CN108493396A - A kind of O3 types sodium-ion battery layered cathode material, preparation method and the usage - Google Patents
A kind of O3 types sodium-ion battery layered cathode material, preparation method and the usage Download PDFInfo
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- CN108493396A CN108493396A CN201810326600.5A CN201810326600A CN108493396A CN 108493396 A CN108493396 A CN 108493396A CN 201810326600 A CN201810326600 A CN 201810326600A CN 108493396 A CN108493396 A CN 108493396A
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- ion battery
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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 O3 types sodium-ion battery layered cathode material, preparation method and the usage, the group of the positive electrode becomes NaNi1/2Co1/6Mn3/8O2.Preparation method is high temperature solid-state method, is comprised the steps of：Metal oxide and sodium source are stoichiometrically mixed, after mixing tabletting, then temperature programming, to required temperature, up to the positive electrode after keeping temperature to cool down for a period of time, the metal oxide is respectively NiO, Co2O3、MnO2.The O3 type sodium-ion battery layered cathode material synthetic methods of the present invention are simple, are easy to amplificationization application；Material character is stablized, uniform particle diameter, has excellent cycle performance, has and stores up usable sodium-ion battery with great potentiality as large size, application prospect is good.
Description
Technical field
The invention belongs to battery technology fields, and in particular to a kind of O3 types sodium-ion battery positive material NaNi1/2Co1/ 6Mn3/8O2, preparation method and the usage.
Background technology
In recent years, environmental pollution for increasingly showing especially and being brought using fossil energy of fossil energy scarcity problem etc. is secondary asks
Topic is on the rise so that for cleaning the research emphasis for being developed into each scientific research institution of sustainable secondary energy sources.Lithium from
Sub- battery has many advantages, such as that capacity is big as a kind of environmentally protective renewable resource, and energy density is high, but due to lithium source
Reserves are limited and being unevenly distributed all over the world, the price of lithium ion battery associated materials is also with lithium ion battery
Develop and constantly rise, this will greatly limit lithium ion battery as the application of massive energy storage device.
Sodium belongs to same main group with lithium, has similar physicochemical property, battery charging and discharging principle almost the same.When charging,
Na+From positive electrode (with NaMnO2For) in abjection, by electrolyte insertion negative material (by taking hard carbon as an example), while electronics
It is transferred to cathode by external circuit, keeps charge balance；It is then opposite when electric discharge.Compared with lithium ion battery, sodium-ion battery tool
There are following characteristics：Sodium is resourceful, accounts for about the 2.64% of crustal elements reserves, and cheap, widely distributed.As it can be seen that with sodium
There is great advantage in cost for the secondary cell of raw material.Moreover, in sodium-ion battery positive material, layered oxide tool
There are the advantages such as specific capacity height, good cycling stability, is a kind of positive electrode with development potentiality.
From the point of view of the application demand of extensive energy storage, ideal secondary cell is in addition to suitable chemical property, also
The economic results in society indexs such as resourceful, price is cheap must be taken into account.Recently, secondary cell is wanted to energy density and volume
Ask the application of the extensive energy storage such as not high intelligent grid and regenerative resource so that it is close that sodium-ion battery obtains people again
Concern.
However, sodium ion heavier mass and radius (0.102nm) is greatly than lithium (0.069nm), this can lead to Na+In electrode material
Deintercalation is slow in material, influences the cycle and high rate performance of battery.Meanwhile Na+/ Na electricity pair standard electrode potential (-
2.71VvsSHE) the about 0.3V (- 3.04VvsSHE) than Li+/Li high, therefore, for conventional electrode material, sodium ion electricity
The energy density in pond is less than lithium ion battery.
Invention content
The object of the present invention is to overcome the problems, such as that existing sodium-ion battery positive material cycle performance is poor, one is provided
Kind O3 type sodium-ion battery positive materials and preparation method thereof.The preparation method of the O3 type sodium-ion battery positive materials is simply easy
Row is easy to industrialization amplification, and synthetic material consistency is good, has excellent cycle performance.Be conducive to long-life sodium-ion battery
Exploitation.
In order to achieve the above object, the present invention provides a kind of novel O3 type sodium-ion battery positive materials, the anodes
Material group becomes NaNi1/2Co1/6Mn3/8O2。
Preferably, the grain size of the positive electrode is 1-5um.
The present invention also provides a kind of preparation method according to above-mentioned O3 type sodium-ion battery layered cathode materials, the party
Method is high temperature solid-state method, is comprised the steps of：Metal oxide and sodium source are stoichiometrically mixed, pressed after mixing
Piece, then temperature programming keep temperature for a period of time to required temperature, up to the positive electrode, the metal oxygen after cooling
Compound is respectively NiO, Co2O3、MnO2。
Preferably, the sodium source is natrium carbonicum calcinatum.
Preferably, the mixed method refers to wet ball grinding, specifically, metal oxide and sodium source mixed-powder are added
Enter in ball grinder, add the ethyl alcohol of powder gross mass 40%, after planetary ball mill 350r/min ball millings 12 hours, uses
Then 250r/min ball millings 2 hours are dried extra ethyl alcohol at 80 DEG C and are obtained.
Preferably, the tabletting method is using stainless steel grinding tool, by oil pressure pump by powder be pressed into 5mm thickness,
The disk of 14mm diameters, compaction pressure 15mbar.
Preferably, the heating rate of temperature programming is 1-5 DEG C/min, required temperature is 850-950 DEG C.Preferably, it heats up
Rate is 5 DEG C/min, and required temperature is 900 DEG C, and calcination atmosphere is air atmosphere, and roasting time is 12 hours.
Preferably, the cool-down method cools down for natural cooling.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that：Sodium-ion battery positive material NaNi provided by the invention1/2Co1/6Mn3/ 8O2With very excellent cycle performance, capacity retention ratio is higher than 90% after 0.1C is recycled 150 times.For the energy storage device of long-life
Research and development provide one and have very much potential positive electrode.In addition, synthetic method of the present invention is simple, it is easy to industry
Change enhanced processing.The positive electrode specific capacity measurement error being synthesized every time is small, and material each batch consistency is good, repeated
It is good.
The sodium-ion battery positive material of the present invention can be applied to prepare sodium-ion battery, and sodium-ion battery has bigger
Cost advantage has potentiality and advantage as large-scale energy storage system application.
Description of the drawings
Fig. 1 is the SEM that presoma is mixed in embodiment（Scanning electron microscope, scanning electron are aobvious
Micro mirror）Figure.
Fig. 2 is positive electrode NaNi obtained by embodiment1/2Co1/6Mn3/8O2SEM figure.
Fig. 3 is the sodium-ion battery positive material assembled using material prepared by embodiment as positive electrode at 0.1C
Loop test curve graph.
Fig. 4 is the sodium-ion battery positive material assembled using material prepared by embodiment as positive electrode in different multiplying
Under charging and discharging curve test chart.
Specific implementation mode
Below in conjunction with drawings and examples, the following further describes the technical solution of the present invention.
It is further illustrated the present invention below by the mode of embodiment, the experiment of actual conditions is not specified in following embodiment
Method according to conventional methods and conditions, or is selected according to product manual.
Embodiment
Sodium-ion battery positive material NaNi1/2Co1/6Mn3/8O2Preparation method
Sodium carbonate, NiO, Co are weighed successively2O3、MnO2And TiO2, it is 1.05 to make the molar ratio of Na, Ni, Co, Mn atom：1/2：
1/6：3/8.
The powder weighed is poured into ball grinder, the ethyl alcohol of 40% mass of powder gross mass is added, ball is covered tightly after being simply mixed
Grinding jar lid is sealed with parafilm films, is sandwiched on planetary ball mill, ball milling 350r/min ball millings use 250r/ after 12 hours
Min ball millings 2 hours.
Slurry after ball milling is placed directly at 80 DEG C and dries, and simple grinding, bulk particle is ground and is dissipated later, and Fig. 1 is mixing
The SEM of presoma schemes, and material is evenly distributed, and average grain diameter is about 1-3um.Using stainless steel mould, using oil pressure pump by powder
It is compacted into the disk of 14mm diameters, 5mm thickness, compaction pressure 15mbar.
The raw material of compacting is placed in batch-type furnace and is roasted, heating rate is 5 DEG C/min, and calcination temperature is 900 DEG C, roasting
Burning atmosphere is air atmosphere, and roasting time is 12 hours.
Cooled to room temperature after roasting, you can obtain the positive electrode NaNi1/2Co1/6Mn3/8O2.Fig. 2 is gained anode
Material NaNi1/2Co1/6Mn3/8O2SEM figure, material surface is smooth, present laminar structured, average grain diameter 1um.Experiment hair
Existing, which contributes to sodium ion insertion abjection, and product is made to have better performance.
Weigh the NaNi of 0.8g above-described embodiments preparation1/2Co1/6Mn3/8O2Sodium-ion battery positive material is added 0.1g and leads
Electrical carbon is black and 0.1g Kynoar is dispersed in N, in N '-methyl pyrrolidones.It is coated on aluminium foil and makes after mixing
It is to electrode with metallic sodium piece, glass fibre Whatman is diaphragm, 0.9M in argon atmospher glove box at electrode slice
NaPF6/ DME is electrolyte, is assembled into button cell.
In 2-3.75V voltage ranges, charge-discharge test is carried out to battery, Fig. 3 is the sodium-ion battery of embodiment synthesis
Loop test curve graph of the positive electrode at 0.1C, in 150 circle cycles, the specific capacity of material is stablized in 100mAhg-1It is left
The right side, average often circle specific capacity reduce 0.067%, it is seen that its cycle performance is good.Fig. 4 is the sodium-ion battery anode of embodiment synthesis
Charging and discharging curve test chart of the material at 0.1C, with the progress of cycle, the specific discharge capacity of material slightly reduces, and polarization is omited
There is increase.As seen from the figure, the sodium-ion battery positive material cycle performance is preferable, in cyclic process voltage platform be not in compared with
Big reduction, capacity are not in greater attenuation.
Although present disclosure is discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read the above, for the present invention's
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. a kind of O3 types sodium-ion battery layered cathode material, which is characterized in that the positive electrode group becomes NaNi1/2Co1/ 6Mn3/8O2。
2. O3 types sodium-ion battery layered cathode material as described in claim 1, which is characterized in that the grain of the positive electrode
Diameter is 1-5um.
3. a kind of preparation method of O3 types sodium-ion battery layered cathode material according to claim 1, which is characterized in that
This method is high temperature solid-state method, is comprised the steps of：Metal oxide and sodium source are stoichiometrically mixed, after mixing
Tabletting, then temperature programming obtain NaNi to required temperature after keeping temperature to cool down for a period of time1/2Co1/6Mn3/8O2Positive electrode,
The metal oxide includes NiO, Co2O3、MnO2。
4. the preparation method of O3 types sodium-ion battery layered cathode material as claimed in claim 3, which is characterized in that described
Sodium source is natrium carbonicum calcinatum.
5. the preparation method of O3 types sodium-ion battery layered cathode material as claimed in claim 3, which is characterized in that mixing
Method refers to that metal oxide and sodium source mixed-powder are added in ball grinder, adds the ethyl alcohol of powder gross mass 40%, makes
After planetary ball mill 350r/min ball millings 12 hours, with 250r/min ball millings 2 hours, drying removed ethyl alcohol.
6. the preparation method of O3 types sodium-ion battery layered cathode material as claimed in claim 3, which is characterized in that tabletting
Method is that powder is pressed into using grinding tool by oil pressure pump the disk of 5mm thickness, 14mm diameters；The compaction pressure of tabletting is
15mbar。
7. the preparation method of O3 types sodium-ion battery layered cathode material as claimed in claim 3, which is characterized in that program liter
The heating rate of temperature is 1-5 DEG C/min, and required temperature is 850-950 DEG C.
8. the preparation method of O3 types sodium-ion battery layered cathode material as claimed in claim 7, which is characterized in that program liter
The heating rate of temperature is 5 DEG C/min, and required temperature is 900 DEG C, and calcination atmosphere is air atmosphere, and roasting time is 12 hours.
9. the preparation method of O3 types sodium-ion battery layered cathode material as claimed in claim 3, which is characterized in that cooling side
Method cools down for natural cooling.
10. a kind of purposes of O3 types sodium-ion battery layered cathode material according to claim 1, which is characterized in that its
Positive electrode as sodium-ion battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110416601A (en) * | 2019-08-07 | 2019-11-05 | 哈尔滨师范大学 | A kind of preparation method of sode cell bath surface metal oxide layer |
| CN110970612A (en) * | 2018-09-29 | 2020-04-07 | 中国科学院大连化学物理研究所 | Preparation of transition metal oxide positive electrode material and application of transition metal oxide positive electrode material in sodium ion battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110970612A (en) * | 2018-09-29 | 2020-04-07 | 中国科学院大连化学物理研究所 | Preparation of transition metal oxide positive electrode material and application of transition metal oxide positive electrode material in sodium ion battery |
| CN110416601A (en) * | 2019-08-07 | 2019-11-05 | 哈尔滨师范大学 | A kind of preparation method of sode cell bath surface metal oxide layer |
| CN110416601B (en) * | 2019-08-07 | 2022-08-02 | 哈尔滨师范大学 | Preparation method of metal oxide layer on electrolyte surface of sodium battery |
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Application publication date: 20180904 |