CN108666562B - Cobalt-manganese-doped tin dioxide nanotube and preparation method thereof - Google Patents

Cobalt-manganese-doped tin dioxide nanotube and preparation method thereof Download PDF

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CN108666562B
CN108666562B CN201810345338.9A CN201810345338A CN108666562B CN 108666562 B CN108666562 B CN 108666562B CN 201810345338 A CN201810345338 A CN 201810345338A CN 108666562 B CN108666562 B CN 108666562B
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cobalt
manganese
acetate
nanotube
tin dioxide
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CN108666562A (en
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舒苗
李星
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Ningbo University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 discloses a cobalt manganese doped stannic oxide nanotube and a preparation method thereof, wherein a certain amount of manganese acetate, cobalt acetate and dibutyltin oxalate are dissolved in N, N-dimethylformamide and ethanol with a certain volume, then a proper amount of polyvinylpyrrolidone is added, and stirring is carried out to obtain a brownish red precursor mixture solution; then electrostatic spinning is carried out under certain voltage, flow rate and relative humidity atmosphere; and then sintering the electrostatic spinning product to obtain the cobalt manganese doped stannic oxide nanotube. Electrochemical experiment tests prove that the cobalt manganese doped stannic oxide nanotube prepared by the method has wide application prospect as a lithium ion battery cathode material. In the whole preparation process, the operation is simple, the raw material cost is low, the equipment investment is low, and the method is suitable for batch production.

Description

Cobalt-manganese-doped tin dioxide nanotube and preparation method thereof
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to cobalt-manganese-doped SnO2Nanotubes and methods of making the same.
Background
Compared with macroscopic materials, the nano-structure electrode material has large specific surface area, can shorten the transmission distance of electrons and ions, increases the area and reaction sites of an electrode/electrolyte interface, and particularly can buffer the internal stress generated by volume change in the charge-discharge process, thereby improving the cycle stability of the electrode material. Therefore, nanomaterials are an effective way to develop high performance lithium ion battery materials (pioneer, research progress on lithium storage materials for lithium ion battery cathodes 2015,29(6): 9-10; Nam K T et al Science,2006,312(5775): 885-.
SnO2The nano material as the lithium storage material has the advantages of high theoretical capacity, large energy density, wide raw material source and low cost, and improves SnO2The specific surface area of (A) is favorable for buffering the volume change during the charge and discharge process, and the specific surface effect is favorable for more lithium to be deintercalated, so that the lithium battery negative electrode material is a very potential lithium battery negative electrode material (Idota Y et al, Science,1997,276, 1395-1397; Besenhard J O et al, Journal of Power Sources,1997,68(1): 87-90). Tin dioxide nano-material (a preparation method of tin dioxide nano-material with publication number of CN106915765A) is prepared by the method of hydrothermal method in 2017 Shaotong Ting et al. Wang Y et al prepared SnO2Nanofibers, and their optical and photoconductive properties were studied (Wang Y et al, J.Appl.Phys,2007,102,093517-1, 093517-5). Although SnO2The nano material has a plurality of good aspects, but the nano material has larger volume change during charge and discharge cycles, and the material is easy to pulverize and collapse, so that the cycle number is low. And has the problems of large irreversible capacity for the first time, poor circulation stability and the like. Researches find that the doping of transition metal is beneficial to improving SnO2The electrochemical performance of (2). VO was first reported by Dahn et al in 19942/LiNO3/LiMn204The electrochemical performance of aqueous lithium ion battery materials (Science,1994,264(5162): 1115-. At present, the cycle performance of the stannate material applied to the lithium ion battery needs to be improved.
The positive electrode material of the lithium ion battery is generally cobalt lithium oxide, nickel lithium oxide, and manganese lithium oxide. Because of the characteristics of high voltage, stable discharge and the like of the cobalt lithium oxide, the application prospect of the lithium cobalt oxide is better. 2011 LiuhaoWen et al prepared 3 different nano-scale cobaltates by a hydrothermal method and tested the charge and discharge performance (Journal of South-Central University for national industries, 2011,30(4): 11-15). However, cobalt-based materials have poor thermal stability and are expensive. Lithium manganate and ternary materials also hold an important position in the market. The raw material for preparing lithium manganate has been reported to have manganese series products: electrolytic manganese dioxide, high-purity manganous-manganic oxide and spherical high-purity manganous oxide; the manganese series product for preparing the ternary material mainly comprises high-purity manganese sulfate monohydrate. Wangshangcai et al used electrolytic manganese dioxide as a raw material, and explored the cycle performance of spinel lithium manganate prepared by a solid-phase method (research on stone-type lithium manganate, mineral smelting engineering, 2012,32(6): 113-115). But the application of the manganate as a lithium battery material has the problems of short cycle service life and the like. In order to improve the electrochemical performance of the lithium ion battery, the invention discloses a cobalt-manganese-doped tin dioxide nanotube and a preparation method thereof.
Disclosure of Invention
The invention aims to solve the technical problem of providing a cobalt and manganese doped stannic oxide nanotube and a preparation method thereof by doping cobalt manganese metal ions in stannic oxide in the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: a cobalt-manganese doped stannic oxide nanotube with chemical formula of Co0.25Mn0.25Sn0.5O2。
The invention also provides a preparation method of the cobalt-manganese-doped tin dioxide nanotube, which is characterized in that the preparation method comprises the following steps of preparing an electrostatic spinning product by taking manganese acetate, cobalt acetate and dibutyltin oxalate as main raw materials and adding a proper amount of high polymers as an adhesive under the condition of high voltage by using an electrostatic spinning technology, and sintering in a muffle furnace to obtain the cobalt-manganese-doped tin dioxide nanotube, wherein the preparation method comprises the following steps:
1) weighing a certain amount of manganese acetate (Mn (CH)3COO)2) Cobalt acetate (Co (CH)3COO)2) Dibutyl tin oxalate dissolved in certain volume of N, N-dimethyl formamide (DMF) and ethanol (CH)3CH2OH), then adding a proper amount of PVP (K-120, polyvinylpyrrolidone), and stirring for 14-16 h to obtain a brownish red precursor mixture solution, wherein the molar ratio of metal elements in the mixture solution is Co: mn: sn is 1: 1: 2;
2) performing electrostatic spinning on the brownish red precursor mixture solution under the conditions of 18-20 kv voltage, 0.7-0.9 mL/h flow rate and 35-45% relative humidity;
3) and (2) placing the obtained electrostatic spinning product in a crucible, then placing the crucible in a muffle furnace for sintering at 650-700 ℃ for 2-4 h, then naturally cooling to room temperature to obtain a brown solid, carrying out composition structure analysis on the brown solid by using X rays (figure 1), and observing the appearance of the brown solid as a nano tube by using a scanning electron microscope (figure 2) to obtain the cobalt-manganese-doped tin dioxide nano tube.
The invention also provides the application of the cobalt-manganese-doped tin dioxide nanotube obtained by the preparation method, and the nanotube is used as a lithium ion battery cathode material and has a specific first discharge capacity of 1114mAh g-1And the charge-discharge efficiency is still kept above 99% after the circulation for 90 times.
Compared with the prior art, the invention has the following characteristics:
the cobalt-manganese-doped tin dioxide nanotube prepared by the invention has a larger specific surface, and the initial discharge specific capacity of the nanotube used as a battery cathode material is 1114mAh g-1The charge-discharge efficiency remained above 99% after 90 cycles (fig. 3).
Drawings
FIG. 1 is an XRD pattern of a cobalt and manganese doped stannic oxide nanotube prepared in accordance with the present invention;
FIG. 2 is an SEM image of a cobalt and manganese doped tin dioxide nanotube prepared according to the present invention;
FIG. 3 is an electrochemical spectrum of a cobalt-manganese doped tin dioxide nanotube prepared according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
1.0mmol (0.173g) of manganese acetate (Mn (CH)3COO)2) 1.0mmol (0.177g) of cobalt acetate (Co (CH)3COO)2) And 2.0mmol (0.702g) of dibutyltin oxalate (C12H24O4Sn) in 10mL of N, N-Dimethylformamide (DMF) and 10mL of ethanol (CH)3CH2OH) and then 2.8g of PVP (K-120, polyvinylpyrrolidone), stirring for 14h to obtain a brownish red precursor mixture solution; carrying out electrostatic spinning on the brownish red precursor mixture solution under the conditions of 18kv voltage, 0.7mL/h flow rate and 35% relative humidity; and (3) placing the obtained electrostatic spinning product in a crucible, then placing the crucible in a muffle furnace to sinter for 3 hours at 700 ℃, and then naturally cooling to room temperature to obtain a brown solid.
Example 2
0.5mmol (0.0865g) of manganese acetate (Mn (CH)3COO)2) 0.5mmol (0.0885g) of cobalt acetate (Co (CH)3COO)2) And 1.0mmol (0.351g) of dibutyltin oxalate (C12H24O4Sn) in 10mL of N, N-Dimethylformamide (DMF) and 10mL of ethanol (CH)3CH2OH), then adding 2.1g of PVP (K-120, polyvinylpyrrolidone) and stirring for 15h to obtain a brownish red precursor mixture solution; carrying out electrostatic spinning on the brownish red precursor mixture solution under the conditions of 19kv voltage, 0.8mL/h flow rate and 40% relative humidity; and (3) placing the obtained electrostatic spinning product in a crucible, then placing the crucible in a muffle furnace for sintering at 650 ℃ for 4h, and then naturally cooling to room temperature to obtain a brown solid.
Example 3
0.5mmol (0.0865g) of manganese acetate (Mn (CH)3COO)2) 0.5mmol (0.0885g) of cobalt acetate (Co (CH)3COO)2) And 1.0mmol (0.351g) of dibutyltin oxalate (C12H24O4Sn) in 10mL of N, N-Dimethylformamide (DMF) and 10mL of ethanol (CH)3CH2OH), then adding 3.1g of PVP (K-120, polyvinylpyrrolidone) and stirring for 16h to obtain a brownish red precursor mixture solution; carrying out electrostatic spinning on the brownish red precursor mixture solution under the conditions of 20kv voltage, 0.9mL/h flow rate and 45% relative humidity; and (3) placing the obtained electrostatic spinning product in a crucible, then placing the crucible in a muffle furnace for sintering at 700 ℃ for 2h, and then naturally cooling to room temperature to obtain a brown solid.
The substances participating in the reaction in the above examples are all chemically pure and above grade.
The brown solid obtained in the above example was subjected to compositional structure analysis with X-ray (fig. 1), and observed by scanning electron microscopy to be nanotube-shaped (fig. 2), and the charge-discharge and cycle properties are shown in fig. 3.

Claims (2)

1. A cobalt-manganese-doped tin dioxide nanotube is characterized in that the chemical formula of the element composition of the nanotube is Co0.25Mn0.25Sn0.5O2(ii) a The preparation method of the nanotube comprises the following steps:
1) weighing a certain amount of manganese acetate, cobalt acetate and dibutyltin oxalate, dissolving the manganese acetate, the cobalt acetate and the dibutyltin oxalate in N, N-dimethylformamide and ethanol with a certain volume, adding a proper amount of PVP, and stirring for 14-16 hours to obtain a brownish red precursor mixture solution, wherein the molar ratio of metal elements in the mixture solution is Co: mn: sn is 1: 1: 2;
2) performing electrostatic spinning on the obtained brownish red precursor mixture solution under the conditions of 18-20 kv voltage, 0.7-0.9 mL/h flow rate and 35-45% of relative humidity;
3) and placing the obtained electrostatic spinning product in a crucible, then placing the crucible in a muffle furnace for sintering at 650-700 ℃ for 2-4 h, and then naturally cooling to room temperature to obtain the cobalt-manganese-doped tin dioxide nanotube.
2. The use of the cobalt-and manganese-doped tin dioxide nanotubes of claim 1 as negative electrode material of lithium ion battery with a specific first discharge capacity of 1114mAh g-1And the charge-discharge efficiency is still kept above 99% after the circulation for 90 times.
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