CN113346070A - Preparation method of lantern-shaped metal-oxygen-carbon composite material and application of lantern-shaped metal-oxygen-carbon composite material in non-aqueous potassium ion battery - Google Patents
Preparation method of lantern-shaped metal-oxygen-carbon composite material and application of lantern-shaped metal-oxygen-carbon composite material in non-aqueous potassium ion battery Download PDFInfo
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Abstract
The invention discloses a preparation method of a lantern-shaped metal-oxygen-carbon composite material and application thereof in a non-aqueous potassium ion battery, and M-O is obtained by a hydrolysis methodOvAnd (3) calcining the CNTs precursor at the C-layer in a weak reducing atmosphere, and introducing oxygen vacancy defects into the nano amorphous body to finally obtain the lantern-shaped metal-oxygen-carbon composite material with the crystal form nanotube inserted with the oxygen vacancy defects. The lantern-shaped metal-oxygen-carbon composite material prepared by the invention has superior potassium storage performance and can be used as a negative electrode material of a high-performance non-aqueous potassium ion battery.
Description
Technical Field
The invention belongs to the technical field of preparation of advanced secondary battery materials, and particularly relates to a preparation method of a lantern-shaped metal-oxygen-carbon composite material with oxygen vacancy defects interpenetrated by crystal nanotubes and application of the composite material in a non-aqueous potassium ion battery.
Background
The rapid development of the lithium battery industry and the widespread commercialization of lithium ion batteries has led in recent decades to a doubling of the consumption of lithium resources, the price of which has also rapidly increased to unacceptable levels. Therefore, research and development of low-cost non-lithium-based electrochemical energy storage devices with excellent energy storage performance to replace increasingly expensive lithium ion batteries have become an irreparable research task for researchers in the field of energy storage. In recent years, research on related electrode materials of potassium ion batteries becomes a new research hotspot in the field of energy storage, and the potassium ion batteries are taken as a class of advanced rechargeable batteries with rich, green and low-price raw material resources, so that research and development of the potassium ion batteries are beneficial to further improving the utilization level of green renewable energy. Therefore, the development of studies on potassium ion batteries (KIBs) is of great practical and academic interest. As for transition metal matrix composites of the conversion reaction type, due to their abundant resources and higher theoretical specific capacity, they have attracted extensive attention from researchers in the field of energy storage. Among transition metal oxides, manganese monoxide (MnO) is preferred because of its high density (5.43 g cm)-3) Higher theoretical specific capacity (756 mA h g)-1) Low voltage hysteresis (<0.7V) and environmental friendliness, etc. become a promising candidate material for the negative electrode of the potassium ion battery. However, similar to other transition metal oxide negative electrode materials, MnO negative electrodes also suffer from relatively poor rate capability and relatively poor cycle stability, which are caused by their inherent poor conductivity and large volume expansion during charge and discharge.
In order to improve the poor potassium storage performance of metal oxides, a more effective method is to use conductive carbon materials (e.g., crystalline carbon nanotubes) to interpenetrate the metal oxides. The reason for selecting the crystal form carbon nanotube interpenetration composite material is as follows: (1) amorphous MnO undergoes only slight volume expansion (< 6%) after sylation and the sylated MnO can improve electrochemical conductivity during discharge; (2) the potassium MnO has good thermal stability and higher safety, and inhibits the thermal reaction of a high-potassium metal oxide phase and an electrolyte, so that the rate capability and the stable interface of the MnO are improved.
Another effective method for improving the potassium storage performance of metal oxides is to design and construct various special nanocomposite materials (such as nano sheets, crystalline/amorphous nano wires, nano cones, multi-wall/single-wall nano tubes, nano particles or hollow nano microspheres) containing oxygen vacancy defects. Because oxygen vacancy defects can not only induce the change of the electronic structure of the metal oxide and promote electron transmission, but also improve the surface thermodynamics of the electrode/electrolyte interface, thereby promoting the phase change thereof and maintaining the integrity of the electrode surface interface. In addition, the larger contact area and more active vacancy defects of the nano material can provide more potassium ion storage sites and improve the electron transfer kinetics of the nano material, so that the electrochemical energy storage performance of the nano material is effectively enhanced.
Disclosure of Invention
The invention solves the technical problem of providing a lantern-shaped manganese-oxygen-carbon (abbreviated as M-O) with oxygen vacancy defects interpenetrated by a crystal type nanotubeOvCNTs at the C-line, M for metal, and the line for interpenetration, OvAn abbreviation for Oxygen Vacancy) nanocomposite and its use in a non-aqueous potassium ion battery. The lantern-shaped M-OOvThe CNTs nano composite material with the-C layer contains M-OOvThe mass percent of the-C-layer CNTs nano composite material is 10-80%, and C accounts for M-OOvThe mass percent of the CNTs nano composite material at the-C layer is 10-85%, and the balance is O. Researches show that the lantern-shaped metal-oxygen-carbon composite material has superior potassium storage performance and can be used as a negative electrode material of a high-performance non-aqueous potassium ion battery.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the lantern-shaped metal-oxygen-carbon composite material is characterized by comprising the following specific steps of:
step S1: soaking the carbon nano tube in a mixed solution of nitric acid and sulfuric acid, heating in a water bath, stirring, filtering, collecting the obtained product, washing the product with deionized water for several times, and drying the product to obtain an oxidized carbon nano tube;
step S2: dispersing the oxidized carbon nano tube obtained by the pretreatment in the step S1 and polyvinylpyrrolidone in a methanol solution, uniformly dispersing the carbon nano tube under the action of ultrasound, and uniformly mixing the obtained dispersion with a manganese source, a cobalt source or a nickel source to obtain a mixed system, wherein the manganese source is one or more of manganese chloride, manganese nitrate, manganese carbonate or manganese acetate, the cobalt source is one or more of cobalt chloride, cobalt nitrate, cobalt carbonate or cobalt acetate, and the nickel source is one or more of nickel chloride, nickel nitrate, nickel carbonate or nickel acetate;
step S3: dissolving a trimesic acid solution in a methanol solution to form a transparent solution, then adding the transparent solution into the mixed system obtained in the step S2 at a constant speed under the stirring condition, standing, then collecting precipitates through centrifugation, thoroughly washing the precipitates with methanol for multiple times to remove a surfactant and residual ions, and then drying the obtained product to obtain a precursor of the lantern-shaped manganese-based material;
step S4: the precursor obtained in the step S3 is added with 1-20 percent of nitrogen gas under the condition of high-purity nitrogen atmosphereoC min-1The temperature rise rate is increased to 300-900-oC, performing heat treatment for 0.5-10h to obtain the lantern-shaped metal-oxygen-carbon composite material with the crystal form nanotube inserted with the oxygen vacancy defect.
Further limiting, the feeding molar ratio of the manganese source, the cobalt source or the nickel source to the trimesic acid is 0.328-0.667:1, and the feeding molar ratio of the oxidized carbon nano tube to the polyvinylpyrrolidone is 1.28-1.61: 1.
The application of the lantern-shaped metal-oxygen-carbon composite material as a negative electrode material of a high-performance non-aqueous potassium ion battery is provided.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the preparation method is simple, mild in reaction conditions, low in cost and beneficial to industrial production.
2. The invention provides a preparation method of a lantern-shaped metal-oxygen-carbon composite material with oxygen vacancy defects interpenetrated by crystalline nanotubes, which obtains M-O by a hydrolysis methodOvCNTs precursor at the-C-axis, then by calcination in a weakly reducing atmosphere, oxygen vacancy defects are introduced into the nano-amorphous.
3. The oxygen vacancy defect in the invention can not only induce the change of the electronic structure of the metal oxide, so that the transmission process of electrons and ions becomes possible; phase changes may also be promoted by altering the surface thermodynamics in the presence of the electrode/electrolyte interface, helping to maintain the integrity of the electrode surface.
4. The potassium storage mechanism of the lantern-shaped metal-oxygen-carbon composite material with the crystalline form nanotube interpenetrated with the oxygen vacancy defect prepared by the invention is different from other metal oxides. Firstly, oxygen vacancy defects in the lantern-shaped metal-oxygen-carbon composite material can not only improve the conductivity of the material, but also store potassium active sites; secondly, the potassium storage performance of the lantern-shaped metal-oxygen-carbon structure is more stable, and the metal oxide can not generate agglomeration, cracking and other adverse phenomena during the kalification/potassium removal process; thirdly, the lantern-shaped metal-oxygen-carbon composite material can effectively prevent the occurrence of side reaction of the interface between the electrolyte and the electrodes and can better infiltrate the electrolyte to form a uniform solid electrolyte membrane; finally, the crystal form nanotube in the lantern-shaped metal-oxygen-carbon composite material not only plays a role in high electron transmission, but also can store potassium ions. In contrast, not only do common metal oxides agglomerate and crack during cycling, their surfaces can also undergo side reactions with the electrolyte, producing more and thicker solid electrolyte membranes, ultimately leading to severe performance degradation. Therefore, the construction of the electrode material with a special structure has great significance for improving the potassium storage performance of the metal oxide.
Drawings
FIG. 1 shows Mn-O in example 1Ov-X-ray diffraction (XRD) pattern of CNTs nanocomposite at the C-line;
FIG. 2 shows Mn-O in example 1Ov-Scanning Electron Microscope (SEM) image of CNTs nanocomposite at C-line;
FIG. 3 shows Mn-O in example 1OvA corresponding multiplying power performance diagram when the CNTs nano composite material at the C-axis is used as a negative electrode material of the potassium ion battery;
FIG. 4 shows Mn-O in example 1OvAnd (3) a corresponding cycle performance diagram of the CNTs nano composite material at the-C line as a negative electrode material of the potassium ion battery.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Preparation of Mn-OOvCNTs nano composite material of-C-layer
0.5 g of carbon nanotubes was immersed in 60 mL of a mixed solution of nitric acid and sulfuric acid, 80%oStirring in water bath for 3h, filtering, collecting the obtained product, washing with deionized water for several times, and filtering at 80 deg.CoAnd C, drying the product to obtain the oxidized carbon nano tube. Then, 0.1 g of the oxidized carbon nano tube obtained by pretreatment and 0.4 g of polyvinylpyrrolidone (PVP) are dispersed in 50 mL of methanol solution, the carbon nano tube is uniformly dispersed under the action of ultrasonic waves, and then the obtained dispersion liquid is mixed with 0.5 g of manganese acetate to obtain a mixed solution A; dissolving 1.9 g of trimesic acid solution in 50 mL of methanol solution to form transparent solution B, slowly adding the transparent solution B into the mixed solution A at a constant speed under the stirring condition, standing for 24h, then collecting precipitates by centrifugation, thoroughly washing the precipitates with methanol for multiple times to remove a surfactant and residual ions, and then drying the obtained product at 70 ℃ for 12h to obtain precursor powder of the two-dimensional spherical lantern-shaped manganese-based material; finally, under the condition of high-purity nitrogen atmosphere, the mixture is heated in a tubular furnace by 1-2oC min-1The temperature rise rate is increased to 500oC calcining precursor powder for 2h, and naturally cooling to room temperature to obtain Mn-OOvCNTs nano composite material at the-C-layer.
Example 2
Preparation of Co-OOvCNTs nano composite material of-C-layer
0.8 g of pristine multi-walled carbon nanotubes were immersed in 70 mL of a mixed solution of nitric acid and sulfuric acid, 80oStirring in water bath for 4h, filtering, collecting the obtained product, washing with deionized water for several times, and filtering at 80 deg.CoAnd C, drying the product to obtain the oxidized multi-walled carbon nano tube. Then 0.09 g of the oxidized multi-walled carbon nanotubes obtained by pretreatment and 0.7 g of polyvinylpyrrolidone (PVP) were dispersed in 10mL of methanol solution, the carbon nanotubes were uniformly dispersed under the action of ultrasound, and then the obtained dispersion was mixed with 0.85 g of acetic acid tetrahydrateMixing cobalt to obtain a mixed solution A; then, 1.9 g of a trimesic acid solution was dissolved in 60 mL of a methanol solution to form a transparent solution B, which was then slowly added to the mixed solution A at a uniform rate while stirring, allowed to stand for 24 hours, followed by collecting the resulting precipitate by centrifugation, washing the precipitate thoroughly with methanol several times to remove a surfactant and residual ions, and then subjecting the resulting product to a washing with methanol at 70 ℃ to obtain a solution BoC, drying for 12 hours to obtain precursor powder of the two-dimensional spherical lantern-shaped cobalt-based material; finally, under the condition of high-purity nitrogen atmosphere, the mixture is heated in a tubular furnace by 1-2oC min-1The temperature rise rate is increased to 600oC calcining precursor powder for 2h, and naturally cooling to room temperature to obtain Co-OOvCNTs nano composite material at the-C-layer.
Example 3
Preparation of Ni-OOvCNTs nano composite material of-C-layer
1 g of the original carbon nanotubes were immersed in 90 mL of a mixed solution of nitric acid and sulfuric acid, 80%oStirring in water bath for 3h, filtering, collecting the obtained product, washing with deionized water for several times, and filtering at 80 deg.CoDrying the product under the condition of C to obtain an oxidized carbon nano tube; then adding 0.07 g of the oxidized carbon nano tube obtained by pretreatment and 0.35 g of polyvinylpyrrolidone (PVP) into 90 mL of methanol solution, uniformly dispersing the carbon nano tube under the action of ultrasonic waves, and mixing the obtained dispersion liquid with 1.2 g of nickel acetate to obtain a mixed solution A; then, 1.9 g of a trimesic acid solution was dissolved in 50 mL of a methanol solution to form a transparent solution B, which was then slowly added to the mixed solution A at a uniform speed with stirring, allowed to stand for 24 hours, followed by collecting the resulting precipitate by centrifugation, washing the precipitate thoroughly with methanol several times to remove a surfactant and residual ions, and then subjecting the resulting product to 80 ℃oC, drying for 12 hours to obtain precursor powder of the lantern-shaped nickel-based material; finally, under the condition of high-purity nitrogen atmosphere, the mixture is heated in a tubular furnace by 1-2oC min-1The temperature rise rate is up to 700oC calcining precursor powder for 2h, and naturally cooling to room temperature to obtain Ni-OOvCNTs nano composite material at the-C-layer.
Example 4
Mn-O prepared in example 1Ov-C-lineMixing a CNTs nano composite material, carbon black and a binder in a mass ratio of 70:20:10 to prepare a slurry, uniformly coating the slurry on a copper foil current collector to obtain a working electrode, taking potassium metal as a counter electrode, taking a glass fiber microporous filter membrane as a diaphragm and 1 mol L of the working electrode-1 KPF6(the solvent is a mixed solution of ethylene carbonate and dimethyl carbonate in a volume ratio of 1: 1) as an electrolyte, and the battery is assembled in a glove box.
And (3) carrying out charge and discharge tests on the assembled battery on a charge and discharge tester, wherein the tested charge and discharge interval is 0.005-3V. At 20 mA g-1、30 mA g-1、50 mA g-1、80 mA g-1、100 mA g-1、150 mA g-1And 200 mA g-1The rate performance of the assembled battery was tested at charge and discharge rates of (a). Then at 30 mA g-1The cycle performance of the assembled battery was tested under the rate conditions of (1).
As shown in FIG. 3, Mn-O synthesized in example 1OvComparison of the rate performance of the CNTs nanocomposite at the-C-line and commercial MnO as the negative electrode material of potassium ion batteries. As can be seen from the figure, the specific capacity of the material is much higher than that of commercial MnO at the same current density, for example, the material is 20 mA g-1The charging specific capacity can reach 318 mA g under the current density-1While commercial MnO is only 80 mA g-1FIG. 4 shows Mn-O in example 1OvAnd (3) a cycle performance diagram of the CNTs nano composite material at the-C-line as a potassium ion battery negative electrode material. As can be seen from the figure, the material is at 30 mA g-1Under the current density, the first reversible specific capacity reaches 248 mA h g-1After circulating for 100 circles, the pressure can still be kept at 189 mA h g-1The specific capacity retention rate reaches 76%. The Mn-OOvThe CNTs nano composite material at the-C-line shows better rate performance and cycle performance when being used as a negative electrode material of a potassium ion battery.
The Mn-O obtained in examples 1-3 was characterized by XRD and SEMOvCNTs nanosphere composite material at-C-layer, FIG. 1 shows Mn-O obtained in example 1OvThe XRD pattern of the CNTs nano composite material at the-C layer shows that the synthesized material contains carbon nano tubes. Since the MnO obtained is amorphous, there is no diffraction thereofPeak(s). FIG. 2 shows Mn-O in example 1OvScanning Electron Microscope (SEM) picture of CNTs nano composite material at-C-layer, and Mn-O is foundOvThe CNTs nanocomposite material of the-C-line is spherical and is stacked by sheets.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (4)
1. A preparation method of a lantern-shaped metal-oxygen-carbon composite material is characterized by comprising the following specific steps:
step S1: soaking the carbon nano tube in a mixed solution of nitric acid and sulfuric acid, heating in a water bath, stirring, filtering, collecting the obtained product, washing the product with deionized water for several times, and drying the product to obtain an oxidized carbon nano tube;
step S2: dispersing the oxidized carbon nano tube obtained by the pretreatment in the step S1 and polyvinylpyrrolidone in a methanol solution, uniformly dispersing the carbon nano tube under the action of ultrasound, and uniformly mixing the obtained dispersion with a manganese source, a cobalt source or a nickel source to obtain a mixed system, wherein the manganese source is one or more of manganese chloride, manganese nitrate, manganese carbonate or manganese acetate, the cobalt source is one or more of cobalt chloride, cobalt nitrate, cobalt carbonate or cobalt acetate, and the nickel source is one or more of nickel chloride, nickel nitrate, nickel carbonate or nickel acetate;
step S3: dissolving a trimesic acid solution in a methanol solution to form a transparent solution, then adding the transparent solution into the mixed system obtained in the step S2 at a constant speed under the stirring condition, standing, then collecting precipitates through centrifugation, thoroughly washing the precipitates with methanol for many times to remove a surfactant and residual ions, and then drying the obtained product to obtain a precursor of the lantern-shaped metal-oxygen-carbon composite material;
step S4: the precursor obtained in the step S3 is put under the condition of high-purity nitrogen atmosphereIn the range of 1-20oC min-1The temperature rise rate is increased to 300-900-oC, performing heat treatment for 0.5-10h to obtain the lantern-shaped metal-oxygen-carbon composite material with the crystal form nanotube inserted with the oxygen vacancy defect.
2. The method of making a lantern-shaped metal-oxygen-carbon composite of claim 1, wherein: the feeding molar ratio of the manganese source, the cobalt source or the nickel source to the trimesic acid is 0.328-0.667:1, and the feeding molar ratio of the oxidized carbon nano tube to the polyvinylpyrrolidone is 1.28-1.61: 1.
3. A lantern-shaped metal-oxygen-carbon composite material prepared by the method of claim 1 or 2, wherein: the metal in the lantern-shaped metal-oxygen-carbon composite material accounts for 10-80% of the metal-oxygen-carbon composite material by mass, the C accounts for 10-85% of the metal-oxygen-carbon composite material by mass, and the balance is O.
4. Use of the lantern-shaped metal-oxygen-carbon composite material prepared by the method of claim 1 as a negative electrode material of a high-performance non-aqueous potassium ion battery.
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| CN113571674A (en) * | 2021-09-22 | 2021-10-29 | 河南师范大学 | Preparation method and application of in-situ carbon-coated binary transition metal oxide heterojunction bowl-shaped nano composite material |
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