CN106800312B - 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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- CN106800312B CN106800312B CN201710135198.8A CN201710135198A CN106800312B CN 106800312 B CN106800312 B CN 106800312B CN 201710135198 A CN201710135198 A CN 201710135198A CN 106800312 B CN106800312 B CN 106800312B
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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
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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
- 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
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- 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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- C01—INORGANIC CHEMISTRY
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- C01P2006/40—Electric properties
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- 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
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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 the following steps are included: by the manganese source compound of certain stoichiometric ratio and sodium source compound, ground and mixed is uniform；Resulting mixture is transferred in tube furnace, under inert gas protection, is cooled to room temperature after pyroreaction at 400 ~ 700 DEG C；By the grinding of above-mentioned presoma through distillation water washing to neutrality, up to target product manganous acid sodium after dry water removal grinding.This method is added at one time 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 reproducibility.Prepared Na2MnO3Material potential plateau is high, shows excellent chemical property, will provide new approaches for the further research and functionization of this kind of high-energy density positive electrode.
Description
Technical field
The present invention relates to a kind of sodium-ion battery high-voltage anode material manganous acid sodium Na2MnO3Preparation method, especially
The method for relating to the use of the sodium-ion battery positive material manganous acid sodium of simple and easy solid phase method preparation high-purity, belong to sodium from
Sub- battery material technical field.
Background technique
With the growth of population, combustion of fossil fuel bring global warming, the raising of fossil fuel face cost, the mankind
It has increasing need for freeing from the dependence to non-renewable energy resources.Inexhaustible energy source is not yet
In the presence of, wind energy, solar energy are exactly ideal selection, however its round the clock, seasonal be unevenly distributed limit large-scale exploitation
And utilization.The electric energy that wind energy, solar energy are transformed, which must be concentrated, to be stored in order to meet electric power in different time periods and supply
Answer demand.Our facing challenges are exactly the energy conversion from solar energy and wind energy into portable or static power source, and
It realizes efficiently and effectively mutually conversion, realizes the Sustainable Development and Utilization of renewable energy.
Energy storage device of the lithium ion battery as a new generation, have operating voltage is high, energy density is high, have extended cycle life,
The advantages that self-discharge rate is low, small in size, Environmental compatibility is good, has become after lead-acid battery, nickel-cadmium cell, nickel-metal hydride battery
A kind of important energy storage device, be widely used in the fields such as electronic product, power vehicle, aerospace.However, with lithium from
The exploitation and application of sub- battery, the demand of lithium improve rapidly, and price also goes up therewith, and the reserves of lithium resource are extremely limited,
This will generate certain obstruction to the development of lithium ion battery.In contrast, have similar with lithium ion battery energy storage mechnism
The advantage of sodium-ion battery just highlights.Content of the sodium in the earth's crust comes the 6th, and rich reserves are cheap.Na+/
The standard electrode potential (- 2.71 V vs SHE) of Na electricity pair only compares Li+/ Li (- 3.04 V vs SHE) is higher by about 0.3V.
Under extensive energy storage or the application conditions not having high requirements to portability, so that it may play the sodium reserves of sodium-ion battery
Advantage high, at 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 makes the reduction of sodium-ion battery energy density.Although the starting 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 it researches and develops a kind of with high voltage, the sodium-ion battery positive material important in inhibiting of high capacity.Lithium ion cell positive material
In material, the lithium-rich manganese-based layered oxide based on manganous acid lithium is ground extensively because the characteristic of its high capacity high voltage receives
Study carefully, 2013, the Liang Ge seminar of AIST successively reports (the Development of High of the research to rich sodium material
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 be by rich lithium material into
Row electrochemistry takes off lithium and the mode of embedding sodium has tentatively obtained rich sodium material.Rich sodium material Central Asia sodium manganate is a unstable phase,
It is difficult to directly synthesize.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 reproducibility.
The invention has the characteristics that (1) provides Na2MnO3Simple preparation process, raw material is easy to get, and process is short, energy consumption
Low, production cost is small.(2) voltage range of the obtained material of the present invention in 2.0 ~ 4.6V of normal temperature and pressure, the electric current of 15mA/g
First discharge specific capacity is up to 120 mAh/g under density.
Summary of the invention
The purpose of the present invention is to provide a kind of technological operation is simple, product purity is high, and electrochemical performance
Na2MnO3Positive electrode simple preparation method.
Preparation method of the invention the following steps are included:
1) by the manganese source compound of certain stoichiometric ratio and sodium source compound, ground and mixed is uniform；
2) the resulting mixture of step 1) is cooled to room temperature after pyroreaction under inert gas shielding；
3) up to target product Asia manganese after water washing to neutrality water removal drying being distilled in the resulting product grinding of step 2
Sour sodium.
The present invention relates to a kind of sodium-ion battery high-voltage anode material manganous acid sodium Na2MnO3Preparation method, especially
The method for relating to the use of the sodium-ion battery positive material manganous acid sodium of simple and easy solid phase method preparation high-purity, belong to sodium from
Sub- battery material technical field.
The molar ratio of the manganese source compound and sodium source compound is 1:2.0 ~ 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 of manganese, mangano-manganic oxide, manganese sesquioxide managnic oxide.
The sodium source compound is one or more of sodium hydroxide, 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 of 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, dry temperature for removing water are 60 ~ 150 DEG C.
The type of cooling is process control slow cooling, natural cooling, post-calcination sample directly take out in tube furnace
Fast cooling plunges the sample into quenching-in water, plunges the sample into the one of which in liquid nitrogen in quenching.
Detailed description of the invention
In order to illustrate more clearly of technical solution of the present invention, below to required use in the present invention and embodiment description
Attached drawing do simple introduction.It should be evident that drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill in field, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is Na prepared by the present invention2MnO3The X-ray diffractogram of positive electrode sample.As seen from Figure 1, prepared
Na2MnO3Material is mutually with high purity, good crystallinity.
Fig. 2 is Na prepared by 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 apparent redox under high voltages
Reaction.
Fig. 3 is Na prepared by the present invention2MnO3The first charge-discharge curve graph of positive electrode sample.As seen from Figure 3,
Prepared Na2MnO3Material specific discharge capacity with higher.
Fig. 4 is Na prepared by the present invention2MnO3The charge and discharge cycles curve graph of positive electrode sample.As seen from Figure 4,
Prepared Na2MnO3Material has good cycle performance and reaction invertibity.
Specific embodiment
To facilitate the understanding of the present invention, present invention is further described in detail combined with specific embodiments below.Obviously, institute
The embodiment of description is only section Example of the invention, instead of all the embodiments.Based on the embodiment of the present invention, originally
Field those of ordinary skill every other embodiment obtained without creative efforts, belongs to the present invention
Protection scope.
Embodiment 1
0.015mol manganese dioxide, 0.037mol sodium hydroxide are added separately in mortar, slightly ground and mixed is equal
It is even, then powder is transferred in porcelain boat, in tube furnace, in 500 DEG C of reaction 10h under argon atmosphere, is then naturally cooled to
Room temperature, taking-up product are washed to filtrate and are in neutrality, then 80 DEG C of vacuum drying, up to product after the sample after drying is ground
Na2MnO3.The X-ray powder diffraction figure of sample shows that resulting product is pure phase Na referring to Fig. 12MnO3, crystallinity height.By institute
The product obtained is assembled into experiment button sodium rechargeable battery as positive electrode in the glove box full of argon gas, with times of 0.1C
Rate carries out charge and discharge cycles in the potential region of 2.0 ~ 4.6V, and first discharge specific capacity 120mAh/g is shown excellent
Chemical property.
Embodiment 2
0.015mol manganese dioxide, 0.03mol sodium acetate are added separately in mortar, slightly ground and mixed is uniform, connects
Powder is transferred in porcelain boat, in tube furnace, in 450 DEG C of reaction 12h under nitrogen atmosphere, then naturally cool to room temperature,
Taking-up product is washed to filtrate and is in neutrality, then 110 DEG C of vacuum drying, up to product Na after the sample after drying is ground2MnO3。
Embodiment 3
0.015mol manganese dioxide, 0.03mol sodium nitrate are added separately in mortar, slightly ground and mixed is uniform, connects
Powder is transferred in porcelain boat, in tube furnace, in 600 DEG C of reaction 8h under nitrogen atmosphere, then naturally cool to room temperature, take
Product is washed to filtrate and is in neutrality out, then 70 DEG C of vacuum drying, up to product Na after the sample after drying is ground2MnO3。
Claims (4)
1. a kind of preparation method for sodium-ion battery high-voltage anode material manganous acid sodium, which is characterized in that use for the first time
Solid phase method prepares the material, and is used for sodium-ion battery, mainly comprises the steps that
1) by the manganese source compound of certain stoichiometric ratio and sodium source compound, ground and mixed is uniform；
2) the resulting mixture of step 1) is cooled to room after 450~500 DEG C of 10~12h of pyroreaction under protective atmosphere
Temperature；
3) up to target product manganous acid sodium after water washing to neutrality water removal drying being distilled in the resulting product grinding of step 2)；
The molar ratio of the manganese source compound and sodium source compound is 1:2.0~1:2.5；The manganese source compound is titanium dioxide
One or more of manganese, mangano-manganic oxide, manganese sesquioxide managnic oxide；The sodium source compound is sodium hydroxide, sodium acetate, sulfuric acid
One or more of sodium, sodium nitrate and sodium chloride；
Protective atmosphere is one or more of nitrogen, argon gas, helium, hydrogen；
Prepared manganous acid sodium is pure phase Na2MnO3, close in the electric current of the voltage range of normal temperature and pressure 2.0-4.6V, 15mA/g
It spends lower first discharge specific capacity and reaches 120mAh/g.
2. a kind of preparation method for sodium-ion battery high-voltage anode material manganous acid sodium as described in claim 1,
It is characterized in that, the type of cooling is process control slow cooling, natural cooling, post-calcination sample directly take out in tube furnace
Fast cooling plunges the sample into quenching-in water, plunges the sample into the one of which quenched in liquid nitrogen.
3. a kind of preparation method for sodium-ion battery high-voltage anode material manganous acid sodium as described in claim 1,
It is characterized in that the water removal drying mode of gained mixture after pyroreaction can be dry for heating water bath evaporation, drying box drying, vacuum
One or more of dry, dry temperature for removing water is 60~150 DEG C.
4. the manganous acid sodium of any one of claim 1-3 the method preparation is in as sodium-ion battery high-voltage anode material
Purposes.
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Citations (4)
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| WO2003063273A2 (en) * | 2001-10-09 | 2003-07-31 | Valence Technology Inc. | Stabilized electrochemical cell active material |
| 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 |
| 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 |
Family Cites Families (3)
| 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 |
| CN103259009B (en) * | 2013-04-18 | 2019-06-14 | 恩力能源科技有限公司 | A kind of water-system alkali 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 |
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- 2017-03-08 CN CN201710135198.8A patent/CN106800312B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003063273A2 (en) * | 2001-10-09 | 2003-07-31 | Valence Technology Inc. | Stabilized electrochemical cell active 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 |
| 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 |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| Powder property and electrochemical characterization of Li2MnO3 material;Sang-Ho Park et al.;《Materials Chemistry and Physics》;20071231;第102卷;225-230 * |
| 锂离子电池正极材料Li2MnO3的显微组织与电化学性能;邵威等;《中国有色金属学报》;20150331;第25卷(第3期);705-713 * |
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