CN106800312A - A kind of preparation method for sodium-ion battery positive material manganous acid sodium - Google Patents
A kind of preparation method for sodium-ion battery positive material manganous acid sodium Download PDFInfo
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- CN106800312A CN106800312A CN201710135198.8A CN201710135198A CN106800312A CN 106800312 A CN106800312 A CN 106800312A CN 201710135198 A CN201710135198 A CN 201710135198A CN 106800312 A CN106800312 A CN 106800312A
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- CN
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- Prior art keywords
- sodium
- acid sodium
- solid phase
- positive electrode
- manganous acid
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Classifications
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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
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- 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 kind of sodium rechargeable battery high-voltage anode material manganous acid sodium Na2MnO3Method for preparing solid phase.It is characterized in that prepared method is comprised the following steps：By the manganese source compound of certain stoichiometric proportion and sodium source compound, ground and mixed is uniform；The mixture of gained is transferred in tube furnace, under inert gas shielding, room temperature is cooled to after pyroreaction at 400 ~ 700 DEG C；By the grinding of above-mentioned presoma through distilling water washing to neutrality, target product manganous acid sodium is obtained final product after drying water removal grinding.The method disposably adds material, and technological operation is simple, and raw material is cheap and easy to get, and product purity is high, and process control and properties of product all have good reappearance.Prepared Na2MnO3Material potential plateau is high, shows excellent chemical property, will be the further research of this kind of high-energy-density positive electrode and practical offer new approaches.
Description
Technical field
The present invention relates to a kind of sodium-ion battery high-voltage anode material manganous acid sodium Na2MnO3Preparation method, especially
Relate to the use of the method that solid phase method simple and easy to apply prepares the sodium-ion battery positive material manganous acid sodium of high-purity, belong to sodium from
Sub- battery material technical field.
Background technology
With the growth of population, the global warming that combustion of fossil fuel brings, the raising of fossil fuel face cost, the mankind
Have increasing need for being freed from the dependence to non-renewable energy resources.Inexhaustible energy source is not yet
In the presence of, wind energy, solar energy are exactly preferably selection, but its round the clock, seasonal skewness limit large-scale exploitation
And utilization.The electric energy that wind energy, solar energy are transformed must be concentrated to store and supplied in order to meet the electric power of different time sections
Answer demand.Our facing challenges be exactly from solar energy and the energy conversion of wind energy be into portable or static power source, and
Efficiently and effectively mutually conversion is realized, the Sustainable Development and Utilization of regenerative resource is realized.
Lithium ion battery as a new generation energy storage device, with operating voltage it is high, energy density is high, have extended cycle life,
The advantages of self-discharge rate is low, small volume, Environmental compatibility are good, has become after lead-acid battery, nickel-cadmium cell, Ni-MH battery
A kind of important energy storage device, be widely used in the fields such as electronic product, power vehicle, Aero-Space.However, with lithium from
The exploitation and application of sub- battery, the demand of lithium are improved rapidly, and price also goes up therewith, and the reserves of lithium resource are extremely limited,
This will produce certain obstruction to the development of lithium ion battery.By contrast, have similar to lithium ion battery energy storage mechnism
The advantage of sodium-ion battery is just highlighted.Content of the sodium in the earth's crust comes the 6th, and rich reserves are cheap.Na+/
Na electricity to standard electrode potential (- 2.71 V vs SHE) only compare Li+/ Li (- 3.04 V vs SHE) is higher by about 0.3V.
Under the application conditions not having high requirements in extensive energy storage or to portability, it is possible to play the sodium reserves of sodium-ion battery
The high, advantage of low cost.
Sodium and lithium belong to the first main group, there is similar chemical property, and sodium ion radius ratio lithium ion is big by 30%, compared with
Big atomic mass causes the reduction of sodium-ion battery energy density.Although the initial search time with lithium ion battery is close,
The progress of sodium-ion battery relatively lags behind, and existing sodium-ion battery positive material specific capacity is low, and operating voltage is low.Cause
And, research and development are a kind of to have high voltage, the sodium-ion battery positive material important in inhibiting of high power capacity.Lithium ion cell positive material
In material, the lithium-rich manganese-based layered oxide based on manganous acid lithium grinds extensively because the high-tension characteristic of its high power capacity is received
Study carefully, 2013, the Liang Ge seminars of AIST successively report the research to rich sodium material（Development of High
Capacity Cathode Material for Sodium Ion Batteries Na0.95Li0.15(Ni0.15Mn0.55Co0.1)
O2. Journal of The Electrochemical Society, 2013, 160 (6): 933-939. //
Designing high-capacity cathode materials for sodium-ion batteries.
Electrochemistry Communications, 2013, 34: 215–218.）, the two is entered by rich lithium material
The mode of the de- lithium of row electrochemistry and embedding sodium has tentatively obtained rich sodium material.Rich sodium material Central Asia sodium manganate is a unstable phase,
It is difficult to be directly synthesized.The present invention successfully synthesizes manganous acid sodium material with simple solid phase method, and raw material is cheap and easy to get, technological operation
Simply, product purity is high, and process control and properties of product all have good reappearance.
It is characteristic of the invention that：（1）There is provided Na2MnO3Simple preparation process, raw material is easy to get, and flow is short, energy consumption
Low, production cost is small.（2）Material obtained by the present invention 2.0 ~ 4.6V of normal temperature and pressure voltage range, the electric current of 15mA/g
First discharge specific capacity is up to 120 mAh/g under density.
The content of the invention
Simple it is an object of the invention to provide a kind of technological operation, product purity is high, and electrochemical performance
Na2MnO3Positive electrode simple preparation method.
Preparation method of the invention is comprised the following steps：
1）By the manganese source compound of certain stoichiometric proportion and sodium source compound, ground and mixed is uniform；
2）By step 1）The mixture of gained is cooled to room temperature after pyroreaction under inert gas shielding；
3）By step 2）The product grinding of gained obtains final product target product manganous acid sodium through distilling after water washing is dried to neutrality water removal.
The present invention relates to a kind of sodium-ion battery high-voltage anode material manganous acid sodium Na2MnO3Preparation method, especially
Relate to the use of the method that solid phase method simple and easy to apply prepares the sodium-ion battery positive material manganous acid sodium of high-purity, belong to sodium from
Sub- battery material technical field.
The manganese source compound is 1 with the mol ratio of sodium source compound:2.0~1:2.5.
The method for preparing solid phase of the manganous acid sodium positive electrode, it is characterised in that the manganese source compound is titanium dioxide
One or more in manganese, mangano-manganic oxide, manganese sesquioxide managnic oxide.
The sodium source compound is one or more in NaOH, sodium acetate, sodium sulphate, sodium nitrate and sodium chloride.
The temperature of the pyroreaction is 400 ~ 700 DEG C, and the pyroreaction time is 8 ~ 20h.
The inert atmosphere can be one or more in nitrogen, argon gas, helium, hydrogen.
The water removal drying mode of gained mixture is heating water bath evaporation, drying box drying, vacuum after the pyroreaction
One of which in drying, dries temperature for removing water for 60 ~ 150 DEG C.
The type of cooling is programme-control slow cooling, natural cooling, post-calcination sample directly take out in tube furnace
Fast cooling, quenching-in water is plunged the sample into, plunge the sample into the one of which in quenching in liquid nitrogen.
Brief description of the drawings
In order to illustrate more clearly of technical scheme, below to be used needed for the present invention and embodiment description
Accompanying drawing do simple introduction.It should be evident that drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill in field, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 is the prepared Na of the present invention2MnO3The X-ray diffractogram of positive electrode sample.As seen from Figure 1, it is prepared
Na2MnO3Material phase purity is high, good crystallinity.
Fig. 2 is the prepared Na of the present invention2MnO3Positive electrode sample is swept under fast 0.05mV/s in voltage range 2.0-4.6V
Cyclic voltammetry curve figure.As seen from Figure 2, prepared Na2MnO3Material has obvious redox under high voltages
Reaction.
Fig. 3 is the prepared Na of the present invention2MnO3The first charge-discharge curve map of positive electrode sample.As seen from Figure 3,
Prepared Na2MnO3Material has specific discharge capacity higher.
Fig. 4 is the prepared Na of the present invention2MnO3The charge and discharge cycles curve map of positive electrode sample.As seen from Figure 4,
Prepared Na2MnO3Material has good cycle performance and reaction invertibity.
Specific embodiment
For the ease of understanding the present invention, the present invention is described in further detail with reference to specific embodiment.Obviously, institute
The embodiment of description is only section Example of the invention, rather than whole embodiments.Based on embodiments of the invention, this
The every other embodiment that field those of ordinary skill is obtained under the premise of creative work is not made, belongs to the present invention
Protection domain.
Embodiment 1
0.015mol manganese dioxide, 0.037mol NaOH are added separately in mortar, slightly ground and mixed is uniform, connects
And powder be transferred in porcelain boat, in tube furnace, 10h is reacted at 500 DEG C under argon gas atmosphere, then naturally cool to room temperature,
Take out product and be washed to filtrate in neutrality, then 80 DEG C of vacuum drying, product Na is obtained final product after dried sample is ground2MnO3.Sample
The X-ray powder diffraction figure of product is pure phase Na referring to Fig. 1, the product for showing gained2MnO3, crystallinity is high.The product of gained is made
Be positive electrode, experiment button sodium rechargeable battery be assembled into the glove box full of argon gas, with the multiplying power of 0.1C 2.0 ~
Charge and discharge cycles are carried out in the potential region of 4.6V, first discharge specific capacity is 120mAh/g, shows excellent electrochemistry
Energy.
Embodiment 2
0.015mol manganese dioxide, 0.03mol sodium acetates are added separately in mortar, slightly ground and mixed is uniform, then will
Powder is transferred in porcelain boat, in tube furnace, 12h is reacted at 450 DEG C under nitrogen atmosphere, then naturally cools to room temperature, is taken out
Product is washed to filtrate in neutrality, then 110 DEG C of vacuum drying, and product Na is obtained final product after dried sample is ground2MnO3。
Embodiment 3
0.015mol manganese dioxide, 0.03mol sodium nitrate are added separately in mortar, slightly ground and mixed is uniform, then will
Powder is transferred in porcelain boat, in tube furnace, 8h is reacted at 600 DEG C under nitrogen atmosphere, then naturally cools to room temperature, is taken out and is produced
Thing is washed to filtrate in neutrality, then 70 DEG C of vacuum drying, and product Na is obtained final product after dried sample is ground2MnO3。
Claims (8)
1. a kind of preparation method of sodium-ion battery high-voltage anode material manganous acid sodium, it is characterised in that first using solid phase method
The material is prepared, and for sodium-ion battery, is mainly included the following steps that：
1）By the manganese source compound of certain stoichiometric proportion and sodium source compound, ground and mixed is uniform；
2）By step 1）The mixture of gained is cooled to room temperature after pyroreaction under inert gas shielding；
3）By step 2）The product grinding of gained obtains final product target product manganous acid sodium through distilling after water washing is dried to neutrality water removal.
2. the method for preparing solid phase of manganous acid sodium positive electrode as claimed in claim 1, it is characterised in that the manganese source chemical combination
Thing is 1 with the mol ratio of sodium source compound:2.0~1:2.5.
3. the method for preparing solid phase of manganous acid sodium positive electrode as claimed in claim 1, it is characterised in that the manganese source chemical combination
Thing is one or more in manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide.
4. the method for preparing solid phase of manganous acid sodium positive electrode as claimed in claim 1, it is characterised in that the sodium source chemical combination
Thing is one or more in NaOH, sodium acetate, sodium sulphate, sodium nitrate and sodium chloride.
5. the method for preparing solid phase of manganous acid sodium positive electrode as claimed in claim 1, it is characterised in that the temperature of pyroreaction
It is 400 ~ 700 DEG C to spend, and the pyroreaction time is 8 ~ 20h.
6. the method for preparing solid phase of manganous acid sodium positive electrode as claimed in claim 1, it is characterised in that inert atmosphere is nitrogen
One or more in gas, argon gas, helium, hydrogen.
7. the method for preparing solid phase of manganous acid sodium positive electrode as claimed in claim 1, it is characterised in that institute after pyroreaction
The water removal drying mode for obtaining mixture can be one or more in heating water bath evaporation, drying box drying, vacuum drying, dry
Temperature for removing water is 60 ~ 150 DEG C.
8. the method for preparing solid phase of manganous acid sodium positive electrode as claimed in claim 1, it is characterised in that the type of cooling
For programme-control slow cooling, in tube furnace, natural cooling, post-calcination sample directly take out fast cooling, plunge the sample into water
Middle quenching, the one of which for plunging the sample into quenching in liquid nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710135198.8A CN106800312B (en) | 2017-03-08 | 2017-03-08 | A kind of preparation method for sodium-ion battery positive material manganous acid sodium |
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| CN201710135198.8A CN106800312B (en) | 2017-03-08 | 2017-03-08 | A kind of preparation method for sodium-ion battery positive material manganous acid sodium |
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| CN106800312B CN106800312B (en) | 2019-11-19 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003063273A2 (en) * | 2001-10-09 | 2003-07-31 | Valence Technology Inc. | Stabilized electrochemical cell active material |
| CN103259009A (en) * | 2013-04-18 | 2013-08-21 | 恩力能源科技（南通）有限公司 | Water system alkaline metal ion electrochemical energy-storing device |
| CN103427112A (en) * | 2013-08-22 | 2013-12-04 | 郭建国 | Controlled electric field effect charge-discharge sodium ion battery and rapid charge-discharge method thereof |
| CN103441259A (en) * | 2013-08-12 | 2013-12-11 | 恩力能源科技（南通）有限公司 | Anode material of high-magnification aqueous alkali metal electrochemical battery and preparation method of anode material |
| 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 |
| CN103896339A (en) * | 2012-12-27 | 2014-07-02 | 北京汉能创昱科技有限公司 | Preparation method of sodium manganese oxide |
| CN104036965A (en) * | 2014-07-02 | 2014-09-10 | 江苏腾方新能源科技有限公司 | Sodium ion hybrid supercapacitor |
-
2017
- 2017-03-08 CN CN201710135198.8A patent/CN106800312B/en active Active
Patent Citations (7)
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|---|---|---|---|---|
| WO2003063273A2 (en) * | 2001-10-09 | 2003-07-31 | Valence Technology Inc. | Stabilized electrochemical cell active material |
| 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 |
| CN103896339A (en) * | 2012-12-27 | 2014-07-02 | 北京汉能创昱科技有限公司 | Preparation method of sodium manganese oxide |
| CN103259009A (en) * | 2013-04-18 | 2013-08-21 | 恩力能源科技（南通）有限公司 | Water system alkaline metal ion electrochemical energy-storing device |
| CN103441259A (en) * | 2013-08-12 | 2013-12-11 | 恩力能源科技（南通）有限公司 | Anode material of high-magnification aqueous alkali metal electrochemical battery and preparation method of anode material |
| CN103427112A (en) * | 2013-08-22 | 2013-12-04 | 郭建国 | Controlled electric field effect charge-discharge sodium ion battery and rapid charge-discharge method thereof |
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Non-Patent Citations (4)
| Title |
|---|
| SANG-HO PARK ET AL.: "Powder property and electrochemical characterization of Li2MnO3 material", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
| Z.GONTARZ ET AL.: "Solid phase reactivity of sodium oxosalts of manganese", 《JOURNAL OF THERMAL ANALYSIS》 * |
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