CN108923040B - Preparation method and application of anion-cation co-doped molybdenum oxyhydroxide nanosheet - Google Patents

Preparation method and application of anion-cation co-doped molybdenum oxyhydroxide nanosheet Download PDF

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CN108923040B
CN108923040B CN201810663554.8A CN201810663554A CN108923040B CN 108923040 B CN108923040 B CN 108923040B CN 201810663554 A CN201810663554 A CN 201810663554A CN 108923040 B CN108923040 B CN 108923040B
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CN108923040A (en
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王海
逯慧兵
李惠敏
李阳
杨彩虹
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Guilin University of Technology
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Abstract

The invention discloses a preparation method and application of anion and cation co-doped molybdenum oxyhydroxide nanosheets. Adding analytically pure sodium dodecyl sulfate into deionized water, and uniformly stirring; then adding the analytically pure dodecanethiol into the solution, and uniformly stirring; adding analytically pure ammonium molybdate into the solution, and uniformly stirring; dropwise adding analytically pure nitric acid into the mixed solution, and uniformly stirring; adding analytically pure chromium nitrate into the mixed solution, and uniformly stirring; transferring the obtained solution into a reaction kettle, stirring, transferring the solution into a stainless steel reaction kettle with a polytetrafluoroethylene substrate, carrying out hydrothermal reaction, and cooling to room temperature to obtain a dark blue precipitate; washing with deionized water or absolute ethyl alcohol, and drying to obtain anion and cation co-doped MoO2.5(OH)0.5Nanosheets. The invention has low cost, simple process control process and easy large-scale production.

Description

Preparation method and application of anion-cation co-doped molybdenum oxyhydroxide nanosheet
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a cation and anion co-doped molybdenum oxyhydroxide (MoO)2.5(OH)0.5) The preparation method of the negative electrode material of the nano-sheet battery can be used as the negative electrode material of the lithium ion battery.
Background
The development of novel two-dimensional layered electrode materials is always a research hotspot in the field of energy storage. The invention uses MoO3The anion and cation co-doped MoO with excellent performance is obtained by taking the parent structure as a reference object and adopting proper chemical reaction conditions2.5(OH)0.5A negative electrode material of a nanosheet battery.
As is well known, MoO3Have gained a great deal of application in the field of lithium ion batteries and supercapacitors. Its unique structural features, such as being composed of [ MoO ]6]Octahedron is a basic structural unit, and forms chain connection by sharing angle, every two are similarThe chains of (a) constitute a layered structure by a framework formed by the common edges, and the layers are connected by van der waals forces. MoO3The unique layered structure characteristic has a large number of ion channels, Mo in the frame layer is easy to change valence state, and the valence state change is very favorable for the application of Mo in the fields of lithium ion batteries and supercapacitors. However, one not negligible fact is that MoO3Intrinsic conductivity and ion diffusion rate are poor.
To the above problems, to MoO3Tailoring of the crystal structure is one of the effective ways to solve the above problems. The method for cutting structures such as oxygen vacancy, low-valence element doping substituted high-valence Mo and the like has been verified theoretically and experimentally. However, for MoO3The co-doping of the framework with anions and cations, and the introduction of a large amount of OH in the framework structure have not been reported yet. From the perspective of crystal structure, because of MoO2.5(OH)0.5Mo in the structure has mixed valence state, and the conductivity of Mo is improved to result in MoO2.5(OH)0.5Comparative MoO3Is expected to have more excellent potential for lithium ion lithium storage. However, currently about MoO2.5(OH)0.5The synthesis, modification and performance of the material are not reported.
Disclosure of Invention
The invention aims to solve the problems and provide an anion and cation co-doped MoO2.5(OH)0.5A preparation method and application of a nano-sheet battery cathode material.
The method comprises the following specific steps:
(1) adding 1-3 g of analytically pure sodium dodecyl sulfate into 30-50 ml of deionized water, stirring for 10-30 minutes, and uniformly stirring.
(2) Adding 5-10 ml of analytically pure dodecyl mercaptan into the solution obtained in the step (1), stirring for 10-30 minutes, and stirring uniformly.
(3) And (3) adding 1-3 g of analytically pure ammonium molybdate into the product obtained in the step (2), stirring for 10-30 minutes, and uniformly stirring.
(4) And (4) dropwise adding 1-3 ml of analytically pure nitric acid into the product obtained in the step (3), stirring for 10-30 minutes, and uniformly stirring.
(5) Adding 1-2 g of analytically pure chromium nitrate into the product obtained in the step (4), stirring for 10-30 minutes, and stirring uniformly.
(6) Transferring the solution obtained in the step (5) into a reaction kettle, stirring, transferring the solution into a stainless steel reaction kettle with a polytetrafluoroethylene substrate, carrying out hydrothermal reaction at the temperature of 150 ℃ and 220 ℃ for 24-30 hours, and cooling to room temperature to obtain a dark blue precipitate; repeatedly cleaning the dark blue precipitate with deionized water or anhydrous ethanol for 2-3 times, and drying in drying oven at 60-80 deg.C for 10-12 hr to obtain anion and cation co-doped MoO2.5(OH)0.5Nanosheets.
The anion and cation co-doped MoO2.5(OH)0.5The nano sheet can be used as a negative electrode material of a lithium ion battery.
The method has simple process, low cost and easy large-scale production, and the unique anion and cation co-doped MoO is prepared2.5(OH)0.5The two-dimensional nanosheet structure of the nanosheet is beneficial to lithium ion diffusion; on the other hand, MoO2.5(OH)0.5The nano-sheet is doped with anions and cations, and the Mo-O bond bonding energy is reduced due to the poor electronegativity of sulfur compared with oxygen, and in addition, the chromium doping replaces high valence molybdenum to form the mixed valence molybdenum, which is also beneficial to electron transmission. When the material is used as a lithium ion battery cathode material, 535 mAmp hours/g is obtained after 150 cycles under the current density of 1A/g; at a current density of 5 amps/g, 376 mAmp-hrs/g after 150 cycles. The results indicate that the sulfur and chromium are codoped with MoO2.5(OH)0.5The nano-sheet has excellent cycle stability and is a potential application material of a promising high-performance lithium ion battery.
In addition, anion and cation codope MoO2.5(OH)0.5The nanosheet is subjected to one-step simple hydrothermal synthesis, so that a new way and a new idea are provided for exploring a novel two-dimensional electrode material in the future.
Drawings
FIG. 1 is an X-ray diffraction pattern of example 1 of the present invention.
FIG. 2 is a SEM image of field emission display in example 1 of the present invention. (a) Low magnification (b) and high magnification (c) to (d).
FIG. 3 is an elemental energy spectrum of example 1 of the present invention.
FIG. 4 is a cycle chart at a current density of 1 ampere/gram for example 1 of the present invention.
FIG. 5 is a cycle chart at a current density of 5 amps/gram for example 2 of the present invention.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1:
sulfur and chromium codoped MoO2.5(OH)0.5A method of preparing a nanoplatelet material, comprising the steps of:
(1) add 1 analytically pure sodium dodecyl sulfate to 30 ml deionized water, stir for 15 minutes, stir well.
(2) Adding 5 ml of analytically pure dodecyl mercaptan into the solution obtained in the step (1), stirring for 15 minutes, and stirring uniformly.
(3) Adding 1 g of analytically pure ammonium molybdate into the product obtained in the step (2), stirring for 15 minutes, and stirring uniformly.
(4) Dropwise adding 1 ml of analytically pure nitric acid into the product obtained in the step (3), stirring for 15 minutes, and uniformly stirring.
(5) 1 g of analytically pure chromium nitrate was added to the product obtained in step (4), stirred for 15 minutes and stirred well.
(6) Transferring the solution obtained in the step (5) into a reaction kettle, stirring, transferring the solution into a stainless steel reaction kettle with a polytetrafluoroethylene substrate, carrying out hydrothermal reaction at 150 ℃ for 26 hours, and cooling to room temperature to obtain a dark blue precipitate; repeatedly washing the dark blue precipitate with deionized water for 3 times, and drying in a drying oven at 80 deg.C for 10 hr to obtain sulfur and chromium co-doped MoO2.5(OH)0.5Nanosheets.
Prepared sulfur and chromium codoped MoO2.5(OH)0.5Nano sheet material as lithium ion battery cathode material, and lithium ion battery assembling method and traditional assembling method thereofAnd (5) the consistency is achieved. The preparation method of the negative plate comprises the following steps: adopts sulfur and chromium codoped MoO2.5(OH)0.5The nano-sheet material powder is used as a negative electrode material, polytetrafluoroethylene is used as a binder, and acetylene black is used as a conductive agent. The mass ratio of the three raw materials is 70:20: 10. Fully and uniformly stirring the components in proportion, then coating the mixture on a copper sheet by using a film scraper method, and pressing an electrode sheet with the thickness of about 0.15 mm on a tablet press; and drying the pressed negative plate in an oven at 90 ℃ for 14 hours for later use. 1 mol/l LiPF6The lithium ion battery is dissolved in ethylene carbonate and dimethyl carbonate to be used as electrolyte, a lithium sheet is used as a positive electrode, CR2025 type stainless steel is used as a battery shell, and Celgard2025 is used as a diaphragm to assemble the button type lithium ion battery.
Obtained sulfur and chromium codoped MoO2.5(OH)0.5The electrochemical performance of the nanosheet material as a negative electrode material of a lithium ion battery is shown in fig. 4, and the negative electrode material is 535 mAmp hours/g after 150 cycles at a current density of 1 Amp/g. The results indicate that the sulfur and chromium co-doped MoO2.5(OH)0.5The nano-sheet has excellent cycle stability and is a potential application material of a promising high-performance lithium ion battery.
Example 2:
sulfur and chromium codoped MoO2.5(OH)0.5A method of preparing a nanoplatelet material, comprising the steps of:
(1) add 3 g of analytically pure sodium dodecyl sulfate to 50 ml of deionized water, stir for 15 minutes, and stir well.
(2) Adding 10 ml of analytically pure dodecyl mercaptan into the solution obtained in the step (1), stirring for 15 minutes, and stirring uniformly.
(3) Adding 3 g of analytically pure ammonium molybdate into the product obtained in the step (2), stirring for 15 minutes, and stirring uniformly.
(4) Dropwise adding 3 ml of analytically pure nitric acid into the product obtained in the step (3), stirring for 15 minutes, and uniformly stirring.
(5) 2 g of analytically pure chromium nitrate was added to the product obtained in step (4), stirred for 15 minutes and stirred well.
(6) The step (A) is5) Transferring the obtained solution into a reaction kettle, stirring, transferring the solution into a stainless steel reaction kettle with a polytetrafluoroethylene substrate, carrying out hydrothermal reaction at 220 ℃ for 30 hours, and cooling to room temperature to obtain a dark blue precipitate; repeatedly washing the dark blue precipitate with anhydrous ethanol for 2 times, and drying at 80 deg.C for 12 hr in drying oven to obtain sulfur and chromium co-doped MoO2.5(OH)0.5Nanosheets.
Prepared sulfur and chromium codoped MoO2.5(OH)0.5The nano sheet material is used as the lithium ion battery cathode material, and the assembly method of the lithium ion battery is consistent with the traditional assembly method. The preparation method of the negative plate comprises the following steps: adopts sulfur and chromium codoped MoO2.5(OH)0.5The nano-sheet material powder is used as a negative electrode material, polytetrafluoroethylene is used as a binder, and acetylene black is used as a conductive agent. The mass ratio of the three raw materials is 70:20: 10. Fully and uniformly stirring the components in proportion, then coating the mixture on a copper sheet by using a film scraper method, and pressing an electrode sheet with the thickness of about 0.15 mm on a tablet press; and drying the pressed negative plate in an oven at 90 ℃ for 14 hours for later use. 1 mol/l LiPF6The lithium ion battery is dissolved in ethylene carbonate and dimethyl carbonate to be used as electrolyte, a lithium sheet is used as a positive electrode, CR2025 type stainless steel is used as a battery shell, and Celgard2025 is used as a diaphragm to assemble the button type lithium ion battery.
Obtained sulfur and chromium codoped MoO2.5(OH)0.5The electrochemical performance of the nanosheet material as the negative electrode material of the lithium ion battery is shown in fig. 5, and the negative electrode material is 376 mAmp hour/g after 150 cycles at a current density of 5 Amp/g. The results indicate that the sulfur and chromium co-doped MoO2.5(OH)0.5The nano-sheet has excellent cycle stability and is a potential application material of a promising high-performance lithium ion battery.

Claims (2)

1. A preparation method of anion and cation co-doped molybdenum oxyhydroxide nanosheets is characterized by comprising the following specific steps:
(1) adding 1-3 g of analytically pure sodium dodecyl sulfate into 30-50 ml of deionized water, stirring for 10-30 minutes, and uniformly stirring;
(2) adding 5-10 ml of analytically pure dodecyl mercaptan into the solution obtained in the step (1), stirring for 10-30 minutes, and uniformly stirring;
(3) adding 1-3 g of analytically pure ammonium molybdate into the product obtained in the step (2), stirring for 10-30 minutes, and uniformly stirring;
(4) dropwise adding 1-3 ml of analytically pure nitric acid into the product obtained in the step (3), stirring for 10-30 minutes, and uniformly stirring;
(5) adding 1-2 g of analytically pure chromium nitrate into the product obtained in the step (4), stirring for 10-30 minutes, and uniformly stirring;
(6) transferring the solution obtained in the step (5) into a reaction kettle, stirring, transferring the solution into a stainless steel reaction kettle with a polytetrafluoroethylene substrate, carrying out hydrothermal reaction at the temperature of 150 ℃ and 220 ℃ for 24-30 hours, and cooling to room temperature to obtain a dark blue precipitate; repeatedly cleaning the dark blue precipitate with deionized water or anhydrous ethanol for 2-3 times, and drying in drying oven at 60-80 deg.C for 10-12 hr to obtain sulfur and chromium anion co-doped molybdenum oxyhydroxide compound (MoO)2.5(OH)0.5Nanosheets.
2. The application of the sulfur and chromium anion and cation co-doped molybdenum oxyhydroxide nanosheet prepared by the preparation method according to claim 1, wherein the sulfur and chromium anion and cation co-doped molybdenum oxyhydroxide nanosheet can be applied as a negative electrode material of a lithium ion battery.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105140478A (en) * 2015-07-31 2015-12-09 桂林理工大学 Preparation method of MoO3-H0.4MoO3 core-shell structure nanobelt
CN105680037A (en) * 2016-03-23 2016-06-15 武汉理工大学 Cathode material for lithium-ion battery and preparation method of cathode material
CN105932233A (en) * 2016-05-04 2016-09-07 合肥国轩高科动力能源有限公司 Preparation method for lithium-rich manganese-based positive electrode material of lithium ion battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105140478A (en) * 2015-07-31 2015-12-09 桂林理工大学 Preparation method of MoO3-H0.4MoO3 core-shell structure nanobelt
CN105680037A (en) * 2016-03-23 2016-06-15 武汉理工大学 Cathode material for lithium-ion battery and preparation method of cathode material
CN105932233A (en) * 2016-05-04 2016-09-07 合肥国轩高科动力能源有限公司 Preparation method for lithium-rich manganese-based positive electrode material of lithium ion battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Highly efficient MoO2.5(OH)0.5-doped ZnO nanoflower for photodecolorization of azo dye;RasolAbdullah Mirzaie etal;《Solid State Sciences》;20131231;第9-15页 *

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