CN108923040A - The preparation method and application of the miscellaneous molybdenum oxygen hydroxy compounds nanometer sheet of cation-anion co-doping - Google Patents
The preparation method and application of the miscellaneous molybdenum oxygen hydroxy compounds nanometer sheet of cation-anion co-doping Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and applications of the miscellaneous molybdenum oxygen hydroxy compounds nanometer sheet of cation-anion co-doping.Pure lauryl sodium sulfate will be analyzed to be added in deionized water, stirred evenly；Then pure lauryl mercaptan step will be analyzed to be added in above-mentioned solution, stirred evenly；Pure ammonium molybdate will be analyzed to be added in above-mentioned solution, stirred evenly；Pure nitric acid dropping will be analyzed into above-mentioned mixed solution, stirred evenly；Pure chromic nitrate will be analyzed to be add to the above mixed solution, stirred evenly；Above-mentioned acquired solution is transferred in reaction kettle, is transferred to after stirring in the stainless steel cauldron of polytetrafluoroethylsubstrate substrate, after hydro-thermal reaction, room temperature is cooled to and obtains dark blue precipitate object；It is dry with deionized water or washes of absolute alcohol, obtain the miscellaneous MoO of cation-anion co-doping2.5(OH)0.5Nanometer sheet.The present invention is at low cost, process control procedure is simple, easily large-scale production.
Description
Technical field
The invention belongs to technical field of material chemistry, and in particular to a kind of miscellaneous molybdenum oxygen hydroxy compounds of cation-anion co-doping（MoO2.5
(OH)0.5）The preparation method of nanometer sheet cell negative electrode material, the material can be used as lithium ion cell electrode negative electrode material.
Background technique
Exploitation New Two Dimensional layered electrode material is always the research hotspot of energy storage field.The present invention is with MoO3For parent knot
Structure is reference object, the miscellaneous MoO of cation-anion co-doping for obtaining a kind of superior performance by chemical reaction condition appropriate2.5
(OH)0.5Nanometer sheet cell negative electrode material.
It is well known that MoO3Widely applied in lithium ion battery and supercapacitor field.Its is unique
Structure feature, as it is by [MoO6] it is octahedra be basic structural unit, by corner-sharing, form chain link, every two is similar
Chain constitutes layer structure by the frame that total side is formed, and is connected between layers by Van der Waals force.MoO3It is this unique
Layer structure feature is there are a large amount of ion channel, and Mo is easy to appear the change of valence state in ccf layer, these are all very beneficial for
Its application in lithium ion battery and supercapacitor field.However, one cannot be neglected the fact is that, MoO3It is intrinsic to lead
Electrically and ion diffusion rates are poor.
In view of the above-mentioned problems, to MoO3The cutting of crystal structure is one of the effective way to solve the above problems.Lacking oxygen,
Low price element doping replaces the method for the structural tailorings such as high-valence state Mo to obtain theoretical and experimental verification.However, to MoO3Frame
It is miscellaneous that frame carries out cation-anion co-doping, while introducing a large amount of OH in frame structure and also never reporting.Consider from crystal structure angle,
Because of MoO2.5(OH)0.5Mo has mixed valence in structure, and electric conductivity is promoted, and leads to MoO2.5(OH)0.5Compared to MoO3It is expected to
Potential with more outstanding lithium ion storage lithium.However, at present about MoO2.5(OH)0.5Synthesis, modification and the performance of material
It has not been reported.
Summary of the invention
It is an object of the invention in view of the above problems, provide a kind of miscellaneous MoO of cation-anion co-doping2.5(OH)0.5
The preparation method and application of nanometer sheet cell negative electrode material.
The specific steps are：
（1）The 1-3 grams of pure lauryl sodium sulfate of analysis is added in 30-50 ml deionized water, stirs 10-30 minutes, stirs
It mixes uniformly.
（2）The 5-10 milliliters of pure lauryl mercaptan steps of analysis are added to step（1）In acquired solution, 10-30 points of stirring
Clock stirs evenly.
（3）The 1-3 grams of pure ammonium molybdate of analysis is added to step（2）In products therefrom, stirs 10-30 minutes, stir evenly.
（4）By the 1-3 milliliters of pure nitric acid droppings of analysis to step（3）In products therefrom, stirs 10-30 minutes, stir evenly.
（5）The 1-2 grams of pure chromic nitrate of analysis is added to step（4）In products therefrom, stirs 10-30 minutes, stir evenly.
（6）By step（5）Acquired solution is transferred in reaction kettle, and the stainless of polytetrafluoroethylsubstrate substrate is transferred to after stirring
In steel reaction kettle, 150-220 DEG C after hydro-thermal reaction 24-30 hours, is cooled to room temperature and obtains dark blue precipitate object；By dark blue precipitate
Object deionized water or dehydrated alcohol clean 2-3 times repeatedly, then dry 10-12 hour at 60-80 DEG C in drying box,
Obtain the miscellaneous MoO of cation-anion co-doping2.5(OH)0.5Nanometer sheet.
The miscellaneous MoO of the cation-anion co-doping2.5(OH)0.5Nanometer sheet can be used as lithium ion battery negative material application.
Simple, at low cost, the easy large-scale production of present invention process, it is miscellaneous due to preparing its unique cation-anion co-doping
MoO2.5(OH)0.5Nanometer sheet, on the one hand its two-dimensional nano chip architecture is conducive to lithium ion diffusion；On the other hand, MoO2.5(OH)0.5
Since zwitterion adulterates, the electronegativity difference Mo-O bonding energy due to sulphur than oxygen reduces nanometer sheet;In addition, chromium doped and substituted is high
Valence state molybdenum, the mixed valence for forming molybdenum are also beneficial to electron-transport.When the material is as lithium ion battery negative material, 1 pacify/
It is 535 MAhs/g after 150 circulations under gram current density；It is 376 millis after 150 circulations under 5 peace/gram current densities
Ampere-hour/gram.It should be the result shows that the sulphur, chromium codope MoO2.5(OH)0.5Nanometer sheet has excellent cyclical stability, is to be hopeful
High performance lithium ion battery potential application material.
In addition, the miscellaneous MoO of cation-anion co-doping2.5(OH)0.5Nanometer sheet is new to explore from now on by the simple hydrothermal synthesis of a step
Type two-dimensional electrode material provides new approach and new thinking.
Detailed description of the invention
Fig. 1 is the x-ray diffraction pattern of the embodiment of the present invention 1.
Fig. 2 is the field emission scanning electron microscope figure of the embodiment of the present invention 1.(a)-(b) low range, (c)-(d) high magnification.
Fig. 3 is the element energy spectrum diagram of the embodiment of the present invention 1.
Fig. 4 is circulation figure of the embodiment of the present invention 1 under 1 peace/gram current density.
Fig. 5 is circulation figure of the embodiment of the present invention 2 under 5 peace/gram current densities.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1：
Sulphur, chromium codope MoO2.5(OH)0.5The preparation method of nanometer sheet material, it includes the following steps：
（1）The 1 pure lauryl sodium sulfate of analysis is added in 30 ml deionized waters, stirs 15 minutes, stirs evenly.
（2）5 milliliters of pure lauryl mercaptan steps of analysis are added to step（1）It in acquired solution, stirs 15 minutes, stirring
Uniformly.
（3）1 gram of pure ammonium molybdate of analysis is added to step（2）In products therefrom, stirs 15 minutes, stir evenly.
（4）By 1 milliliter of pure nitric acid dropping of analysis to step（3）In products therefrom, stirs 15 minutes, stir evenly.
（5）1 gram of pure chromic nitrate of analysis is added to step（4）In products therefrom, stirs 15 minutes, stir evenly.
（6）By step（5）Acquired solution is transferred in reaction kettle, and the stainless of polytetrafluoroethylsubstrate substrate is transferred to after stirring
In steel reaction kettle, 150 DEG C after hydro-thermal reaction 26 hours, are cooled to room temperature and obtain dark blue precipitate object；Dark blue precipitate object is spent
Ionized water cleans 3 times repeatedly, then dries 10 hours at 80 DEG C in drying box, obtains sulphur, chromium codope MoO2.5
(OH)0.5Nanometer sheet.
Prepared sulphur, chromium codope MoO2.5(OH)0.5Nanometer sheet material as lithium ion battery negative material, lithium from
The assembly method of sub- battery is consistent with traditional assembly method.The preparation method of negative electrode tab is as follows：Using sulphur, chromium codope MoO2.5
(OH)0.5For nanometer sheet material powder as negative electrode material, polytetrafluoroethylene (PTFE) is binder, and acetylene black is conductive agent.Above-mentioned three kinds of originals
The mass ratio of material is 70:20:10.They are stirred in proportion, is then coated on copper sheet, is being pressed with blade applicator method
The electrode slice of about 0.15 millimeters thick is pressed on piece machine；The negative electrode tab pressed is spare after being placed in oven drying 14 hours of 90 DEG C.1 is rubbed
You/liter LiPF6It is dissolved in ethylene carbonic ether and dimethyl carbonate as electrolyte, lithium piece is as anode, and CR2025 type is not
Rust steel is battery case, and Celgard2025 is that diaphragm is assembled into fastening lithium ionic cell.
Sulphur obtained, chromium codope MoO2.5(OH)0.5Nanometer sheet material is as lithium ion battery negative material, electrification
Performance is as shown in figure 4, the negative electrode material is 535 MAhs/g after 150 circulations under 1 peace/gram current density.The result
Show the sulphur, chromium codope MoO2.5(OH)0.5Nanometer sheet has excellent cyclical stability, is promising high-performance lithium ion
The potential application material of battery.
Embodiment 2：
Sulphur, chromium codope MoO2.5(OH)0.5The preparation method of nanometer sheet material, it includes the following steps：
（1）3 grams of pure lauryl sodium sulfate of analysis are added in 50 ml deionized waters, stirs 15 minutes, stirs evenly.
（2）10 milliliters of pure lauryl mercaptans of analysis are added to step（1）Solution in, stir 15 minutes, stir evenly.
（3）3 grams of pure ammonium molybdates of analysis are added to step（2）In products therefrom, stirs 15 minutes, stir evenly.
（4）By 3 milliliters of pure nitric acid droppings of analysis to step（3）In products therefrom, stirs 15 minutes, stir evenly.
（5）2 grams of pure chromic nitrates of analysis are added to step（4）In products therefrom, stirs 15 minutes, stir evenly.
（6）By step（5）Acquired solution is transferred in reaction kettle, and the stainless of polytetrafluoroethylsubstrate substrate is transferred to after stirring
In steel reaction kettle, 220 DEG C after hydro-thermal reaction 30 hours, are cooled to room temperature and obtain dark blue precipitate object；By dark blue precipitate object nothing
Water-ethanol respectively cleans 2 times repeatedly, then dries 12 hours at 80 DEG C in drying box, obtains sulphur, chromium codope MoO2.5
(OH)0.5Nanometer sheet.
Prepared sulphur, chromium codope MoO2.5(OH)0.5Nanometer sheet material as lithium ion battery negative material, lithium from
The assembly method of sub- battery is consistent with traditional assembly method.The preparation method of negative electrode tab is as follows：Using sulphur, chromium codope MoO2.5
(OH)0.5For nanometer sheet material powder as negative electrode material, polytetrafluoroethylene (PTFE) is binder, and acetylene black is conductive agent.Above-mentioned three kinds of originals
The mass ratio of material is 70:20:10.They are stirred in proportion, is then coated on copper sheet, is being pressed with blade applicator method
The electrode slice of about 0.15 millimeters thick is pressed on piece machine；The negative electrode tab pressed is spare after being placed in oven drying 14 hours of 90 DEG C.1 is rubbed
You/liter LiPF6It is dissolved in ethylene carbonic ether and dimethyl carbonate as electrolyte, lithium piece is as anode, and CR2025 type is not
Rust steel is battery case, and Celgard2025 is that diaphragm is assembled into fastening lithium ionic cell.
Sulphur obtained, chromium codope MoO2.5(OH)0.5Nanometer sheet material is as lithium ion battery negative material, electrification
Performance is as shown in figure 5, the negative electrode material is 376 MAhs/g after 150 circulations under 5 peace/gram current densities.The result
Show the sulphur, chromium codope MoO2.5(OH)0.5Nanometer sheet has excellent cyclical stability, is promising high-performance lithium ion
The potential application material of battery.
Claims (2)
1. a kind of preparation method of the miscellaneous molybdenum oxygen hydroxy compounds nanometer sheet of cation-anion co-doping, it is characterised in that the specific steps are：
（1）The 1-3 grams of pure lauryl sodium sulfate of analysis is added in 30-50 ml deionized water, stirs 10-30 minutes, stirs
It mixes uniformly；
（2）The 5-10 milliliters of pure lauryl mercaptan steps of analysis are added to step（1）In acquired solution, stirs 10-30 minutes, stir
It mixes uniformly；
（3）The 1-3 grams of pure ammonium molybdate of analysis is added to step（2）In products therefrom, stirs 10-30 minutes, stir evenly；
（4）By the 1-3 milliliters of pure nitric acid droppings of analysis to step（3）In products therefrom, stirs 10-30 minutes, stir evenly；
（5）The 1-2 grams of pure chromic nitrate of analysis is added to step（4）In products therefrom, stirs 10-30 minutes, stir evenly；
（6）By step（5）Acquired solution is transferred in reaction kettle, and the stainless steel that polytetrafluoroethylsubstrate substrate is transferred to after stirring is anti-
It answers in kettle, 150-220 DEG C after hydro-thermal reaction 24-30 hours, is cooled to room temperature and obtains dark blue precipitate object；Dark blue precipitate object is used
Deionized water or dehydrated alcohol clean 2-3 times repeatedly, then dry 10-12 hour at 60-80 DEG C in drying box, obtain
The miscellaneous molybdenum oxygen hydroxy compounds, that is, MoO of cation-anion co-doping2.5(OH)0.5Nanometer sheet.
2. the miscellaneous molybdenum oxygen hydroxy compounds nanometer sheet of cation-anion co-doping of preparation method preparation according to claim 1 is answered
With, it is characterised in that the miscellaneous molybdenum oxygen hydroxy compounds nanometer sheet of cation-anion co-doping can be answered as lithium ion battery negative material
With.
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Citations (3)
| 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 |
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- 2018-06-25 CN CN201810663554.8A patent/CN108923040B/en active Active
Patent Citations (3)
| 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)
| Title |
|---|
| RASOLABDULLAH MIRZAIE ETAL: "Highly efficient MoO2.5(OH)0.5-doped ZnO nanoflower for photodecolorization of azo dye", 《SOLID STATE SCIENCES》 * |
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