CN115924957A - Pomegranate-shaped carbon sphere for packaging zinc oxide nanoparticles and preparation method and application thereof - Google Patents
Pomegranate-shaped carbon sphere for packaging zinc oxide nanoparticles and preparation method and application thereof Download PDFInfo
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- CN115924957A CN115924957A CN202211700447.0A CN202211700447A CN115924957A CN 115924957 A CN115924957 A CN 115924957A CN 202211700447 A CN202211700447 A CN 202211700447A CN 115924957 A CN115924957 A CN 115924957A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 215
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 79
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000004806 packaging method and process Methods 0.000 title description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 11
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 239000004246 zinc acetate Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 11
- 239000007773 negative electrode material Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 43
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 description 13
- 239000011800 void material Substances 0.000 description 12
- 210000001787 dendrite Anatomy 0.000 description 9
- 230000008021 deposition Effects 0.000 description 9
- 230000006911 nucleation Effects 0.000 description 9
- 238000010899 nucleation Methods 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- -1 ZIF-8 compound Chemical class 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 230000002829 reductive effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
Images
Classifications
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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
Abstract
The invention relates to the technical field of material preparation, in particular to a pomegranate-shaped carbon sphere for encapsulating zinc oxide nanoparticles and a preparation method and application thereof. A preparation method of pomegranate-shaped carbon spheres for encapsulating zinc oxide nanoparticles comprises the following steps: mixing zinc acetate and diethylene glycol, ultrasonically dissolving, stirring to obtain a milky mixed solution, centrifuging, washing collected filter residues with deionized water and absolute ethyl alcohol in sequence, drying to obtain zinc oxide nanoparticle cluster spheres, adding the zinc oxide nanoparticle cluster spheres and dimethyl imidazole into a mixed solution of N, N-dimethylformamide and deionized water, ultrasonically reacting and stirring to obtain a mixed solution, washing the filter residues collected after centrifuging in sequence with deionized water and absolute ethyl alcohol, drying to obtain a precursor, calcining in an inert atmosphere to obtain pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles, and using the pomegranate-shaped carbon spheres as a lithium metal cathode host material to prevent separation of lithium parent sites and realize the growth of a metal lithium confinement.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a pomegranate-shaped carbon sphere for encapsulating zinc oxide nanoparticles and a preparation method and application thereof.
Background
Commercial lithium ion batteries using graphite as a negative electrode have been developed and widely used in electric vehicles and portable electronic devices in the 90 s of the 20 th century, but have a lower theoretical specific capacity (372 mAhg) with the development of technology -1 ) The graphite anode material of (a) has no longer been able to meet the demand of high energy density batteries. Thus has ultrahigh theoretical specific capacity (3860 mAhg) compared with graphite -1 ) And the lowest redox potential (-3.04V compared to a standard hydrogen electrode) are considered to be the most potential negative electrode material for next generation rechargeable batteries.
However, lithium metal has a host-free property, and during the electroplating/stripping process of metal lithium, uncontrolled lithium dendrite growth and infinite volume expansion result in low coulombic efficiency, rapid capacity decay, and even after the separator is penetrated by lithium dendrite, a short circuit occurs inside the battery to cause serious safety accidents. According to research, the formation of lithium dendrites is mainly due to the lack of lithium affinity of the nucleation substrate and the uneven distribution of the electric field on the electrode surface, which causes lithium ions to selectively deposit at the positions where the nucleation barrier is low, and then "hot spots" are formed, so that as repeated lithium plating/stripping progresses, the metallic lithium deposited on the "hot spots" continuously accumulates, and finally lithium dendrites are formed.
At present, in order to adjust the deposition behavior of metallic lithium and realize a dendrite-free metallic lithium negative electrode, a three-dimensional porous carbon-based framework (such as carbon nanospheres, carbon nanotubes, graphene and the like) with large specific surface area and high conductivity is generally adopted as a metallic lithium negative electrode host material, and the metallic lithium is deposited into the three-dimensional carbon framework to effectively relieve the volume expansion of the metallic lithium, but the host material in the prior art still has the problem of poor affinity with the metallic lithium.
Disclosure of Invention
The invention provides a pomegranate-shaped carbon sphere for encapsulating zinc oxide nanoparticles, and a preparation method and application thereof, which are used for solving the problem of poor affinity between a host material and lithium metal in the prior art.
The invention provides a preparation method of pomegranate-shaped carbon spheres for encapsulating zinc oxide nanoparticles, which comprises the following steps:
s1: adding zinc acetate into diethylene glycol, dissolving by using ultrasound, and stirring in a constant-temperature oil bath to obtain a milky mixed solution;
s2: centrifuging the milky white mixed solution, collecting filter residues, washing the filter residues by deionized water and absolute ethyl alcohol in sequence, and then drying to obtain zinc oxide nanoparticle cluster spheres;
s3: adding the zinc oxide nanoparticle cluster balls and dimethyl imidazole into a mixed solution of N, N-dimethylformamide and deionized water, carrying out ultrasonic treatment, and then carrying out constant-temperature oil bath stirring reaction to obtain a mixed solution;
s4: centrifuging the mixed solution, collecting filter residues, washing the filter residues with deionized water and absolute ethyl alcohol in sequence, and drying to obtain a precursor;
s5: and calcining the precursor in an inert atmosphere to obtain the pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles.
Preferably, in step S1: the dosage of the zinc acetate is 0.985g to 1.129g, and the dosage of the diethylene glycol is 50mL to 80mL.
More preferably, in step S1: the dosage of the zinc acetate is 1.095g, and the dosage of the diethylene glycol is 50mL.
Preferably, in step S1: the reaction temperature is 140-170 ℃, and the reaction time is 1.5-10 h.
More preferably, in step S1: the reaction temperature is 160 ℃, and the reaction time is 2h.
Preferably, in step S2: the rotating speed of the centrifugal machine is 5000-10000rpm, and the centrifugal time is 5min;
the washing times with the deionized water are 1 to 3 times, and the washing times with the absolute ethyl alcohol are 1 to 3 times;
the vacuum drying time is 12-24 h.
More preferably, in step S2: the rotating speed of the centrifugal machine for centrifugation is 6000rpm, and the centrifugation time is 5min;
the washing times with the deionized water are 2 times, and the washing times with the absolute ethyl alcohol are 2 times;
the vacuum drying time is 12h.
Preferably, in step S3: the usage amount of the zinc oxide nanoparticle cluster ball is 1g, the usage amount of the dimethyl imidazole is 1.0 g-2.0 g, the usage amount of the N, N-dimethylformamide solvent is 50 mL-150 mL, and the usage amount of the deionized water is 25mL;
the reaction temperature is 70-100 ℃, and the stirring time is 12-24 h.
More preferably, in step S3: the usage amount of the zinc oxide nanoparticle cluster ball is 1g, the usage amount of the dimethyl imidazole is 1.2g, the usage amount of the N, N-dimethylformamide solvent is 75mL, and the usage amount of the deionized water is 25mL;
the reaction temperature is 70 ℃, and the stirring time is 24h.
Preferably, in step S4: the rotating speed of the centrifugal machine is 5000rpm, and the centrifugal time is 5min;
the washing times with the deionized water are 1 to 3 times, and the washing times with the absolute ethyl alcohol are 1 to 3 times;
the drying time is 12-24 h.
More preferably, in step S4: the rotating speed of the centrifugal machine for centrifugation is 5000rpm, and the centrifugation time is 5min;
the washing times with the deionized water are 2 times, and the washing times with the absolute ethyl alcohol are 2 times;
the drying time was 24h.
Preferably, in step S5: the inert atmosphere is N 2 The heating rate of heating to the calcining temperature is 3-5 ℃/min, the calcining temperature is 700-800 ℃, and the time for keeping the calcining temperature is 2h.
More preferably, in step S5: the heating rate of heating to the calcining temperature is 3-5 ℃/min, and the calcining temperature is 750 ℃.
Specifically, the calcination temperature in S5 may affect the void space of the pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles, and when the calcination temperature is low, the void space of the pomegranate-shaped carbon spheres may be relatively small; when the temperature of calcination is higher, the void space of the pomegranate-shaped carbon spheres is larger.
The invention also provides a pomegranate-shaped carbon sphere for encapsulating the zinc oxide nano-particles, which is prepared by the preparation method.
The third aspect of the invention provides an application of the pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles in preparation of a lithium metal battery negative electrode host material.
In particular, when the pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles are used as a host material of a lithium metal negative electrode, the pomegranate-shaped carbon spheres have excellent lithium-philic performance, excellent functions of limiting lithium-philic sites and limiting the growth of lithium metal, and good cycling stability.
The fourth aspect of the present invention provides a lithium metal negative electrode material, and a preparation method of the lithium metal negative electrode material comprises the following steps:
dissolving the pomegranate-shaped carbon spheres and the carbon black for packaging the zinc oxide nanoparticles in a polyvinylidene fluoride solution of N-methyl pyrrolidone, then grinding and uniformly mixing, coating on a copper foil current collector and drying to obtain a lithium metal negative electrode material;
the mass ratio of the pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles to the polyvinylidene fluoride solution of the carbon black and the N-methylpyrrolidone is 8:1:1, the temperature of the oven is 100 ℃, and the drying time is 12h.
According to the technical scheme, the invention has the following advantages:
the invention provides a preparation method of pomegranate-shaped carbon spheres for encapsulating zinc oxide nanoparticles, which comprises the following steps: s1: adding zinc acetate into diethylene glycol, dissolving by using ultrasound, and stirring in a constant-temperature oil bath to obtain a milky mixed solution; s2: centrifuging the milky white mixed solution, collecting filter residues, washing the filter residues with deionized water and absolute ethyl alcohol in sequence, and drying to obtain zinc oxide nanoparticle cluster balls; s3: adding the zinc oxide nanoparticle cluster balls and dimethyl imidazole into a mixed solution of N, N-dimethylformamide and deionized water, carrying out ultrasonic treatment, and then carrying out constant-temperature oil bath stirring reaction to obtain a mixed solution; s4: centrifuging the mixed solution, collecting filter residues, washing the filter residues by deionized water and absolute ethyl alcohol in sequence, and then drying to obtain a precursor; s5: and calcining the precursor in an inert atmosphere to obtain the pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles.
The preparation method is simple and convenient to operate, low in reaction temperature, low in equipment requirement, moderate in cost and suitable for large-scale production, and the prepared pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles have excellent lithium affinity, and can be used as a host material applied to a lithium metal battery cathode to effectively inhibit the formation of lithium dendrites, so that the assembled battery has the advantages of high coulombic efficiency and good cycle stability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without inventive labor.
Fig. 1 is a transmission electron microscope image of a first pomegranate-shaped carbon sphere encapsulating zinc oxide nanoparticles provided in example 1 of the present invention;
fig. 2 is a scanning electron microscope image of a pomegranate-shaped carbon sphere encapsulating zinc oxide nanoparticles provided in embodiment 1 of the present invention;
fig. 3 is a transmission electron microscope image of a second pomegranate-shaped carbon sphere encapsulating zinc oxide nanoparticles provided in embodiment 2 of the present invention;
fig. 4 is a transmission electron microscope image of a third pomegranate-shaped carbon sphere encapsulating zinc oxide nanoparticles provided in embodiment 3 of the present invention;
fig. 5 is a nucleation overpotential diagram of the pomegranate-shaped carbon spheres encapsulating zinc oxide nanoparticles prepared in example 1 provided in example 5 of the present invention as a negative electrode material of a lithium metal battery;
FIG. 6 is a graph showing the long cycle performance of the pomegranate-shaped carbon spheres encapsulating zinc oxide nanoparticles prepared in examples 1 to 3 of the present invention as a negative electrode material for a lithium metal battery in example 5;
fig. 7 is a graph showing rate performance of pomegranate-shaped carbon spheres encapsulating zinc oxide nanoparticles prepared in examples 1 to 3 according to example 5 of the present invention as a negative electrode material for a lithium metal battery.
Detailed Description
In order to adjust the deposition behavior of metallic lithium and realize a dendrite-free metallic lithium negative electrode, a great deal of research and effort is made, and a three-dimensional porous carbon-based framework (such as carbon nanospheres, carbon nanotubes, graphene and the like) with a large specific surface area and high conductivity is adopted as a metallic lithium negative electrode host material, which is considered as an effective strategy for inhibiting lithium dendrite, but the affinity between a pure carbon substrate and metallic lithium is generally poor.
In view of the above, the invention provides a pomegranate-shaped carbon sphere encapsulating zinc oxide nanoparticles, and a preparation method and an application thereof, which are used for solving the problem of poor affinity between a host material and lithium metal in the prior art.
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the embodiments described below are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The reagents used in the examples of the present application are all commercially available.
Example 1
The embodiment provides a first pomegranate-shaped carbon sphere for encapsulating zinc oxide nanoparticles, and the preparation method comprises the following steps:
s1: adding 1.095g of zinc acetate into 50mL of diethylene glycol reagent, ultrasonically dissolving, and adding into a constant-temperature heating magnetic stirrer at 160 ℃ for oil bath stirring for 2h;
s2: centrifuging the milky white mixed solution prepared in the step S1 to separate and collect, wherein the centrifugation speed is 6000rpm, the centrifugation time is 5min, washing twice with deionized water and absolute ethyl alcohol respectively to remove residual diglycol solution and impurity ions, and drying in a vacuum drying oven for 12h to obtain white powder, namely the zinc oxide nanoparticle cluster spheres;
s3: adding 1g of the zinc oxide nanoparticle cluster ball prepared in the step S2 and 1.2g of dimethyl imidazole into a mixed solution of 75mLN, N-dimethylformamide and 25mL of deionized water, carrying out ultrasonic treatment for a certain time, and then putting the mixture into a constant-temperature heating magnetic stirrer to carry out stirring in a constant-temperature oil bath at 70 ℃ for 24 hours;
s4: separating and collecting the mixed solution prepared in the step S3 by centrifugation, wherein the centrifugation rotation speed is 5000rpm, the centrifugation time is 5min, washing the mixed solution twice by using deionized water and absolute ethyl alcohol respectively, removing residual solvent and impurities, and drying the washed mixed solution in a forced air drying oven for 12h to obtain white powder, namely the zinc oxide and ZIF-8 compound precursor;
s5: and (3) putting the precursor prepared in the step (S4) in a tube furnace N2 atmosphere, raising the temperature to 750 ℃ at the rate of 5 ℃/min, keeping the temperature for 2 hours, and obtaining pomegranate-shaped carbon spheres for encapsulating the zinc oxide nanoparticles after the reaction is finished and the temperature returns to room temperature, wherein the pomegranate-shaped carbon spheres are marked as ZnO @ NPCS.
In the scheme of the embodiment, zinc oxide is used as a self-sacrificial template, divalent zinc ions ionized from zinc oxide in a mixed solution of N, N-dimethylformamide and deionized water are coordinated with a nitrogen-containing ligand provided by dimethylimidazole, a ZIF-8 shell is formed to coat the surfaces of zinc oxide nanoparticles, then a large amount of zinc oxide is evaporated under high-temperature treatment, a proper amount of zinc oxide nanoparticles are left to be uniformly distributed in a carbon sphere, and the in-situ synthesized ZIF-8 shell can still be kept in a carbon skeleton after carbonization treatment, so that a pomegranate-shaped three-dimensional conductive network is formed, and the electronic and ionic conductivity of the material is effectively improved.
Referring to fig. 1 and 2, transmission electron microscope images and scanning electron microscope images of the pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles prepared in this example are shown. As can be seen from the figure, the pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles prepared in this example are a pomegranate-shaped three-dimensional conductive network. The special pomegranate-shaped structure of the pomegranate-shaped carbon sphere for encapsulating the zinc oxide nanoparticles prepared by the embodiment can play a role in preventing separation of lithium-philic sites and realizing the growth of lithium metal confinement.
Example 2
The embodiment provides a second pomegranate-shaped carbon sphere encapsulating zinc oxide nanoparticles, and the preparation method has the same steps as those of embodiment 1 in S1 to S4, except that the step S5:
putting the precursor prepared by the step S4 into a tube furnace N 2 Heating to 700 ℃ at a heating rate of 5 ℃/min in the atmosphere, keeping for 2h, and obtaining the pomegranate-shaped carbon spheres containing the encapsulated zinc oxide nanoparticles with small void space after the reaction is finished and returns to the room temperature, wherein the label is ZnO @ NPCS-L.
Referring to fig. 3, a transmission electron microscope image of the pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles prepared in this example is shown. As is clear from FIG. 3, the calcination temperature used in this example was lower than that of example 1, and the ZnO @ NPCS-L material contained a smaller void space than that of the ZnO @ NPCS material.
Example 3
The embodiment provides a third pomegranate-shaped carbon sphere for encapsulating zinc oxide nanoparticles, wherein in the preparation method, S1 to S4 are the same as those in embodiment 1, except that S5:
putting the precursor prepared by the step S4 into a tube furnace N 2 Heating to 800 ℃ respectively at the heating rate of 5 ℃/min in the atmosphere, keeping for 2h, and obtaining the pomegranate-shaped carbon spheres with larger void space and encapsulating the zinc oxide nanoparticles and marked as ZnO @ NPCS-M after the reaction is finished and returns to the room temperature.
Referring to fig. 4, a transmission electron microscope image of pomegranate-shaped carbon spheres encapsulating zinc oxide nanoparticles prepared in this example is shown. As is clear from FIG. 4, the calcination temperature employed in this example was higher than that of example 1, and the ZnO @ NPCS-M material contained a larger void space than that of the ZnO @ NPCS material.
Example 4
The embodiment provides a pomegranate-shaped carbon sphere pole piece for encapsulating zinc oxide nanoparticles, and the preparation method comprises the following steps:
the ZnO @ NPCS, znO @ NPCS-L and ZnO @ NPCS-M materials prepared in examples 1 to 3 were mixed with carbon black, a polyvinylidene fluoride solution dissolved in N-methylpyrrolidone, and the mixture was stirred at a ratio of 8:1:1, uniformly coating the mixture on a copper foil by using a scraper, and drying the copper foil in a vacuum oven at 100 ℃ for 12 hours to obtain three different pomegranate-shaped carbon sphere pole pieces for packaging zinc oxide nanoparticles.
It can be understood that the pomegranate-shaped carbon sphere pole piece encapsulating the zinc oxide nanoparticles is prepared to facilitate battery assembly, and the host material is the pomegranate-shaped carbon sphere material encapsulating the zinc oxide nanoparticles on the pole piece.
Example 5
This example is an application example of the pomegranate-shaped carbon sphere electrode sheet encapsulating the zinc oxide nanoparticles prepared in examples 1 to 3 as a negative electrode material of a lithium metal battery.
And cutting the dried three different pomegranate-shaped carbon ball pole pieces for packaging the zinc oxide nanoparticles into 12mm round pole pieces which are respectively marked as ZnO @ NPCS, znO @ NPCS-L and ZnO @ NPCS-M and used as the negative electrode material of the lithium metal battery to carry out electrochemical performance test. Wherein ZnO @ NPCS pole pieces are the preferred samples of the present invention. It can be understood that, in the half cell, the pomegranate-shaped carbon sphere pole piece encapsulating the zinc oxide nanoparticles is directly used as an electrode; in the full battery, a pomegranate-shaped carbon sphere pole piece for encapsulating the zinc oxide nanoparticles is used with lithium metal as an electrode, wherein the pomegranate-shaped carbon sphere material for encapsulating the zinc oxide nanoparticles on the pole piece is a lithium metal battery negative host material.
1. Characterization of nucleation overpotentials
Assembling the half cell: and respectively assembling a pomegranate-shaped carbon sphere pole piece with the diameter of 12mm and used for packaging zinc oxide nanoparticles and a metal lithium piece into a Li | ZnO @ NPCS, li | ZnO @ NPCS-L and Li | ZnO @ NPCS-M half-cell in a glove box which is filled with argon and has the water-oxygen content lower than 0.01 ppm. The electrolyte system selectively contains 2wt% of lithium nitrate (LiNO) 3 ) Electrolyte additive and 1,3-Dioxolane (DOL)/ethylene glycol dimethyl ether (DME) (v/v = 1:1) solution of 1mol/L lithium bistrifluoromethanesulfonylimide (LiTFSI), and the separator adopts commercial polypropylene porous membrane.
Electrochemical testing: firstly, li | ZnO @ NPCS half-cell is firstly processed at 0.05mA/cm 2 Is cycled for 5 times between 0.01 and 3V and then at 1mA/cm 2 Repeatedly depositing/stripping at a current of 1mAh/cm 2 The nucleation overpotential of the lithium metal of (4) is shown in FIG. 5. The nucleation overpotential is the difference between the lowest voltage value and the stable voltage value during lithium deposition, and it can be known from fig. 5 that the nucleation overpotential of the Li | zno @ npcs half-cell is only 8mV, which indicates that the pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles synthesized in example 1, which are used as the negative electrode host material of the lithium metal cell, can reduce the nucleation barrier of the metal lithium by performing an alloy reaction with lithium ions, thereby reducing the deposition resistance, inducing the uniform deposition of the metal lithium, and playing a significant role in reducing the deposition resistance of the metal lithium.
2. Characterization of cycling Performance
Assembling the symmetrical battery: electrodepositing half-cells of Li | ZnO @ NPCS, li | ZnO @ NPCS-L and Li | ZnO @ NPCS-M at a discharge current of 0.5mA/cm 2 Pre-deposition of 10mAh/cm 2 The metallic lithium of (4); then the half-cell was disassembled in a glove box, and the composite lithium negative electrode Li @ ZnO @ NPCS, li @ ZnO @ NPCS-L and Li @ ZnO @ NPCS-M were taken out, and the electrolyte remaining on the surface was washed with excess DME, and two composite electrode sheets of the same metal lithium capacity, li @ ZnO @ NPCS-L and Li @ ZnO @ NPCS-M were assembled to assembleThe electrolyte system is characterized in the same manner as the characterization of the symmetric battery.
Electrochemical testing: for symmetric battery of 1mA/cm at Li @ ZnO @ NPCS |, li @ ZnO @ NPCS-L | Li @ ZnO @ NPCS-L and Li @ ZnO @ NPCS-M | Li @ ZnO @ NPCS-M 2 Repeatedly depositing/stripping 1mAh/cm under current 2 The cycle performance of the lithium metal (2) is shown in FIG. 6. Among them, the li @ zno @ npcs symmetric battery composed of the material prepared in preferred embodiment 1 of the present invention exhibits a stable long cycle performance of 3000 hours (i.e., 1500 cycles), and the overpotential is as low as 27mV, indicating no lithium dendrite deposition of metallic lithium in the zno @ npcs electrode; li @ ZnO @ NPCS-L and Li @ ZnO @ NPCS-M symmetrical batteries have appeared more serious polarization phenomenon at 1500h and 700h respectively, indicate that the battery is inside to have formed unstable SEI interface, initiate dendrite growth, lead to the battery inefficacy. Therefore, the calcination temperature can affect the void space of the pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles, and when the calcination temperature is low or high, the void space of the prepared pomegranate-shaped carbon spheres is small or large, which can affect the performance of the material and reduce the ability of the pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles to induce the uniform deposition of metal lithium.
3. Characterization of the Rate Properties
Assembling the full cell: electrodepositing the half-cell with discharge current of 0.5mA/cm by using Li | ZnO @ NPCS, li | ZnO @ NPCS-L and Li | ZnO @ NPCS-M 2 Pre-deposition of 10mAh/cm 2 The metallic lithium of (4); then, the half cell was disassembled in a glove box, and the lithium composite metal negative electrodes li @ zno @ npcs, li @ zno @ npcs-L, and li @ zno @ npcs-M were taken out, and the electrolyte remaining on the surface was washed with excess DME; the loading of the active matter is about 3mg/cm 2 The lithium iron phosphate (LFP) positive pole piece and the composite metal lithium negative pole are placed in a glove box to be assembled into the Li @ ZnO @ NPCS | LFP full-cell. The system using the electrolyte was 1mol/L lithium hexafluorophosphate (LiPF) 6 ) Ethylene Carbonate (EC)/diethyl carbonate (DEC) (v/v = 1:1) solution, polypropylene porous membrane was used as the separator material.
Electrochemical testing: the rate performance of the full cells Li @ ZnO @ NPCS | LFP, li @ ZnO @ NPCS-L | LFP and Li @ ZnO @ NPCS-M | LFP was shown in FIG. 7, in which the full cells were subjected to charge-discharge tests at a rate of 0.1 to 2C and a voltage of 2.4 to 4V, respectively. The reversible capacity of the Li @ ZnO @ NPCS | LFP full battery under 1C and 2C is respectively as high as 120 mAh/g and 100mAh/g, and the reversible capacity of the Li @ ZnO @ NPCS electrode and the Li-shaped frame containing a proper void space can effectively buffer huge volume expansion of metal lithium in the charging and discharging process, so that the full battery has excellent rate performance, and the capacity of the full battery taking the ZnO @ NPCS-M containing a large void space and the ZnO @ NPCS-L electrode containing a small void space as the negative electrode under the 1C rate is slightly lower than that of the ZnO @ NPCS electrode, but the capacity under the 2C rate is only 22 and 30mAh/g. Therefore, the pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles synthesized by the method have high coulombic efficiency.
In conclusion, the scheme of the invention has the following advantages:
(1) The method is simple, easy and convenient to operate, low in temperature, simple in post-treatment, simple in equipment requirement, moderate in cost and suitable for large-scale production.
(2) According to the invention, zinc oxide is used as a self-sacrifice template, divalent zinc ions ionized from zinc oxide in a mixed solution of N, N-dimethylformamide and deionized water are coordinated with a nitrogen-containing ligand provided by dimethyl imidazole to form a ZIF-8 shell to coat the surface of zinc oxide nanoparticles, a large amount of zinc oxide is evaporated under high-temperature treatment, a proper amount of zinc oxide nanoparticles are left to be uniformly distributed in carbon spheres, and the in-situ synthesized ZIF-8 shell can still be kept in a carbon skeleton during carbonization treatment to form a pomegranate-shaped three-dimensional conductive network, so that the electronic and ionic conductivity of the material can be effectively improved.
(3) The pomegranate-shaped carbon sphere for encapsulating the zinc oxide nanoparticles synthesized by the method has a large specific surface area, can effectively reduce local current density, and can be used for uniformly distributing an electric field, and meanwhile, the pomegranate-shaped space formed in the carbon sphere can effectively limit the agglomeration of lithium-philic sites in the charging and discharging processes, and can effectively limit the growth of metallic lithium, so that the formation of lithium dendrites is inhibited.
(4) The pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles synthesized by the method are used as a lithium metal battery negative electrode framework material, and can reduce the nucleation potential barrier of the metal lithium by performing alloy reaction with lithium ions, so that the deposition resistance is reduced, and the metal lithium is induced to be uniformly deposited.
(5) The pomegranate-shaped carbon spheres for encapsulating the zinc oxide nanoparticles synthesized by the method have the advantages of high coulombic efficiency, good cycle stability and the like.
The pomegranate-shaped carbon spheres encapsulating zinc oxide nanoparticles and the preparation method and application thereof provided by the present invention are described in detail above, and a person skilled in the art may change the specific implementation manner and the application scope according to the idea of the embodiment of the present invention.
Claims (10)
1. A preparation method of pomegranate-shaped carbon spheres for encapsulating zinc oxide nanoparticles is characterized by comprising the following steps:
s1: adding zinc acetate into diethylene glycol, dissolving by using ultrasound, and stirring in a constant-temperature oil bath to obtain a milky mixed solution;
s2: centrifuging the milky white mixed solution, collecting filter residues, washing the filter residues with deionized water and absolute ethyl alcohol in sequence, and drying to obtain zinc oxide nanoparticle cluster balls;
s3: adding the zinc oxide nanoparticle cluster balls and dimethyl imidazole into a mixed solution of N, N-dimethylformamide and deionized water, carrying out ultrasonic treatment, and then carrying out constant-temperature oil bath stirring reaction to obtain a mixed solution;
s4: centrifuging the mixed solution, collecting filter residues, washing the filter residues by deionized water and absolute ethyl alcohol in sequence, and then drying to obtain a precursor;
s5: and calcining the precursor in an inert atmosphere to obtain the pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles.
2. The method according to claim 1, wherein in step S1: the dosage of the zinc acetate is 0.985g to 1.129g, and the dosage of the diethylene glycol is 50mL to 80mL.
3. The method according to claim 1, wherein in step S1: the reaction temperature is 140-170 ℃, and the reaction time is 1.5-10 h.
4. The method according to claim 1, wherein in the step S2: the rotating speed of the centrifugal machine for centrifugation is 5000-10000rpm, and the time for centrifugation is 5min;
the washing times with the deionized water are 1 to 3 times, and the washing times with the absolute ethyl alcohol are 1 to 3 times;
the drying time is 12-24 h.
5. The method according to claim 1, wherein in the step S3: the usage amount of the zinc oxide nanoparticle cluster ball is 1g, the usage amount of the dimethyl imidazole is 1.0-2.0 g, the usage amount of the N, N-dimethylformamide solvent is 50-150 mL, and the usage amount of the deionized water is 10-50 mL;
the reaction temperature is 70-100 ℃, and the stirring time is 12-24 h.
6. The method according to claim 1, wherein in the step S4: the rotating speed of the centrifugal machine is 5000rpm, and the centrifugal time is 5min;
the washing times with the deionized water are 1 to 3 times, and the washing times with the absolute ethyl alcohol are 1 to 3 times;
the drying time is 12-24 h.
7. The method according to claim 1, wherein in the step S5:
the inert atmosphere is N 2 The heating rate of heating to the calcining temperature is 3-5 ℃/min, the calcining temperature is 700-800 ℃, and the time for keeping the calcining temperature is 2h.
8. Pomegranate-shaped carbon spheres encapsulating zinc oxide nanoparticles prepared by the preparation method of any one of claims 1 to 7.
9. The use of the pomegranate-shaped carbon spheres encapsulating zinc oxide nanoparticles of claim 8 in a lithium metal battery negative host material or a lithium metal battery negative material.
10. The lithium metal battery negative electrode material is characterized in that the preparation method comprises the following steps:
dissolving the pomegranate-shaped carbon spheres and the carbon black of the zinc oxide nanoparticles encapsulated in the zinc oxide nanoparticles in a polyvinylidene fluoride solution of N-methyl pyrrolidone, grinding and mixing uniformly, coating the mixture on a copper foil current collector, and drying to obtain a lithium metal negative electrode material;
the mass ratio of the pomegranate-shaped carbon spheres encapsulating the zinc oxide nanoparticles to the carbon black to the polyvinylidene fluoride solution of the N-methyl pyrrolidone is 8:1:1, the drying temperature is 100 ℃, and the drying time is 12h.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105680050A (en) * | 2016-01-22 | 2016-06-15 | 南开大学 | Battery anode material obtained by pyrolyzation of 2-methylimidazole zinc salt |
| CN106784687A (en) * | 2016-12-21 | 2017-05-31 | 厦门大学 | A kind of carbon nitrogen compound hollow material and its preparation method and application |
| CN108786781A (en) * | 2018-07-04 | 2018-11-13 | 哈尔滨工业大学 | A kind of carbon coating ZnO core-shell structured nanomaterials and preparation method thereof based on MOFs |
| CN109970355A (en) * | 2019-04-04 | 2019-07-05 | 重庆大学 | Prepare method, ZnO ZIF-8 compound and the gas sensor of ZnO ZIF-8 compound |
| CN111554905A (en) * | 2020-05-14 | 2020-08-18 | 云南民族大学 | Preparation method, product and application of zinc oxide-based carbon composite nano material |
| CN113206228A (en) * | 2021-04-21 | 2021-08-03 | 华南师范大学 | Zn-Mn bimetal lithium ion battery cathode material and preparation method thereof |
| CN114497475A (en) * | 2021-12-24 | 2022-05-13 | 合肥国轩高科动力能源有限公司 | Zinc-containing nitrogen-doped porous carbon-coated zinc-based negative electrode material for lithium ion battery |
-
2022
- 2022-12-28 CN CN202211700447.0A patent/CN115924957A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105680050A (en) * | 2016-01-22 | 2016-06-15 | 南开大学 | Battery anode material obtained by pyrolyzation of 2-methylimidazole zinc salt |
| CN106784687A (en) * | 2016-12-21 | 2017-05-31 | 厦门大学 | A kind of carbon nitrogen compound hollow material and its preparation method and application |
| CN108786781A (en) * | 2018-07-04 | 2018-11-13 | 哈尔滨工业大学 | A kind of carbon coating ZnO core-shell structured nanomaterials and preparation method thereof based on MOFs |
| CN109970355A (en) * | 2019-04-04 | 2019-07-05 | 重庆大学 | Prepare method, ZnO ZIF-8 compound and the gas sensor of ZnO ZIF-8 compound |
| CN111554905A (en) * | 2020-05-14 | 2020-08-18 | 云南民族大学 | Preparation method, product and application of zinc oxide-based carbon composite nano material |
| CN113206228A (en) * | 2021-04-21 | 2021-08-03 | 华南师范大学 | Zn-Mn bimetal lithium ion battery cathode material and preparation method thereof |
| CN114497475A (en) * | 2021-12-24 | 2022-05-13 | 合肥国轩高科动力能源有限公司 | Zinc-containing nitrogen-doped porous carbon-coated zinc-based negative electrode material for lithium ion battery |
Non-Patent Citations (7)
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