CN109935474A - A kind of magnanimity preparation NaxMnO2The method of electrode material - Google Patents
A kind of magnanimity preparation NaxMnO2The method of electrode material Download PDFInfo
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- CN109935474A CN109935474A CN201910200423.0A CN201910200423A CN109935474A CN 109935474 A CN109935474 A CN 109935474A CN 201910200423 A CN201910200423 A CN 201910200423A CN 109935474 A CN109935474 A CN 109935474A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
A kind of magnanimity preparation NaxMnO2The method of electrode material includes the following steps: (1) by MnO2With anhydrous Na NO3It is mixed between in mass ratio 0.5 ~ 2, spheroidal graphite is uniformly mixed；(2) mixture that step (1) obtains is placed in Muffle furnace and is calcined, calcination temperature range is 800 ~ 900 DEG C, the time 5 ~ 10 hours；(3) compound that step (2) obtains is cleaned with deionized water, it is dry.Present invention process is simple, and equipment requirement is low, has practicability, is easy to scale industrial production；The NaxMnO of preparation2With high Na content and excellent chemical property, 0 ~ 1.3V of potential window (vs.Ag/AgCl) including ultra-wide, high 260 F g of specific capacitance‑1And excellent high rate performance and cyclical stability；And special appearance and certain particle size and the NaxMnO of distribution can be prepared by controlling process conditions2Electrode material.
Description
Technical field
The invention belongs to electrochemical energy storage fields, are related to a kind of magnanimity preparation NaxMnO2The method of electrode material.
Background technique
Supercapacitor is as a kind of new type of energy storage device, compared with battery, because it has high power density, quickly fills
The features such as discharge capability, high service life, wide and environmental-friendly temperature range, is widely used in startup power supply, pulse electricity
In the research fields such as source, military affairs, mobile communication device, computer and electric car.But its energy density is far below battery,
It is significantly limited further to apply.Therefore, how large scale preparation has efficient electrode material close to improve its energy
Degree becomes urgent problem to be solved at this stage.
At present the electrode material of supercapacitor mainly have carbon material, metal oxide, metal hydroxides, polymer,
Composite material etc..In addition to carbon material and few part fake capacitance material have been carried out commercial applications, although most of fake capacitances
With the specific capacity much higher relative to carbon material, but because of low electric conductivity, voltage window is narrow, stability is poor, expensive, difficult
It is limited with large scale preparation etc. and is further applied.According to super capacitor energy density formula E=1/2 CV2(its energy is close
Degree (E) is directly proportional to its specific capacity (C) and operating potential window (V)) it is found that electrode voltage window is to determine super electricity
One key factor of container work voltage, but most of fake capacitance material voltage ranges are narrow at present, high specific capacitance with
The carbon based negative electrodes material of low specific capacitance is difficult to be effectively matched, and leads to the more difficult raising of device energy density.So how to make on a large scale
The positive electrode of standby high voltage window is a kind of effective way for improving super capacitor energy density and realizing commercial applications.
MnO2Oxygen evolution potential (1V) with higher and higher specific capacitance are a kind of water system high voltages of great potential
Supercapacitor positive electrode electrode material.Recently, Xia Hui seminar aoxidizes Mn by electrochemical in-situ3O4The Na of preparation0.5MnO2It receives
Rice wall combination electrode, in Na2SO4In electrolyte, voltage window can extend to 0 ~ 1.3 V (vs. Ag/AgCl), specific capacitance
It can reach 366 F g-1(Adv. Mater. 2017,1700804), has further expanded MnO2Sill is as the high electricity of water system
Press the possibility of supercapacitor.But the method for preparing this material at present is excessively complicated, and experiment condition requires high, it is difficult to extensive
Preparation.
Summary of the invention
The object of the present invention is to provide a kind of magnanimities to prepare NaxMnO2The method of electrode material.Overcome and surpasses in the prior art
Grade capacitor high voltage N axMnO2Electrode material preparation difficulty, complex process, it is at high cost, be difficult to the shortcomings that large scale preparation, mention
For the high super capacitor anode material NaxMnO of a kind of low cost, low energy consumption, voltage range2Preparation method, simplify
NaxMnO2The preparation process of electrode is, it can be achieved that large scale preparation NaxMnO2Electrode material.
The present invention is achieved by the following technical solutions.
A kind of magnanimity of the present invention prepares NaxMnO2A kind of method of electrode material, it is characterized in that providing magnanimity system
Standby super capacitor anode material NaxMnO2Method.
A kind of magnanimity of the present invention prepares NaxMnO2The method of electrode material, it is characterized in that including the following steps.
(1) by MnO2With anhydrous Na NO3It is mixed between in mass ratio 0.5 ~ 2, spheroidal graphite is uniformly mixed.
(2) mixture that step (1) obtains being placed in Muffle furnace and is calcined, calcination temperature range is 800 ~ 900 DEG C, when
Between 5 ~ 10 hours.
(3) compound that step (2) obtains is cleaned with deionized water, it is dry, obtain final product.
Preferably, the MnO2For spinel-type.Its specific capacitance of different crystal structure is of different sizes, and increasing law is big
It causes to be pyrolusite < nickeliferous todorokite < ramsdellite < cryptomelane < sodium manganese ore < spinelle.
Preferably, the spheroidal graphite time is 24 hours.
Preferably, the anhydrous Na NO3With MnO2Mass ratio be 0.5.
Preferably, the calcination temperature is 870 DEG C, and the time is 10 hours.
Compared with prior art, present invention has the advantage that MnO2With rich reserves, it is cheap, to environment friend
Well, the advantages that there are many oxidation state and structure-rich, the NaxMnO of preparation2With high Na content, there is excellent electrification
Learn performance, 0 ~ 1.3V of potential window (vs. Ag/AgCl) including ultra-wide, high 260 F g of specific capacitance-1And it is excellent
High rate performance and cyclical stability；Raw materials used is the cheap raw material of industry, the addition without other chemical reagent, technical process
Middle solvent for use is water, without secondary pollution；The cost for preparing electrode material at present is reduced from source, realizes consumption reduction section
It can be with the comprehensive utilization of resource；Special appearance and certain particle size and distribution high potential can be prepared by controlling process conditions
Electrode material for super capacitor；Preparation method simple process, the requirement to equipment are low；Easily realize the doping vario-property of other elements,
The performance of material is improved, practicability is had more, is easy to scale industrial production.
Detailed description of the invention
Fig. 1 is step a) MnO in embodiment 12X-ray diffractogram.
Fig. 2 is step c) NaxMnO in embodiment 12Scanning electron microscope (SEM) photograph.
Fig. 3 is step c) NaxMnO in embodiment 12Cyclic voltammetry curve.
Fig. 4 is step c) NaxMnO in embodiment 12Charging and discharging curve.
Specific embodiment
In order to which superiority of the invention is more clearly understood, below in conjunction with drawings and examples, to the present invention carry out into
One step is described in detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, it is not used to limit this
Invention.In addition, technological means involved in each embodiment described in embodiment can be diversified, it is not limited in institute
State experimental technique means.
Embodiment 1.
a) 9 g MnSO4It is dissolved in 80 mL deionized waters for solution A；6 g KMnO4It is dissolved in 200 mL for solution B；It will
Solution A is slowly added in solution B, is placed in reaction kettle, is reacted 12 hours under the conditions of 140 DEG C, is cooled to room temperature, uses deionization
Water cleaning, it is dry.Then in air, calcined 2 hours under the conditions of 400 DEG C and obtain MnO2。
B) MnO for obtaining step a)2With anhydrous Na NO3It is 2:1 mixing with mass ratio, is put into spheroidal graphite 24 in ball mill
Hour.
C) the obtained mixture of step b) is put into Muffle furnace, is calcined 12 hours in air, under the conditions of 870 DEG C,
Then it is cleaned with deionized water, it is dry, obtain NaxMnO2。
Embodiment 2.
a) 9 g MnSO4It is dissolved in 80 mL deionized waters for solution A；6 g KMnO4It is dissolved in 200 mL for solution B；It will
Solution A is slowly added in solution B, is placed in reaction kettle, is reacted 12 hours under the conditions of 140 DEG C, is cooled to room temperature, uses deionization
Water cleaning, it is dry.Then in air, calcined 2 hours under the conditions of 400 DEG C and obtain MnO2。
B) MnO for obtaining step a)2With anhydrous Na NO3It is 1:1 mixing with mass ratio, is put into spheroidal graphite 24 in ball mill
Hour.
C) the obtained mixture of step b) is put into Muffle furnace, is calcined 12 hours in air, under the conditions of 870 DEG C,
Then it is cleaned with deionized water, it is dry, obtain NaxMnO2。
Embodiment 3.
a) 9 g MnSO4It is dissolved in 80 mL deionized waters for solution A；6 g KMnO4It is dissolved in 200 mL for solution B；It will
Solution A is slowly added in solution B, is placed in reaction kettle, is reacted 12 hours under the conditions of 140 DEG C, is cooled to room temperature, uses deionization
Water cleaning, it is dry.Then in air, calcined 2 hours under the conditions of 400 DEG C and obtain MnO2。
B) MnO for obtaining step a)2With anhydrous Na NO3It is 1:2 mixing with mass ratio, is put into spheroidal graphite 24 in ball mill
Hour.
C) the obtained mixture of step b) is put into Muffle furnace, is calcined 12 hours in air, under the conditions of 870 DEG C,
Then it is cleaned with deionized water, it is dry, obtain NaxMnO2。
Preparation method simple process of the invention, the requirement to equipment is low, has practicability, and it is raw to be easy to large-scale industrial
It produces.The NaxMnO of preparation2Specific capacitance with higher and wide voltage window can prepare special form by controlling process conditions
Looks and certain particle size and the electrode material of distribution have certain application value.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to restrict the invention, all to set in of the invention
Count made any modification within thinking and principle, improve and replace etc., it should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of magnanimity prepares NaxMnO2The method of electrode material, it is characterized in that including the following steps:
(1) by MnO2With anhydrous Na NO3It is mixed between in mass ratio 0.5 ~ 2, spheroidal graphite is uniformly mixed；
(2) mixture that step (1) obtains being placed in Muffle furnace and is calcined, calcination temperature range is 800 ~ 900 DEG C, the time 5 ~
10 hours；
(3) compound that step (2) obtains is cleaned with deionized water, it is dry, obtain final product.
2. a kind of magnanimity according to claim 1 prepares NaxMnO2The method of electrode material, it is characterized in that the MnO2
For spinel-type.
3. a kind of magnanimity according to claim 1 prepares NaxMnO2The method of electrode material, it is characterized in that step (1) is described
The spheroidal graphite time be 24 hours.
4. a kind of magnanimity according to claim 1 prepares NaxMnO2The method of electrode material, it is characterized in that step (1) is described
Anhydrous Na NO3With MnO2Mass ratio be 0.5.
5. a kind of magnanimity according to claim 1 prepares NaxMnO2The method of electrode material, it is characterized in that step (2) is described
Calcination temperature be 870 DEG C, the time 10 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910200423.0A CN109935474A (en) | 2019-03-16 | 2019-03-16 | A kind of magnanimity preparation NaxMnO2The method of electrode material |
| PCT/CN2019/114603 WO2020186766A1 (en) | 2019-03-16 | 2019-10-31 | Method for macro preparation of naxmno2 electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020186766A1 (en) * | 2019-03-16 | 2020-09-24 | 南昌大学 | Method for macro preparation of naxmno2 electrode material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103904317A (en) * | 2012-12-25 | 2014-07-02 | 北京汉能创昱科技有限公司 | Preparing method of sodium-ion battery cathode material |
| CN107045948A (en) * | 2017-04-11 | 2017-08-15 | 南京理工大学 | NaxMnO2Positive electrode, preparation method and applications |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101241802A (en) * | 2008-03-13 | 2008-08-13 | 复旦大学 | A non symmetric water natrium/kalium ion battery capacitor |
| US10243217B2 (en) * | 2017-05-24 | 2019-03-26 | Nanotek Instruments, Inc. | Alkali metal battery having a deformable quasi-solid electrode material |
| CN109935474A (en) * | 2019-03-16 | 2019-06-25 | 南昌大学 | A kind of magnanimity preparation NaxMnO2The method of electrode material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103904317A (en) * | 2012-12-25 | 2014-07-02 | 北京汉能创昱科技有限公司 | Preparing method of sodium-ion battery cathode material |
| CN107045948A (en) * | 2017-04-11 | 2017-08-15 | 南京理工大学 | NaxMnO2Positive electrode, preparation method and applications |
Non-Patent Citations (2)
| Title |
|---|
| DOEFF，M.M. ET AL: "Lithium Insertion Process of Orthorhombic NaxMnO2-Based Electrode Materials", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
| Q.T. QU ET AL: ""A new cheap asymmetric aqueous supercapacitor: Activated carbon // NaMnO2"", 《JOURNAL OF POWER SOURCES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020186766A1 (en) * | 2019-03-16 | 2020-09-24 | 南昌大学 | Method for macro preparation of naxmno2 electrode material |
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Application publication date: 20190625 |