CN111799469A - CoP @ carbon nanotube composite material and preparation and application thereof - Google Patents
CoP @ carbon nanotube composite material and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of lithium ion battery cathode materials, and particularly discloses a 3D lithium-philic CoP @ carbon nanotube composite material as well as preparation and application thereof. The invention adopts the 3D lithium-philic framework material which has short preparation process flow and is easy to be industrially popularized and is applied to the cathode of the lithium metal battery, so that the lithium can be uniformly deposited on the three-dimensional framework, the huge volume effect of the lithium metal in the deposition/dissolution process can be eliminated, the growth of lithium dendrites is effectively inhibited, and the finally obtained lithium metal composite electrode has high coulomb efficiency and long cycle life under high current density.
Description
Technical Field
The invention belongs to the technical field of lithium metal battery materials and preparation thereof, and particularly relates to a lithium metal battery negative electrode material and preparation and application thereof.
Background
The lithium metal has extremely high theoretical specific capacity of 3860mAh g-1And the lowest electrochemical potential of-3.04V (relative to a standard hydrogen electrode), are known as materials which are holy cups in the lithium battery industry. If the metallic lithium is used to replace the graphite cathode, the energy density of the current commercial lithium battery can be improved by 50% -100% under the same conditions in other aspects. Therefore, the real use of metal as a negative electrode material of a secondary battery is a goal of common efforts of numerous material manufacturers and extensive researchers. However, the high activity of the metal lithium cathode leads the metal lithium cathode to be extremely easy to react with nitrogen, oxygen, carbon dioxide, water vapor and the like in the air, and the irreversible reactions bring great potential safety hazards to the preparation of the lithium battery; lithium metal without a host structure is easy to generate a huge volume effect in the repeated deposition/dissolution process, so that the cycle life is greatly reduced; on the other hand, due to the inherent unevenness of the lithium metal surface, the lithium deposition is uneven, the continuous growth of lithium dendrites is caused to pierce an SEI film, the battery is short-circuited and even ignited and exploded, and the further industrial application of the lithium metal negative electrode is hindered.
At present, a great deal of work is done by many researchers on solving the volume effect of a lithium metal negative electrode, and the main strategy is to adopt a three-dimensional porous metal current collector comprising copper foam, nickel foam, titanium foam and the like; the 3D porous skeleton structure comprises graphene, carbon nanotubes, hollow carbon spheres, carbon fibers, glass fibers and the like; by virtue of its excellent mechanical properties, rich specific surface and good electrical conductivity, it becomes an important host material for suppressing volume change. Liangbing Hu et al [ Zhang Y, Liu B, Hitz E, et al.A carbon-based 3D current collector with surface protection for Li metal anode [ J ] at Maryland university].Nano Research,2017,10:1356-1365.]The carbon nano tube sponge prepared by the chemical vapor deposition method is subjected to surface modification to prepare Al2O3The carbon nanotube sponge is modified to have high specific surface area and stable Al2O3Layer interface of the lithiumThe performance of the cathode is greatly improved. Liweii Chen et al, Inc., of Sozhou Nanojue, Wang Y, Shen Y, Du Z, et al].Journal of Materials Chemistry A,2017,5:23434-23439.]And mechanically mixing the carbon nano tube particles prepared by spray drying with molten metal lithium to prepare the lithium-carbon nano tube composite powder. The powder is pressed on foam copper to form a lithium// lithium iron phosphate lithium battery together with lithium iron phosphate, under the multiplying power of 1.0C, after 300 cycles, the capacity retention rate is always as high as 90.1%, and after 120 cycles, the capacity of the lithium// lithium iron phosphate lithium battery consisting of lithium sheets is attenuated to be less than 75.4%.
Therefore, new diversified lithium-philic framework materials are hot spots in the research and development field of lithium metal battery negative electrodes.
Disclosure of Invention
Aiming at the problems of uneven lithium deposition, huge volume effect of lithium metal in the deposition/dissolution process and uncontrollable growth of lithium dendrites, which commonly exist in a metal lithium anode, the primary object of the invention is to provide a novel 3D lithium-philic CoP @ carbon nanotube composite material.
The second purpose of the invention is to provide a preparation method of the 3D lithium-philic CoP @ carbon nanotube composite material.
The third purpose of the invention is to provide an application of the 3D lithium-philic CoP @ carbon nanotube composite material in preparation of a lithium ion battery negative electrode material.
The fourth purpose of the invention is to provide a lithium ion battery cathode prepared by the lithium ion battery cathode material.
The invention provides a brand-new 3D lithium-philic CoP @ carbon nanotube composite material, and finds that the composite material can be used in a lithium metal battery to effectively solve the problem of volume expansion, promote uniform deposition of lithium metal, obviously reduce polarization and improve cycle performance.
A CoP @ carbon nanotube composite material is a series structure formed by carbon nanotubes passing through hollow cobalt phosphide particles with a plurality of holes.
The CoP @ carbon nanotube composite material has the cobalt phosphide content of 35-98 wt.%, preferably 50-95 wt.%.
The specific surface area of the CoP @ carbon nanotube composite material is 10-500m2(ii)/g; preferably 30-400m2(ii)/g; further preferably 58 to 300m2/g。
The porosity of the CoP @ carbon nanotube composite material is 20-99%; preferably 30-90%; more preferably 40 to 60%.
The hole pitch of the CoP @ carbon nanotube composite material is 1-400 nm; preferably 1-200 nm; further preferably 5 to 90 nm.
The effects are more excellent in the preferred ranges, for example, the stability and electrical properties of the composite material are more excellent.
The inventor innovatively finds that the material with the special morphology structure has excellent performance in the lithium metal battery and can improve the cycle stability of the lithium ion metal battery.
The invention provides a preparation method of a 3D lithium-philic CoP @ carbon nanotube composite material, which comprises the following steps:
dispersing the carbon nano tube in a nitric acid solution for pretreatment, stirring in a water bath, collecting and drying; then adding the pretreated carbon nano tube and hexadecyl trimethyl ammonium bromide into a methanol solution, and performing ultrasonic treatment to obtain a uniformly dispersed carbon nano tube suspension; then adding Co (NO)3)2·6H2Continuously stirring the O and the 2-methylimidazole; standing for at least one day, centrifuging to collect precipitate, washing, drying, and annealing to obtain a product containing polyhedral Co3O4The carbon nanotube precursor of (a); and then carrying out phosphating treatment on the mixture and a phosphorus source in an inert atmosphere to obtain the catalyst.
The preparation method of the CoP @ carbon nanotube composite material comprises the following steps:
the addition mass ratio of the carbon nano tube after pretreatment to the cetyl trimethyl ammonium bromide is (0.05-0.1): (0.2-0.5), preferably 0.07: 0.3;
Co(NO3)2·6H2the mass ratio of O and 2-methylimidazole to the pretreated carbon nanotube is (0.3-0.4): (1.5-1.6): 0.2-0.5), and preferably 0.35:1.53: 0.07.
The preparation method of the CoP @ carbon nanotube composite material,
the annealing temperature is 100-600 ℃, preferably 200-400 ℃, and the annealing time is 1-5h, preferably 2-4 h.
The preparation method of the CoP @ carbon nanotube composite material,
the concentration content of the nitric acid solution is 5% -70%, and the concentration content of the nitric acid solution is preferably 20% -45%; further preferably 30%.
The temperature of the phosphating treatment is 250-600 ℃, and the optimization is as follows: 300 ℃ and 400 ℃; the heating rate is 1-5 deg.C/min, preferably 2-3 deg.C/min; the inert gas aeration rate is 140ml/min to 300ml/min, preferably 160 and 200 ml/min.
The phosphorus source is at least one of metaphosphate and hypophosphite;
the phosphating time is 0.5-8.0h, preferably 1-5 h.
Further, the preparation method specifically comprises the following steps: the raw carbon nanotubes were dispersed in a nitric acid solution for pretreatment, magnetically stirred in a water bath (80 ℃) for 6 hours, collected and dried in a vacuum oven at 80 ℃ for 12 hours. And then adding the pretreated carbon nano tube and Cetyl Trimethyl Ammonium Bromide (CTAB) into a methanol solution, and performing ultrasonic treatment to obtain a uniformly dispersed carbon nano tube suspension. Then adding Co (NO) separately3)2·6H2Continuously stirring the O and 2-methylimidazole methanol solution; standing at room temperature for one day, centrifuging to collect precipitate, washing with ethanol for several times, drying in vacuum furnace at 80 deg.C for 12 hr, and air annealing in tubular furnace to obtain polyhedral Co-containing material3O4The carbon nanotube precursor of (a); and then carrying out phosphating treatment on the carbon nano tube and a phosphorus source in argon-containing carrier gas to obtain the 3D lithium-philic CoP @ carbon nano tube composite material.
The research of the invention finds that the shape of the material can be innovatively regulated and controlled by accurately controlling the annealing temperature, the annealing time, the phosphorization heating rate, the carrier gas circulation rate, the phosphorization reaction temperature and the like, so that the electrochemical performance of the material in the lithium ion battery is improved.
The invention aims at the problems of low specific capacity, poor stability and the like of the conventional 3D lithium metal anode. The lithium ion battery cathode material is prepared by depositing the metal lithium on the 3D lithium-philic CoP @ carbon nanotube material, so that high specific capacity and stability are realized.
The invention provides an application of the 3D lithium-philic CoP @ carbon nanotube composite material, which is characterized in that lithium metal is filled in the 3D lithium-philic CoP @ carbon nanotube composite material to prepare a lithium ion battery cathode material of the 3D lithium-philic CoP @ carbon nanotube composite material deposited with metal lithium. The prepared metallic lithium anode can provide good reversible specific capacity.
The method for filling the metal lithium is to fill lithium by melting or electrodeposition; further preferred is electrodeposition lithium filling.
According to the research of the invention, metallic lithium is filled into the 3D lithium-philic CoP @ carbon nanotube composite material by an electrodeposition method, so that the 3D lithium ion battery cathode material with controllable capacity, more uniform lithium layer and better electrochemical performance can be prepared.
The invention also provides a lithium ion battery cathode prepared from the lithium ion battery cathode material.
Mixing the CoP @ carbon nanotube composite material with an adhesive, adding the mixture into a N-methyl pyrrolidone (NMP) solution, performing ball milling and stirring to obtain uniform slurry of a composite layer, coating the slurry of the composite layer on a copper foil current collector, drying for 8 hours in a drying oven at 60 ℃, cutting into 14mm electrode plates, and performing deposition of metal lithium to obtain the 3D lithium-philic CoP @ carbon nanotube composite material lithium metal cathode.
Metal lithium content 10-90 Wt.%; preferably 25-80 wt.%.
Preferably, the lithium ion battery is a lithium sulfur battery, a lithium oxygen battery, a lithium selenium battery, a lithium iodine battery, a lithium tellurium battery, a lithium carbon dioxide battery, a lithium nitrogen battery or a transition metal oxide battery.
The adhesive is polyoxyethylene, polyacrylonitrile, polyvinylidene fluoride, polyolefins, polyvinyl alcohol, fluorinated rubber, polyurethane or sodium carboxymethyl cellulose; polyvinylidene fluoride is preferred.
The content of the adhesive is 5-95%; preferably 10 to 80%; further preferably 10 to 50%.
The thickness of the CoP @ carbon nanotube composite material coated on the pole piece is 10-900 μm; further preferably 5 to 300 μm; more preferably 10 to 100. mu.m.
The lithium carrying capacity of the lithium ion battery cathode can be adjusted according to needs, and the preferable lithium carrying capacity is 1-20 mA/cm2。
The invention also provides a lithium ion metal battery equipped with the lithium ion battery cathode.
Advantageous effects
The invention adopts the 3D lithium-philic framework material which has short preparation process flow and is easy to be industrially popularized and is applied to the negative electrode of the lithium ion battery, so that lithium can be uniformly deposited on the three-dimensional framework, the huge volume effect of lithium metal in the deposition/dissolution process can be eliminated, the growth of lithium dendrite is effectively inhibited, and the finally obtained lithium metal composite electrode has high coulombic efficiency and long cycle life under high current density.
Detailed Description
The following is a detailed description of the preferred embodiments of the invention and is not intended to limit the invention in any way, i.e., the invention is not intended to be limited to the embodiments described above, and modifications and alternative compounds that are conventional in the art are intended to be included within the scope of the invention as defined in the claims.
Example 1
The original carbon nano tube is dispersed in nitric acid solution (diluted to 30 percent by deionized water) for pretreatment, magnetically stirred in water bath (80 ℃) for 6 hours, and the product is collected by suction filtration and dried in a vacuum oven at 80 ℃ for 12 hours. 0.07g of the pretreated carbon nano tube and 0.3g of cetyltrimethylammonium bromide (CTAB) are added into 50ml of methanol solution, and ultrasonic treatment is carried out for 30min to obtain uniformly dispersed carbon nano tube suspension. Then 0.35g Co (NO) is added3)2·6H2O, stirring for another 30min at room temperature. Then, 50ml of a 2-methylimidazole methanol solution (containing 1.53g of 2-methylimidazole) was slowly poured into a reactor containing carbon nanotubes and Co (NO)3)2·6H2In O solution, magnetic stirring was continued for 30 min. After standing at room temperature for 24h, the precipitate was collected by centrifugation, washed with ethanol several times, and finally dried in a vacuum oven at 80 ℃ for 12h, which was designated as CNTs/ZIF-67. Will be provided withPutting the synthesized CNTs/ZIF-67 into a tube furnace, and annealing for 2h at 300 ℃ in the air to obtain the product containing Co3O4A polyhedral carbon nanotube precursor.
Placing the precursor block in an alumina ark crucible, and placing the precursor block in the center of a constant-temperature area of a tube furnace at 180ml/minN2And (2) carrying out phosphating treatment under air flow by using sodium hypophosphite (the molar ratio of Co to phosphorus is 1: 20), wherein the heating rate of the phosphating treatment is 2 ℃/min, the temperature of the phosphating treatment is 300 ℃, and the heat preservation time is 2h, so that the 3D lithium-philic CoP @ carbon nanotube composite material (CoP @ CNTs) is prepared.
Mixing the prepared CoP @ carbon nanotube composite material with polyvinylidene fluoride (PVDF) according to a mass ratio of 9: 1, mixing and adding the mixture into a N-methyl pyrrolidone (NMP) solution, performing ball milling and stirring to obtain a uniform slurry of a composite layer, coating the slurry of the composite layer on a copper foil current collector, wherein the thickness of the coating is 25 mu M, drying the copper foil current collector for 8h in a drying box at 60 ℃, cutting the copper foil current collector into a 14mm pole piece serving as a working electrode, a metal lithium piece serving as a counter electrode, and 1M LiTFSI/DOL DME (volume ratio is 1:1) containing 1 wt.% LiNO3Button cell assembly, lithium deposition testing and charge-discharge cycling testing were performed for the electrolyte. Meanwhile, pure cobalt phosphide (CoP) was used as a control sample to perform the corresponding deposition test and charge-discharge cycle test, as shown in table 1.
The experimental result shows that the P element and the Co element are uniformly distributed on the surface of the composite current collector. In subsequent lithium deposition experiments, metallic lithium was able to be uniformly nucleated and deposited on the CoP @ carbon nanotube composite, avoiding non-uniform lithium deposition and the appearance of lithium dendrites.
At 2mA/cm2And 5mA/cm2The cycle life of the 3D lithium-philic CoP @ carbon nanotube composite current collector electrode under the same coulombic efficiency is more than 3 times of that of pure cobalt phosphide.
Example 2
The original carbon nano-tube is dispersed in nitric acid solution (diluted to 45 percent by deionized water) for pretreatment, magnetically stirred in water bath (80 ℃) for 6 hours, and the product is collected by suction filtration and dried in a vacuum oven at 80 ℃ for 12 hours. 0.07g of the pretreated carbon nanotubes and 0.3g of cetyltrimethylammonium bromide (CTAB) were added to 50ml of a methanol solution,and carrying out ultrasonic treatment for 30min to obtain a uniformly dispersed carbon nanotube suspension. Then 0.35g Co (NO) is added3)2·6H2O, stirring for another 30min at room temperature. Then, 50ml of a 2-methylimidazole methanol solution (containing 1.53g of 2-methylimidazole) was slowly poured into a reactor containing carbon nanotubes and Co (NO)3)2·6H2In O solution, magnetic stirring was continued for 30 min. After standing at room temperature for 24h, the precipitate was collected by centrifugation, washed with ethanol several times, and finally dried in a vacuum oven at 80 ℃ for 12h, which was designated as CNTs/ZIF-67. Putting the synthesized CNTs/ZIF-67 into a tube furnace, and annealing for 2h at 250 ℃ in the air to obtain the product containing Co3O4A polyhedral carbon nanotube precursor.
Placing the precursor block in an alumina ark crucible, and placing the precursor block in the center of a constant-temperature area of a tube furnace at 160ml/minN2And carrying out phosphating treatment under air flow by using sodium hypophosphite (the molar ratio of Co to phosphorus is 1: 20), wherein the temperature rise rate of the phosphating treatment is 2 ℃/min, the temperature of the phosphating treatment is 350 ℃, and the heat preservation time is 3h, so that the 3D lithium-philic CoP @ carbon nanotube composite material is prepared.
Mixing the 3D lithium-philic CoP @ carbon nanotube composite material with polyvinylidene fluoride (PVDF) according to the mass ratio of 9: 1, mixing and adding the mixture into a N-methyl pyrrolidone (NMP) solution, performing ball milling and stirring to obtain a uniform slurry of a composite layer, coating the slurry of the composite layer on a copper foil current collector, wherein the thickness of the coating is 25 mu M, drying the copper foil current collector for 8h in a drying box at 60 ℃, cutting the copper foil current collector into an electrode piece with the thickness of 14mm as a working electrode, taking a metal lithium piece as a counter electrode, and taking 1M LiTFSI/DOL DME (volume ratio is 1:1) containing 1 wt.% LiNO3Button cell assembly, lithium deposition testing and charge-discharge cycling testing were performed for the electrolyte. Meanwhile, pure cobalt phosphide (CoP) is used as a comparison sample to carry out corresponding deposition test and charge-discharge cycle test.
At 4mA/cm2The cycle life of the 3D lithium-philic CoP @ carbon nanotube composite current collector electrode under the same coulombic efficiency is more than 4 times of that of pure cobalt phosphide.
Example 3
The pristine carbon nanotubes were magnetically stirred in a water bath (80 ℃) with nitric acid solution (diluted to 20% with water) (6h), the product was collected by suction filtration at 8Drying in a vacuum oven at 0 ℃ for 12 h. 0.07g of the pretreated carbon nano tube and 0.3g of cetyltrimethylammonium bromide (CTAB) are added into 50ml of methanol solution, and ultrasonic treatment is carried out for 30min to obtain uniformly dispersed carbon nano tube suspension. Then 0.35g Co (NO) is added3)2·6H2O, stirring for another 30min at room temperature. Then, 50ml of a 2-methylimidazole methanol solution (containing 1.53g of 2-methylimidazole) was slowly poured into a reactor containing carbon nanotubes and Co (NO)3)2·6H2In O solution, magnetic stirring was continued for 30 min. After standing at room temperature for 24h, the precipitate was collected by centrifugation, washed with ethanol several times, and finally dried in a vacuum oven at 80 ℃ for 12h, which was designated as CNTs/ZIF-67. Putting the synthesized CNTs/ZIF-67 into a tube furnace, and annealing for 3h at 400 ℃ in the air to obtain the product containing Co3O4A polyhedral carbon nanotube precursor.
The precursor is placed in the middle of the constant temperature area of the tube furnace at 200ml/minN2Carrying out phosphating treatment by using sodium hypophosphite (the molar ratio of Co to phosphorus is 1: 20) under air flow, wherein the temperature rise rate of the phosphating treatment is 5 ℃/min, the temperature of the phosphating treatment is 400 ℃, and the heat preservation time is 2 h; and preparing the 3D lithium-philic CoP @ carbon nanotube composite material.
Mixing the 3D lithium-philic CoP @ carbon nanotube composite material with polyvinylidene fluoride (PVDF) according to the mass ratio of 9: 1, mixing and adding the mixture into a N-methyl pyrrolidone (NMP) solution, performing ball milling and stirring to obtain a uniform slurry of a composite layer, coating the slurry of the composite layer on a copper foil current collector, wherein the thickness of the coating is 25 mu M, drying the copper foil current collector for 8h in a drying box at 60 ℃, cutting the copper foil current collector into an electrode piece with the thickness of 14mm as a working electrode, taking a metal lithium piece as a counter electrode, and taking 1M LiTFSI/DOL DME (volume ratio is 1:1) containing 1 wt.% LiNO3Button cell assembly, lithium deposition testing and charge-discharge cycling testing were performed for the electrolyte. Meanwhile, pure cobalt phosphide (CoP) is used as a comparison sample to carry out corresponding deposition test and charge-discharge cycle test.
At 5mA/cm2The cycle life of the three-dimensional CoP @ carbon nanotube composite material electrode under the same coulombic efficiency is more than 3 times of that of pure cobalt phosphide.
Example 4
Dispersing original carbon nano-tube in nitric acidThe solution (diluted to 30% in deionised water) was pretreated by magnetic stirring in a water bath (80 ℃) for 6h, the product was collected by suction filtration and dried in a vacuum oven at 80 ℃ for 12 h. 0.07g of the pretreated carbon nano tube and 0.3g of cetyltrimethylammonium bromide (CTAB) are added into 50ml of methanol solution, and ultrasonic treatment is carried out for 30min to obtain uniformly dispersed carbon nano tube suspension. Then 0.35g Co (NO) is added3)2·6H2O, stirring for another 30min at room temperature. Then, 50ml of a 2-methylimidazole methanol solution (containing 1.53g of 2-methylimidazole) was slowly poured into a reactor containing carbon nanotubes and Co (NO)3)2·6H2In O solution, magnetic stirring was continued for 30 min. After standing at room temperature for 24h, the precipitate was collected by centrifugation, washed with ethanol several times, and finally dried in a vacuum oven at 80 ℃ for 12h, which was designated as CNTs/ZIF-67. Putting the synthesized CNTs/ZIF-67 into a tube furnace, and annealing for 2h or 4h at 300 ℃ in the air to obtain the product containing Co3O4A polyhedral carbon nanotube precursor.
Placing the precursor block in an alumina ark crucible, and placing the precursor block in the center of a constant-temperature area of a tube furnace at 180ml/minN2And carrying out phosphating treatment under air flow by using sodium hypophosphite (the molar ratio of Co to phosphorus is 1: 20), wherein the temperature rise rate of the phosphating treatment is 2 ℃/min, the temperature of the phosphating treatment is 300 ℃, and the heat preservation time is 2h, so that the 3D lithium-philic CoP @ carbon nanotube composite material is prepared.
Mixing the 3D lithium-philic CoP @ carbon nanotube composite material with polyvinylidene fluoride (PVDF) according to the mass ratio of 9: 1, mixing and adding the mixture into a N-methyl pyrrolidone (NMP) solution, performing ball milling and stirring to obtain a uniform slurry of a composite layer, coating the slurry of the composite layer on a copper foil current collector, wherein the thickness of the coating is 25 mu M, drying the copper foil current collector for 8h in a drying box at 60 ℃, cutting the copper foil current collector into an electrode piece with the thickness of 14mm as a working electrode, taking a metal lithium piece as a counter electrode, and taking 1M LiTFSI/DOL DME (volume ratio is 1:1) containing 1 wt.% LiNO3Button cell assembly, lithium deposition testing and charge-discharge cycling testing were performed for the electrolyte.
Comparative example 4-1
Compared with the example 4, the difference is only that in the annealing treatment, the annealing time is 1h,
as can be seen from examples 4 and 4-1, the 3D lithium-philic CoP @ carbon nanotube composite material treated with the annealing time of 2h has better performance, and the results are shown in Table 1.
Example 5
The original carbon nano tube is dispersed in nitric acid solution (diluted to 30 percent by deionized water) for pretreatment, magnetically stirred in water bath (80 ℃) for 6 hours, and the product is collected by suction filtration and dried in a vacuum oven at 80 ℃ for 12 hours. 0.07g of the pretreated carbon nano tube and 0.3g of cetyltrimethylammonium bromide (CTAB) are added into 50ml of methanol solution, and ultrasonic treatment is carried out for 30min to obtain uniformly dispersed carbon nano tube suspension. Then 0.35g Co (NO3) was added2·6H2O, stirring for another 30min at room temperature. Then, 50ml of a 2-methylimidazole methanol solution (containing 1.53g of 2-methylimidazole) was slowly poured into a reactor containing carbon nanotubes and Co (NO)3)2·6H2In O solution, magnetic stirring was continued for 30 min. After standing at room temperature for 24h, the precipitate was collected by centrifugation, washed with ethanol several times, and finally dried in a vacuum oven at 80 ℃ for 12h, which was designated as CNTs/ZIF-67. Putting the synthesized CNTs/ZIF-67 into a tube furnace, and annealing for 2h at 300 ℃ in the air to obtain the product containing Co3O4A polyhedral carbon nanotube precursor.
Placing the precursor block in an alumina ark crucible, and placing the precursor block in the center of a constant-temperature area of a tube furnace at 160ml/min (or 200ml/min) N2And carrying out phosphating treatment under air flow by using sodium hypophosphite (the molar ratio of Co to phosphorus is 1: 20), wherein the temperature rise rate of the phosphating treatment is 2 ℃/min, the temperature of the phosphating treatment is 300 ℃, and the heat preservation time is 2h, so that the 3D lithium-philic CoP @ carbon nanotube composite material is prepared.
The surface of the carbon nano tube composite material obtained under the nitrogen flow of 160ml/min and 200ml/min is obviously rough, the specific surface area is large, and the 3D lithium-philic CoP @ carbon nano tube composite material is successfully obtained.
Mixing the 3D lithium-philic CoP @ carbon nanotube composite material with polyvinylidene fluoride (PVDF) according to the mass ratio of 9: 1 mixing and adding into N-methyl pyrrolidone (NMP) solution, ball milling and stirring to obtain uniform slurry of a composite layer, coating the slurry of the composite layer on a copper foil current collector, wherein the thickness of the coating is 25 mu m, drying for 8h in a drying oven at 60 ℃, and then cutting the copper foil current collector into 14mm electrode plates serving as working electrodesThe metal lithium sheet is used as a counter electrode, and 1 wt.% LiNO is contained in a volume ratio of 1M LiTFSI/DOL DME (1: 1)3Button cell assembly, lithium deposition testing and charge-discharge cycling testing were performed for the electrolyte. The results are shown in Table 2.
Comparative example 5-1
Compared with example 5, the only difference is that, in the phosphating treatment, N2The flow rate of (a) was 40ml/min, and a 3D lithium-philic CoP @ carbon nanotube composite was prepared. The composite obtained under 40ml/min argon flow had very uneven surface and the bare part of the surface was not composited with CoP.
Comparative examples 5 to 2
Compared with example 5, the only difference is that, in the phosphating treatment, N2The flow rate of (a) was 80ml/min, and a 3D lithium-philic CoP @ carbon nanotube composite was prepared. The composite material surface obtained under the argon gas flow of 80ml/min is obviously more regular than that under the argon gas flow of 40ml/min, the surface has no obvious naked part, but the thickness of the CoP layer is obviously uneven.
Comparative examples 5 to 3
Compared with example 5, the only difference is that, in the phosphating treatment, N2The flow rate of (2) was 120ml/min, and a 3D lithium-philic CoP @ carbon nanotube composite was prepared. The surface of the composite material obtained under the argon flow of 120ml/min is obviously smoother and more uniform than that of the composite material obtained under the argon flow of 40ml/min and 80ml/min, and a layer of uniform CoP is compounded on the surface of the composite material.
Example 6
The pristine carbon nanotubes were magnetically stirred in a water bath (80 ℃) for 6h with nitric acid solution (diluted to 30% with water), the product was collected by suction filtration and dried in a vacuum oven at 80 ℃ for 12 h. 0.07g of the pretreated carbon nano tube and 0.3g of cetyltrimethylammonium bromide (CTAB) are added into 50ml of methanol solution, and ultrasonic treatment is carried out for 30min to obtain uniformly dispersed carbon nano tube suspension. Then 0.35g Co (NO) is added3)2·6H2O, stirring for another 30min at room temperature. Then, 50ml of a methanol solution of 2-methylimidazole (containing 1.53g of 2-methylimidazole)Slowly pouring into a container containing carbon nanotubes and Co (NO)3)2·6H2In O solution, magnetic stirring was continued for 30 min. After standing at room temperature for 24h, the precipitate was collected by centrifugation, washed with ethanol several times, and finally dried in a vacuum oven at 80 ℃ for 12h, which was designated as CNTs/ZIF-67. Putting the synthesized CNTs/ZIF-67 into a tube furnace, and annealing for 2h at 300 ℃ in the air to obtain the product containing Co3O4A polyhedral carbon nanotube precursor.
The precursor is placed in the middle of the constant temperature area of the tube furnace at 160ml/minN2Carrying out phosphating treatment by using sodium hypophosphite (the molar ratio of Co to phosphorus is 1: 20) under air flow, wherein the temperature rise rate of the phosphating treatment is 2 or 3 ℃/min, the temperature of the phosphating treatment is 400 ℃, and the heat preservation time is 2 h; and preparing the 3D lithium-philic CoP @ carbon nanotube composite material.
Mixing the 3D lithium-philic CoP @ carbon nanotube composite material with polyvinylidene fluoride (PVDF) according to the mass ratio of 9: 1, mixing and adding the mixture into a N-methyl pyrrolidone (NMP) solution, performing ball milling and stirring to obtain a uniform slurry of a composite layer, coating the slurry of the composite layer on a copper foil current collector, wherein the thickness of the coating is 25 mu M, drying the copper foil current collector for 8h in a drying box at 60 ℃, cutting the copper foil current collector into an electrode piece with the thickness of 14mm as a working electrode, taking a metal lithium piece as a counter electrode, and taking 1M LiTFSI/DOL DME (volume ratio is 1:1) containing 1 wt.% LiNO3Button cell assembly, lithium deposition testing and charge-discharge cycling testing were performed for the electrolyte. The results are shown in Table 3.
Comparative example 6-1
Compared with example 6, the only difference is that the temperature rise rate of the phosphating treatment is 0.5 ℃/min during the phosphating treatment, and the 3D lithium-philic CoP @ carbon nanotube composite material is prepared.
The composite material obtained at the temperature of 0.5 ℃/min has obviously uneven surface, the edges can see some bulk CoP, but no good phosphorization layer is obtained in the middle of the framework basically.
Comparative examples 6 to 2
Compared with example 6, the only difference is that during the phosphating treatment, the temperature rising rate of the phosphating treatment is 1 or 5 ℃/min, and the 3D lithium-philic CoP @ carbon nanotube composite material is prepared.
The composite material obtained by the phosphating treatment at the temperature rise rate of 1 ℃/min and 5 ℃/min has uneven surface, no good phosphating layer is basically obtained in the middle of the framework, and the condition that the phosphating layer is thicker is inferior to 3 ℃/min but superior to 0.5 ℃/min.
As can be seen from the example 6 and the comparison of 6-1 and 6-2, the surface of the material obtained by controlling the temperature at 3 ℃/min is obviously coarser than that of 0.5, 1 or 5 ℃/min, the specific surface area is larger, the lithium-philic CoP layer can be uniformly seen on the surface, and the 3D lithium-philic CoP @ carbon nanotube composite material can be successfully obtained.
Example 7
The pristine carbon nanotubes were pre-treated by dispersion in a nitric acid solution (diluted to 5% (10%) in deionized water), magnetically stirred in a water bath (80 ℃) for 6h, the product was collected by suction filtration and dried in a vacuum oven at 80 ℃ for 12 h. 0.07g of the pretreated carbon nano tube and 0.3g of cetyltrimethylammonium bromide (CTAB) are added into 50ml of methanol solution, and ultrasonic treatment is carried out for 30min to obtain uniformly dispersed carbon nano tube suspension. Then 0.35g Co (NO) is added3)2·6H2O, stirring for another 30min at room temperature. Then, 50ml of a 2-methylimidazole methanol solution (containing 1.53g of 2-methylimidazole) was slowly poured into a reactor containing carbon nanotubes and Co (NO)3)2·6H2In O solution, magnetic stirring was continued for 30 min. After standing at room temperature for 24h, the precipitate was collected by centrifugation, washed with ethanol several times, and finally dried in a vacuum oven at 80 ℃ for 12h, which was designated as CNTs/ZIF-67. Putting the synthesized CNTs/ZIF-67 into a tube furnace, and annealing for 2h at 300 ℃ in the air to obtain the product containing Co3O4A polyhedral carbon nanotube precursor.
Placing the precursor block in an alumina ark crucible, and placing the precursor block in the center of a constant-temperature area of a tube furnace at 180ml/minN2And carrying out phosphating treatment under air flow by using sodium hypophosphite (the molar ratio of Co to phosphorus is 1: 20), wherein the temperature rise rate of the phosphating treatment is 2 ℃/min, the temperature of the phosphating treatment is 300 ℃, and the heat preservation time is 2h, so that the 3D lithium-philic CoP @ carbon nanotube composite material is prepared.
Mixing the 3D lithium-philic CoP @ carbon nanotube composite material with polyvinylidene fluoride (PVDF) according to the mass ratio of 9: 1 mixing and adding into N-methyl pyrrolidone (NMP) solution, ball milling and stirring to obtain uniform slurry of composite layer, and mixingCoating the composite layer slurry on a copper foil current collector, wherein the thickness of the coating is 25 mu M, drying the copper foil current collector for 8h in a drying oven at 60 ℃, cutting the copper foil current collector into 14mm electrode pieces serving as working electrodes, metal lithium pieces serving as counter electrodes, and 1M LiTFSI/DOL DME (volume ratio of 1:1) containing 1 wt.% LiNO3Button cell assembly, lithium deposition testing and charge-discharge cycling testing were performed for the electrolyte.
By contrast, the chemical properties of the obtained 3D lithium-philic CoP @ carbon nanotube composite material were optimized when nitric acid was diluted to 30% with deionized water. The results are shown in Table 4.
Comparative example 7-1
Compared with example 7, the difference is only that the concentration dilution of nitric acid is 20%, and the 3D lithium-philic CoP @ carbon nanotube composite material is prepared.
Comparative examples 7 to 2
Compared with example 7, the difference is only that the concentration dilution of nitric acid is 45%, and 3D lithium-philic CoP @ carbon nanotube composite material is prepared.
Example 8
Working electrodes were prepared by coating the three-dimensional CoP @ carbon nanotube composites prepared in examples 1 and 4 and comparative examples 4-1 on copper foil, using a lithium metal sheet as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio 1:1) containing 1 wt.% LiNO3Button cell assembly, lithium deposition testing and charge-discharge cycling testing were performed for the electrolyte. At 3mA/cm2The current density of the current sensor was selected for charge-discharge cycle testing, and the test results are shown in table 1 below:
TABLE 1
The result shows that the three-dimensional CoP @ carbon nanotube composite material obtained by annealing for 2.0h has the optimal electrochemical performance.
Example 9
Working electrodes were prepared by coating the five three-dimensional CoP @ carbon nanotube composites prepared in example 5 and comparative examples 5-1, 5-2, and 5-3 on copper foil, using a lithium metal sheet as a counter electrode, and 1MLiTFSI/DOL DME (DME/DOL)1:1) of LiNO of 1 wt.% based on the total volume3Assembling the button cell for the electrolyte at 3mA/cm2The current density of (a) was subjected to a charge-discharge cycle test, and the test results are shown in table 2 below:
TABLE 2
The result shows that the electrochemical performance of the three-dimensional CoP @ carbon nanotube composite electrode subjected to phosphating treatment at the ventilation rates of 160ml/min and 200ml/min is optimal.
Example 10
Working electrodes were prepared by coating the two materials of example 6 and the five three-dimensional CoP @ carbon nanotube composites prepared in comparative examples 6-1 and 6-2 on copper foil, using a lithium metal sheet as a counter electrode, and 1MLiTFSI/DOL: DME (volume ratio 1:1) containing 1 wt.% LiNO3Button cell assembly, lithium deposition testing and charge-discharge cycling testing were performed for the electrolyte. At 3mA/cm2The current density of (a) was subjected to a charge-discharge cycle test, and the test results are shown in table 3 below:
TABLE 3
The result shows that the electrochemical performance of the electrode of the three-dimensional CoP @ carbon nanotube composite material after phosphorization at the temperature rising speed of 2 ℃/min and 3 ℃/min is optimal.
Example 11
Working electrodes were prepared by coating five three-dimensional CoP @ carbon nanotube composites prepared from two materials of example 1 and example 7 and comparative examples 7-1 and 7-2 onto copper foil, using a lithium metal sheet as a counter electrode, and 1MLiTFSI/DOL DME (volume ratio 1:1) containing 1 wt.% LiNO3Button cell assembly, lithium deposition testing and charge-discharge cycling testing were performed for the electrolyte. At 3mA/cm2Current density ofThe charge-discharge cycle test results are shown in table 4 below:
TABLE 4
The result shows that when the nitric acid is diluted to 30%, the electrochemical performance of the obtained three-dimensional CoP @ carbon nanotube composite material is optimal.
Example 12
The 3D lithium-philic CoP @ carbon nanotube composite material prepared in example 1 and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 9: 1, mixing and adding the mixture into a N-methyl pyrrolidone (NMP) solution, performing ball milling and stirring to obtain a uniform slurry of a composite layer, coating the slurry of the composite layer on a copper foil current collector, wherein the thickness of the coating is 25 mu M, drying the copper foil current collector for 8h in a drying box at 60 ℃, cutting the copper foil current collector into an electrode piece with the thickness of 14mm as a working electrode, taking a metal lithium piece as a counter electrode, and taking 1M LiTFSI/DOL DME (volume ratio is 1:1) containing 1 wt.% LiNO3As an electrolyte, at a current density of 0.5mA/cm2Bottom deposition of 5mAh/cm2And preparing the 3D lithium-philic CoP @ carbon nanotube composite lithium metal cathode. And then the lithium sulfur battery is formed with a mesoporous carbon anode rich in S simple substance, and the lithium sulfur battery is formed in a state that 1M LiTFSI/DOL: DME (1: 1 by volume) contains 1 wt.% LiNO3In the electrolyte of (1), a charge-discharge cycle test was performed at 1C.
Example 13
The 3D lithium-philic CoP @ carbon nanotube composite material prepared in example 1 and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 9: 1, mixing and adding the mixture into a N-methyl pyrrolidone (NMP) solution, performing ball milling and stirring to obtain uniform slurry of a composite layer, coating the slurry of the composite layer on a copper foil current collector, wherein the thickness of the coating is 25 mu m, drying the copper foil current collector for 8 hours in a drying oven at 60 ℃, cutting the copper foil current collector into electrode pieces with the thickness of 14mm, and contacting the electrode pieces with molten metal lithium at 250 ℃ under an oxygen-free drying environment to obtain the 3D lithium-philic CoP @ carbon nanotube composite lithium metal negative electrode. Then with the mesoporous carbon rich in S simple substanceThe positive electrode constitutes a lithium-sulfur battery and contains 1 wt.% LiNO in a volume ratio of 1MLiTFSI/DOL to DME (1: 1)3In the electrolyte of (1), a charge-discharge cycle test was performed at 1C.
The relevant results of the experimental tests are shown in the attached table 5
TABLE 5
The result shows that the electrochemical performance of the cathode for depositing the metallic lithium by the 3D lithium-philic CoP @ carbon nanotube composite material obtained by electrodeposition is optimal.
Claims (10)
1. A CoP @ carbon nanotube composite material is characterized in that: is a series structure formed by carbon nano tubes passing through hollow cobalt phosphide particles with a plurality of holes.
2. The CoP @ carbon nanotube composite of claim 1, wherein: the cobalt phosphide content is 35-98 wt.%, preferably 50-95 wt.%.
3. The CoP @ carbon nanotube composite of claim 1, wherein: the specific surface area of the CoP @ carbon nanotube composite material is 10-500m2(ii)/g; preferably 30-400m2(ii)/g; further preferably 58 to 300m2/g；
The porosity of the CoP @ carbon nanotube composite material is 20-99%; preferably 30-90%; further preferably 40 to 60%;
the hole pitch of the CoP @ carbon nanotube composite material is 1-400 nm; preferably 1-200 nm; further preferably 5 to 90 nm.
4. A preparation method of a CoP @ carbon nanotube composite material is characterized in that,
dispersing the carbon nano tube in a nitric acid solution for pretreatment, stirring in a water bath, collecting and drying; then adding the pretreated carbon nano tube and hexadecyl trimethyl ammonium bromide into a methanol solution, and performing ultrasonic treatment to obtain uniformly dispersed carbon nanoSuspension of rice-tube; then adding Co (NO)3)2·6H2Continuously stirring the O and the 2-methylimidazole; standing for at least one day, centrifuging to collect precipitate, washing, drying, and annealing to obtain a product containing polyhedral Co3O4The carbon nanotube precursor of (a); and then carrying out phosphating treatment on the mixture and a phosphorus source in an inert atmosphere to obtain the catalyst.
5. The method of claim 4, wherein the CoP @ carbon nanotube composite material is prepared by the steps of,
the addition mass ratio of the carbon nano tube after pretreatment to the cetyl trimethyl ammonium bromide is (0.05-0.1): (0.2-0.5), preferably 0.07: 0.3;
Co(NO3)2·6H2the mass ratio of O and 2-methylimidazole to the pretreated carbon nanotube is (0.3-0.4): (1.5-1.6): 0.2-0.5), and preferably 0.35:1.53: 0.07.
6. The method for preparing the CoP @ carbon nanotube composite material as claimed in claim 4, wherein the annealing temperature is 100-600 ℃, preferably 200-400 ℃, and the annealing time is 1-5h, preferably 2-4 h.
7. The method for preparing the CoP @ carbon nanotube composite material according to claim 4, wherein the concentration content of the nitric acid solution is 5% -70%, preferably 20% -45%, and more preferably 30%; the temperature of the phosphating treatment is 250-600 ℃, and the optimization is as follows: 300 ℃ and 400 ℃; the heating rate is 1-5 deg.C/min, preferably 2-3 deg.C/min; the inert gas aeration rate is 140ml/min to 300ml/min, preferably 160 and 200 ml/min.
8. The application of the CoP @ carbon nanotube composite material as defined in any one of claims 1-3 or the CoP @ carbon nanotube composite material prepared by the preparation method as defined in any one of claims 4-7 is characterized in that: and filling lithium metal into the CoP @ carbon nanotube composite material to prepare the lithium ion battery cathode material.
9. The use according to claim 8, wherein the method for filling metallic lithium is melting lithium filling or electrodeposition lithium filling; further preferred is electrodeposition lithium filling.
10. A lithium ion battery negative electrode, characterized by being prepared from the lithium ion battery negative electrode material of claim 8.
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