CN108298588A - It is a kind of to prepare δ-MnO2The method of nanometer sheet - Google Patents

It is a kind of to prepare δ-MnO2The method of nanometer sheet Download PDF

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Publication number
CN108298588A
CN108298588A CN201810016165.6A CN201810016165A CN108298588A CN 108298588 A CN108298588 A CN 108298588A CN 201810016165 A CN201810016165 A CN 201810016165A CN 108298588 A CN108298588 A CN 108298588A
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solution
mno
nanometer sheet
washed
naoh solution
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夏傲
于婉茹
宜珏
谈国强
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

It is a kind of to prepare δ MnO2The method of nanometer sheet, includes the following steps：Compound concentration is the NaOH solution of 0.4 0.8mol/L, and compound concentration is the H of 9.0 11.0mol/L2O2Solution；Compound concentration is the Mn (NO of 0.20 0.40mol/L3)2Solution；By H2O2Solution is added rapidly in NaOH solution；Mixed solution is added rapidly to prepared Mn (NO again3)2In solution；It is dried to obtain intermediate product after the deposit of generation is washed to neutrality；Intermediate product is added in NaOH solution, autoclave is transferred to after stirring evenly；After staying in reaction kettle reaction, cools, products therefrom is first washed with distilled water to after neutrality and is washed again with absolute ethyl alcohol, most obtain δ MnO through oven drying afterwards2Nanometer sheet, products therefrom crystalline phase development of the present invention is complete, and purity is high, good dispersion.

Description

It is a kind of to prepare δ-MnO2The method of nanometer sheet
Technical field
The present invention relates to MnO2The preparing technical field of powder, more particularly to it is a kind of to prepare δ-MnO2The method of nanometer sheet.
Background technology
Transition metal oxide is due to its alternative huge number and bulk effect is small, becomes current lithium cell negative pole material The research hotspot of material.MnO2It is a kind of important transition metal oxide, there are a variety of crystal forms such as α, β, γ, δ, ε, λ.Due to it Structure diversity, the rich and feature of environmental protection and be widely used in battery material.Relative to the negative of other transition metal oxides Pole material, manganese dioxide have the advantage that：(1) there is theoretical specific capacity more higher than other many transition metal oxides (1232mAh/g), the lithium cell negative pole material to develop large capacity provide possibility.(2)MnO2With significantly lower than other transition gold Belong to the discharge platform (about 0.4V) of oxide cathode material.As negative material, it will help improve battery entirety voltage with Power.(3)MnO2Also have the characteristics that rich reserves, at low cost, specific surface area is larger, invertibity is excellent, environmentally friendly, this All it is MnO a bit2Correct theoretical foundation is above provided in the application of lithium ion battery negative material.
However, MnO2As lithium ion battery negative material, also it is faced with and other transition metal oxide negative materials Similar problem：(1)MnO2During charge and discharge, it is easy to happen significant volume change.It may result in electrode material in this way Feed powder, each other connection are reduced, and system resistance increases；Or fall off from collection liquid surface, cause active material to lose, from And lead to capacity fast decay.(2)MnO2The electric conductivity of itself is poor, native electronic conductivity (10-5~10-6S/cm) low, because And it is unfavorable for the charge transfer in charge and discharge process.In order to overcome disadvantage mentioned above, it can be modified by the following method： (1) manganese dioxide of special construction, such as nanostructure, porous structure, nucleocapsid, sandwich structure are synthesized；(2) two are synthesized The composite material of manganese oxide and carbon；(3) composite material of synthesis and polymer；(4) metal ion mixing etc..
Currently, preparing MnO2The common method of nanometer sheet has：Solid reaction process, hydrothermal synthesis method, sol-gel method, liquid Phase oxidation-reduction method etc..MnO is prepared using hydro-thermal method2Nanometer sheet, equipment and process are simple, easily-controlled reaction conditions, and particle is pure Degree height, good dispersion.
Invention content
In order to overcome the above-mentioned deficiencies of the prior art, δ-MnO being prepared the purpose of the present invention is to provide a kind of2Nanometer sheet Method has prepared MnO using hydro-thermal method2Nanometer sheet, used preparation process is simple, process control, in addition products therefrom Crystalline phase development is complete, and purity is high, good dispersion.
To achieve the goals above, the technical solution adopted by the present invention is：
It is a kind of to prepare δ-MnO2The method of nanometer sheet, includes the following steps：
Step 1：Compound concentration is the NaOH solution of 0.4-0.8mol/L, and solution stirring a period of time is complete to NaOH Dissolving；
Step 2：Compound concentration is the H of 9.0-11.0mol/L2O2Solution；
Step 3：Compound concentration is the Mn (NO of 0.20-0.40mol/L3)2Solution；
Step 4：The H that step 2 is prepared2O2Solution is added rapidly in the NaOH solution that step 1 obtains, and is uniformly mixed；Again Above-mentioned obtained mixed solution is added rapidly to the prepared Mn (NO of step 33)2In solution, quickly stirring is equal to mixing It is even；Prepared NaOH solution, H in steps 1 and 2,32O2Solution and Mn (NO3)2The molar concentration rate of solution is：0.67：9.79: 0.3；
Step 5：It stands step 4 gained mixed solution to obtain deposit, be dried to obtain after deposit is washed to neutrality Intermediate product；
Step 6：The 80% of the intermediate product that step 5 obtains is added in the NaOH solution of a concentration of 2mol/L, is stirred Autoclave is transferred to after uniformly, liquor capacity controls the 60-80% in reaction kettle volume；
Step 7：It after reaction kettle reacts 10-30h at 100-200 DEG C, cools, by products therefrom first with distillation washing It is washed again with absolute ethyl alcohol after washing to neutrality, most obtains δ-MnO through 80 DEG C of oven dryings afterwards2Nanometer sheet.
Beneficial effects of the present invention：
The present invention has prepared δ-MnO using hydro-thermal method2Nanometer sheet, used preparation process is simple, process control, this Outer products therefrom crystalline phase development is complete, and purity is high, pattern rule, good dispersion；δ-MnO2For the two-dimensional nano piece knot of high dispersive Structure.δ-MnO2The preparation of nanometer sheet is expected to make MnO2Performance as negative material is further improved.
Description of the drawings
Fig. 1 is the XRD spectrum of product prepared by the present invention.
Fig. 2 is the SEM figures of product of the present invention.
Specific implementation mode
With reference to embodiment, invention is further described in detail.
Embodiment 1
MnO2The preparation method of nanometer sheet, includes the following steps：
Step 1：8.04g NaOH are dissolved in 300mL deionized waters, solution stirring a period of time is complete to NaOH Dissolving；
Step 2：The H for being 30% by 35mL mass fractions2O2It is added rapidly in the solution that step 1 obtains, is uniformly mixed；
Step 3：Mn (the NO for being 50% by 10mL mass fractions3)2It is dissolved in the deionized water of 133mL；
Step 4：The mixed solution that step 2 obtains is added rapidly to the prepared Mn (NO of step 33)2In solution, quickly It stirs to uniformly mixed；
Step 5：It stands step 4 gained mixed solution to obtain deposit, be dried to obtain after deposit is washed to neutrality Intermediate product；
Step 6：The 80% of the intermediate product that step 5 obtains is added in the NaOH solution of a concentration of 2mol/L, is stirred Autoclave is transferred to after uniformly, liquor capacity controls the 60-80% in reaction kettle volume；
Step 7：It after reaction kettle reacts 10-30h at 100-200 DEG C, cools, by products therefrom first with distillation washing It is washed again with absolute ethyl alcohol after washing to neutrality, most obtains MnO through 80 DEG C of oven dryings afterwards2Nanometer rods.
Embodiment 2
MnO2The preparation method of nanometer sheet, includes the following steps：
Step 1：12.3g NaOH are dissolved in 458mL deionized waters, solution stirring a period of time is complete to NaOH Dissolving；
Step 2：The H for being 30% by 47mL mass fractions2O2It is added rapidly in the solution that step 1 obtains, is uniformly mixed；
Step 3：Mn (the NO for being 50% by 18mL mass fractions3)2It is dissolved in the deionized water of 240mL；
Step 4：The obtained mixed solution of step 2 is added rapidly to the prepared Mn (NO of step 33)2In solution, soon Speed stirring 30min to be uniformly mixed；
Step 5：Step 4 gained mixed solution is stood, intermediate product is dried to obtain after washing to neutrality；
Step 6：The NaOH solution for being added to a concentration of 2.5mol/L of 80mL by the 80% of the intermediate product that step 5 obtains In, autoclave is transferred to after stirring evenly, liquor capacity is controlled the 75% of reaction kettle volume；
Step 7：After reaction kettle reacts 10h at 200 DEG C, cool, during products therefrom is first washed with distilled water to It is washed again with absolute ethyl alcohol after property, most afterwards through oven drying, obtains MnO2Nanometer rods.
Embodiment 3
MnO2The preparation method of nanometer sheet, includes the following steps：
Step 1：9.6g NaOH are dissolved in 359mL deionized waters, solution stirring a period of time is completely molten to NaOH Solution；
Step 2：The H for being 30% by 41mL mass fractions2O2It is added rapidly in the solution that step 1 obtains, is uniformly mixed；
Step 3：Mn (the NO for being 50% by 14mL mass fractions3)2It is dissolved in the deionized water of 186mL；
Step 4：The obtained mixed solution of step 2 is added rapidly to the prepared Mn (NO of step 33)2In solution, soon Speed stirring 30min to be uniformly mixed；
Step 5：Step 4 gained mixed solution is stood, intermediate product is dried to obtain after washing to neutrality；
Step 6：The 80% of the intermediate product that step 5 obtains is added in the NaOH solution of a concentration of 2mol/L of 100mL, Autoclave is transferred to after stirring evenly, liquor capacity is controlled the 80% of reaction kettle volume；
Step 7：After reaction kettle reacts 16h at 170 DEG C, cool, during products therefrom is first washed with distilled water to It is washed again with absolute ethyl alcohol after property, most afterwards through oven drying, obtains MnO2Nanometer sheet.
Fig. 1 is the XRD spectrum of product prepared by the present invention, complete with the standard card NO.43-1456 in PDF databases It coincide, illustrates that the crystalline phase group of product becomes δ-MnO2, the peak type at visible X-ray diffraction peak is sharp in addition, peak intensity is higher, explanation MnO2Crystal form physically well develops.
Fig. 2 is the SEM figures of product of the present invention；It can be seen that δ-MnO2Presentation two-dimensional nano chip architecture, nanometer sheet thickness 10nm, A diameter of 2 μm.
This research has synthesized MnO using hydro-thermal method2Nanometer sheet, nanometer MnO2With common MnO2It compares, nanometer MnO2With compared with Big specific surface area increases the contact area with electrolyte, and chemical reactivity site is more, thus has preferable electrochemistry Performance.In addition, nanostructure shortens diffusion length of the lithium ion in electrode material, reduces lithium ion and deviate from insertion Bulk effect in journey is conducive to the raising of lithium ion battery high rate performance to accelerate electrochemical reaction.

Claims (1)

1. a kind of preparing δ-MnO2The method of nanometer sheet, which is characterized in that include the following steps：
Step 1：Compound concentration is the NaOH solution of 0.4-0.8mol/L, and solution stirring a period of time is completely molten to NaOH Solution；
Step 2：Compound concentration is the H of 9.0-11.0mol/L2O2Solution；
Step 3：Compound concentration is the Mn (NO of 0.20-0.40mol/L3)2Solution；
Step 4：The H that step 2 is prepared2O2Solution is added rapidly in the NaOH solution that step 1 obtains, and is uniformly mixed；It again will be upper It states obtained mixed solution and is added rapidly to the prepared Mn (NO of step 33)2In solution, quickly stir to uniformly mixed；Step Prepared NaOH solution, H in rapid 1,2,32O2Solution and Mn (NO3)2The molar concentration rate of solution is：0.67：9.79:0.3；
Step 5：It stands step 4 gained mixed solution to obtain deposit, centre is dried to obtain after deposit is washed to neutrality Product；
Step 6：The 80% of the intermediate product that step 5 obtains is added in the NaOH solution of a concentration of 2mol/L, is stirred evenly After be transferred to autoclave, liquor capacity controls the 60-80% in reaction kettle volume；
Step 7：It after reaction kettle reacts 10-30h at 100-200 DEG C, cools, products therefrom is first washed with distilled water to It is washed again with absolute ethyl alcohol after neutrality, most obtains δ-MnO through 80 DEG C of oven dryings afterwards2Nanometer sheet.
CN201810016165.6A 2018-01-08 2018-01-08 It is a kind of to prepare δ-MnO2The method of nanometer sheet Pending CN108298588A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109103429A (en) * 2018-08-10 2018-12-28 陕西科技大学 It is a kind of to prepare lithium ion battery negative material δ-MnO2The method of/PPy
CN109148849A (en) * 2018-08-10 2019-01-04 陕西科技大学 It is a kind of to prepare Zr4+Adulterate δ-MnO2The method of nano-porous materials
CN110655113A (en) * 2019-09-29 2020-01-07 南昌大学 Na-doped MnO2Preparation method of electrode material
CN111333115A (en) * 2020-03-10 2020-06-26 中国石油大学(北京) Two-dimensional porous active manganese oxide, preparation method thereof and curing agent containing same
CN113104896A (en) * 2021-03-19 2021-07-13 天津大学 Preparation method of nano flaky manganese oxide material and application of nano flaky manganese oxide material in water-based zinc ion battery
CN115739107A (en) * 2022-11-22 2023-03-07 安徽工业大学 Manganese dioxide nano composite material and preparation method thereof

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CN106268799A (en) * 2016-08-26 2017-01-04 中国科学院上海硅酸盐研究所 Manganese oxide nanometer sheet material of the crystallization of supporting Pt and its preparation method and application
CN107233796A (en) * 2017-07-10 2017-10-10 陕西科大绿建环保技术服务有限公司 Renewable efficient formaldehyde removes material and preparation method thereof

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CN102502851A (en) * 2011-11-15 2012-06-20 上海大学 Method for synthesizing manganese dioxide film on metal titanium substrate
CN106268799A (en) * 2016-08-26 2017-01-04 中国科学院上海硅酸盐研究所 Manganese oxide nanometer sheet material of the crystallization of supporting Pt and its preparation method and application
CN107233796A (en) * 2017-07-10 2017-10-10 陕西科大绿建环保技术服务有限公司 Renewable efficient formaldehyde removes material and preparation method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109103429A (en) * 2018-08-10 2018-12-28 陕西科技大学 It is a kind of to prepare lithium ion battery negative material δ-MnO2The method of/PPy
CN109148849A (en) * 2018-08-10 2019-01-04 陕西科技大学 It is a kind of to prepare Zr4+Adulterate δ-MnO2The method of nano-porous materials
CN110655113A (en) * 2019-09-29 2020-01-07 南昌大学 Na-doped MnO2Preparation method of electrode material
CN111333115A (en) * 2020-03-10 2020-06-26 中国石油大学(北京) Two-dimensional porous active manganese oxide, preparation method thereof and curing agent containing same
CN113104896A (en) * 2021-03-19 2021-07-13 天津大学 Preparation method of nano flaky manganese oxide material and application of nano flaky manganese oxide material in water-based zinc ion battery
CN115739107A (en) * 2022-11-22 2023-03-07 安徽工业大学 Manganese dioxide nano composite material and preparation method thereof
CN115739107B (en) * 2022-11-22 2024-01-26 安徽工业大学 Manganese dioxide nanocomposite and preparation method thereof

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Application publication date: 20180720