HCL to adjust the pH of the obtained dispersion to 8.5.
7. The method for preparing the carbon-coated cobalt-copper bimetal phosphide composite nanomaterial according to claim 1, wherein S3 is prepared by grinding polydopamine-coated CoCu-ZIF and red phosphorus into powder and calcining.
8. The method for preparing a carbon-coated cobalt-copper bimetal phosphide composite nanomaterial according to claim 7, wherein the calcination in S3 is performed at 600-700 ℃ for 2-3 hours.
9. A carbon-coated cobalt-copper bimetal phosphide composite nanomaterial obtained by the method for producing a carbon-coated cobalt-copper bimetal phosphide composite nanomaterial as claimed in any one of claims 1 to 8.
10. Use of the carbon-coated cobalt-copper bimetallic phosphide composite nanomaterial according to claim 9 in sodium-ion batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410274423.6A CN117954613A (en) | 2024-03-11 | 2024-03-11 | Carbon-coated cobalt-copper bimetallic phosphide composite nano material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410274423.6A CN117954613A (en) | 2024-03-11 | 2024-03-11 | Carbon-coated cobalt-copper bimetallic phosphide composite nano material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117954613A true CN117954613A (en) | 2024-04-30 |
Family
ID=90792825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410274423.6A Pending CN117954613A (en) | 2024-03-11 | 2024-03-11 | Carbon-coated cobalt-copper bimetallic phosphide composite nano material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117954613A (en) |
-
2024
- 2024-03-11 CN CN202410274423.6A patent/CN117954613A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10333141B2 (en) | Silicon-silicon oxide-lithium composite material having nano silicon particles embedded in a silicon:silicon lithium silicate composite matrix, and a process for manufacture thereof | |
| CN108598390B (en) | Preparation method of positive electrode material for lithium-sulfur battery and lithium-sulfur battery | |
| CN102916167B (en) | Mesoporous silicon compound as lithium ion battery negative material and preparation method thereof | |
| WO2021104055A1 (en) | Nanomaterial and preparation method therefor, electrode, and secondary battery | |
| CN111180693A (en) | Negative active material, preparation method and application thereof | |
| CN111769272A (en) | Bi @ C hollow nanosphere composite material and preparation method and application thereof | |
| CN108899499B (en) | Sb/Sn phosphate-based negative electrode material, preparation method thereof and application thereof in sodium ion battery | |
| CN114039051B (en) | MXene/SnO with three-dimensional structure 2 Negative electrode composite material and preparation method thereof | |
| CN109942001B (en) | Silicon negative electrode material with spherical thorn-shaped structure and preparation method thereof | |
| CN114702013A (en) | Sodium ion battery metal selenide negative electrode material and preparation method and application thereof | |
| CN114497475A (en) | Zinc-containing nitrogen-doped porous carbon-coated zinc-based negative electrode material for lithium ion battery | |
| CN114349051A (en) | Multi-metal molybdate, preparation method thereof and lithium ion battery | |
| EP3740982A1 (en) | Silicon micro-reactors for lithium rechargeable batteries | |
| CN113213448A (en) | High-specific-capacity lithium iron phosphate electrode material and preparation method thereof | |
| CN109616656B (en) | Copper-magnesium doped coated nickel lithium phosphate cathode material for lithium battery and preparation method thereof | |
| CN109686962B (en) | Method for preparing lithium iron phosphate composite positive electrode material, positive electrode and battery | |
| CN108023079B (en) | Mixed transition metal borate anode material and preparation method thereof | |
| CN110600710A (en) | Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery | |
| CN115986090A (en) | Nitrogen-doped bismuth/carbon composite microsphere material and preparation method and application thereof | |
| CN114084882B (en) | Manganese doped Na of different valence states 3 V 2 (PO 4 ) 2 F 3 Carbon-coated cubic crystal type material, and preparation method and application thereof | |
| Yang et al. | Mott–Schottky Effect in Core–Shell W@ WxC Heterostructure: Boosting Both Electronic/Ionic Kinetics for Lithium Storage | |
| CN116190591A (en) | Preparation method of modified material modified lithium iron manganese phosphate material | |
| CN115548335A (en) | Hierarchical porous Fe 7 S 8 Preparation method and application of/nitrogen-doped carbon composite nanowire | |
| CN114975907A (en) | Vanadium boride coated nickel cobalt lithium manganate positive electrode material and preparation method thereof | |
| CN117954613A (en) | Carbon-coated cobalt-copper bimetallic phosphide composite nano material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |