CN107946581A - A kind of power-type sodium-ion battery positive material and preparation method thereof - Google Patents
A kind of power-type sodium-ion battery positive material and preparation method thereof Download PDFInfo
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- CN107946581A CN107946581A CN201711228974.5A CN201711228974A CN107946581A CN 107946581 A CN107946581 A CN 107946581A CN 201711228974 A CN201711228974 A CN 201711228974A CN 107946581 A CN107946581 A CN 107946581A
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- Prior art keywords
- ion battery
- battery positive
- sodium
- positive material
- power
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Classifications
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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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- 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
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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 belongs to electrochemical technology field, is specially a kind of power-type sodium-ion battery positive material and preparation method thereof.The sodium-ion battery positive material of the present invention is the ternary layered metal oxide of manganese nickel magnesium, its chemical formula is Na0.66Mn0.6Ni0.4‑x Mg x O2（0 ＜x≤0.4）.The electrode material is prepared using solid-phase synthesis.The reversible capacity of the electrode material is about 50 ~ 140 mAh g‑1, energy density is about 200 400 Wh kg‑1.Superior cyclical stability and fast charging and discharging performance are shown in charge and discharge process.The cathode stratified material is higher than energy, and cycle performance is good, and preparation method is simple, is a kind of excellent power-type sodium-ion battery positive material.
Description
Technical field
The invention belongs to electrochemical technology field, and in particular to can use positive electrode active materials and its preparation side of sodium-ion battery
Method.
Background technology
Energy problem enjoys social concerns always, and as emerging electric energy storage device, lithium ion battery is rapidly sent out in recent years
Exhibition, from mobile electronic device to electric automobile, the demand of people increasingly increases.But lithium source reserves are barren directly to restrict lithium
Ion battery develops, especially extensive storing up electricity, is badly in need of researching and developing new secondary cell system.Sodium has similar atom knot to lithium
Structure and chemical property, and the reserves of global sodium element are extremely abundant, and sodium-ion battery is subject to the extensive concern of researcher.But
Sodium-ion battery positive material can not much meet the needs of sodium-ion battery commercialized development at present, thus find new sodium from
Sub- cell positive material becomes very urgent.
The present invention is prepared for novel lamellar sodium-ion battery positive material Na using solid-phase synthesis0.66Mn0.6Ni0.4- x Mg x O2（0 ＜x≤0.4）, be a kind of novel lamellar positive electrode with P2 structures, had compared with high charge-discharge capacity and good
The sodium-ion battery positive material of good cycle performance.
The content of the invention
It is an object of the invention to propose a kind of layered cathode material and its system of good performance for sodium-ion battery
Preparation Method.
It is proposed by the present invention to be used for power-type sodium-ion battery positive material, it is the ternary layered metal oxide of manganese nickel magnesium,
Its chemical formula is Na0.66Mn0.6Ni0.4-x Mg x O2（0 ＜x≤ 0.4, preferably 0 ＜x＜ 0.4, similarly hereinafter）Stratified material, form metal
The element ratio of the manganese nickel magnesium of oxide meets 0.6:0.4-x:x.Research has shown that such positive electrode has good electrification
Performance is learned, fast charging and discharging performance is good, can be as the positive electrode of high-performance sodium-ion battery.Up to the present do not close also
In such sodium-ion battery positive material and its report of preparation.
Na proposed by the present invention0.66Mn0.6Ni0.4-x Mg x O2（0 ＜x≤0.4）Positive electrode is powder type, it is once
Particle size is at 2 ~ 5 μm.
Na proposed by the present invention0.66Mn0.6Ni0.4-x Mg x O2（0 ＜x≤0.4）The preparation method of positive electrode, using solid phase
Synthetic method, comprises the following steps that：
By Na2CO3、C4H6O4Ni 4H2O、Mn2O3With MgO according to Na0.66Mn0.6Ni0.4-x Mg x O2（0 ＜x≤0.4）Chemistry meter
Amount after grinding, with 10 ~ 20 h of ball mill ball milling, the mixture after ball milling is inserted in tube furnace, 800 ~ 1100 than mixing
DEG C keep 10 ~ 20h, be cooled to room temperature, that is, obtain needed for positive electrode.
In the present invention, Na0.66Mn0.6Ni0.4-x Mg x O2（0 ＜x≤0.4）Crystal structure and thing are mutually by X-ray diffraction（XRD）
Determine.Diffraction patterns show Na prepared by this method0.66Mn0.6Ni0.4-x Mg x O2（0 ＜x≤0.4）Sample is single pure phase, is belonged to
Hexagonal crystal system, space group P63/ mmc, belongs to P2 structure stratified materials.
In the present invention, by Na0.66Mn0.6Ni0.4-x Mg x O2（0 ＜x≤0.4）Electrode is made coated on aluminium foil in material, makees
For the cathode of sodium-ion battery.By 70% sample, 20% conductive black is evenly spread in the nmp solution of 10%PVDF.Uniformly apply
Overlay on aluminium foil, after drying, be washed into the circular electric pole piece of a diameter of 14 mm.
In the present invention, Na0.66Mn0.6Ni0.4-x Mg x O2（0 ＜x≤0.4）Electrochemical property test is used and is made of three electrodes
Sodium ion battery system.Wherein, Na0.66Mn0.6Ni0.4-x Mg x O2（0 ＜x≤0.4）As working electrode, sodium foil is used as to electricity
Pole and reference electrode.Electrolyte is 1M NaClO4+EC+DEC+PC (VEC:VDEC:VPC=1:1:1), battery is in the hand full of argon gas
Assembled in casing.The battery performance of the sodium-ion battery is in blue electricity（Land）Carried out on battery test system.
In the present invention, the Na of solid-phase synthesis synthesis is utilized0.66Mn0.6Ni0.4-x Mg x O2Sample, has preferable discharge and recharge
Performance, in 2.5 ~ 4.2V of voltage range（vs. Na+/Na）With 10 ~ 150mA of current density g-1When, preferable fast charging and discharging
Performance and cyclical stability, average charge and discharge platform have higher energy density between 3.4-4.0 V.In the electricity of 10 C
Under current density, the circle of circulation 500 still has 30-70 mAh g-1Reversible capacity, there is superior fast charging and discharging performance and circulation
Invertibity.
Above-mentioned performance shows, by the Na of solid reaction process preparation0.66Mn0.6Ni0.4-x Mg x O2（0 ＜x≤0.4）For pure phase
Compound, is a kind of new positive electrode, can be used as power-type sodium-ion battery positive material.
Brief description of the drawings
Fig. 1 is Na0.66Mn0.6Ni0.2Mg0.2O2And Na0.66Mn0.6Ni0.3Mg0.1O2XRD diagram.
Fig. 2 is Na0.66Mn0.6Ni0.2Mg0.2O2Electrode is 150mA g in current density-1When the 1st, 2,5,10,20 time circulation
Charging and discharging curve.
Embodiment
Embodiment 1
Use Na2CO3、C4H6O4Ni 4H2O、Mn2O3With MgO as presoma, according to Na:Mn:Ni:Mg is 0.66:0.6:0.2:
0.2 ratio mixes, and after ball milling 12h, by the mixture of acquisition in tube furnace, burns 12h in 900 DEG C, can be obtained after cooling
Na0.66Mn0.6Ni0.2Mg0.2O2Sample.
XRD characterization shows（See attached drawing 1）, the Na of synthesis0.66Mn0.6Ni0.2Mg0.2O2It is single-phase, belongs to hexagonal crystal system, it is empty
Between group be P63/mmc.By 70% sample, 20% conductive black is evenly spread in the nmp solution of 10%PVDF.It is coated uniformly on
On aluminium foil, after drying, the circular electric pole piece of a diameter of 14 mm is washed into.Using the circular electric pole piece as working electrode, with sodium
Paper tinsel is used as forms button cell to electrode.Its electrolyte is 1M NaClO4+EC+DEC+PC (VEC:VDEC:VPC=1:1:1), filling
Battery is assembled in the glove box of full argon gas.The constant current charge-discharge test of battery carries out on Land battery test systems.
Na0.66Mn0.6Ni0.2Mg0.2O2In 2.5 ~ 4.2 V（vs. Na+/Na）Electrochemical window in, 100mA g-1Filled under current density
Electric discharge reversible capacity is 60 ~ 100mAh g-1, capacity can still keep 70 % after circulation 500 is enclosed.
Embodiment 2
Use Na2CO3、C4H6O4Ni 4H2O、Mn2O3With MgO as presoma, according to Na:Mn:Ni:Mg is 0.66:0.6:0.3:
0.1 ratio mixing, after 12 h of ball milling, by the mixture of acquisition in tube furnace, burns 12 h, after cooling i.e. in 900 DEG C
Na can be obtained0.66Mn0.6Ni0.3Mg0.1O2Sample.
XRD characterization shows（See attached drawing 1）, the Na of synthesis0.66Mn0.6Ni0.3Mg0.1O2It is single-phase, belongs to hexagonal crystal system, it is empty
Between group be P63/mmc.By 70% sample, 20% conductive black is evenly spread in the nmp solution of 10%PVDF.It is coated uniformly on
On aluminium foil, after drying, the circular electric pole piece of a diameter of 14 mm is washed into.Using the circular electric pole piece as working electrode, with sodium
Paper tinsel is used as forms button cell to electrode.Its electrolyte is 1M NaClO4+EC+DEC+PC (VEC:VDEC:VPC=1:1:1), filling
Battery is assembled in the glove box of full argon gas.The charge-discharge test of battery carries out on Land battery test systems.
Na0.66Mn0.6Ni0.3Mg0.1O2The electrode of sample is demonstrated by good chemical property.In 2.5 ~ 4.2 V of voltage range（vs. Na+/Na）It is interior, 200 mA g-1Reversible capability of charging and discharging is respectively 50 ~ 90mAh g under current density-1, circulation 500 circle after capacity still
Keep 80 %.
Claims (3)
1. a kind of power-type sodium-ion battery positive material, it is characterised in that be the ternary layered metal oxide of manganese nickel magnesium, it is changed
Formula is Na0.66Mn0.6Ni0.4-x Mg x O2, 0 ＜x≤0.4。
2. power-type sodium-ion battery positive material according to claim 1, it is characterised in that it is powder type, one
Secondary particle size is at 2 ~ 5 μm.
A kind of 3. preparation method of power-type sodium-ion battery positive material as claimed in claim 1, it is characterised in that tool
Body step is：By Na2CO3、C4H6O4Ni 4H2O、Mn2O3With MgO according to Na0.66Mn0.6Ni0.4-x Mg x O2（0 ＜x≤0.4）Change
Metering is learned than mixing, grinding, with 10 ~ 20 h of ball mill ball milling, the mixture after ball milling is inserted in tube furnace, 800 ~ 1100
DEG C keep 10 ~ 20h, be cooled to room temperature, that is, obtain needed for positive electrode.
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| CN201711228974.5A CN107946581A (en) | 2017-11-29 | 2017-11-29 | A kind of power-type sodium-ion battery positive material and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109742365A (en) * | 2019-01-09 | 2019-05-10 | 东北大学秦皇岛分校 | A kind of sodium-ion battery positive material, preparation method and a kind of sodium-ion battery |
| CN111864200A (en) * | 2020-08-25 | 2020-10-30 | 南开大学 | High-capacity sodium ion battery positive electrode material |
| CN111933943A (en) * | 2020-08-10 | 2020-11-13 | 苏州科技大学 | Sodium ion battery Na with high energy density0.67Mn0.65Fe0.2Ni0.15O2Efficient and stable preparation method of anode material |
| KR20210092775A (en) * | 2019-01-11 | 2021-07-26 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | Positive electrode active material, manufacturing method thereof, sodium ion battery, and apparatus provided with sodium ion battery |
| US20210408541A1 (en) * | 2019-08-07 | 2021-12-30 | Panasonic Intellectual Property Management Co., Ltd. | Positive-electrode active material and battery |
| CN114122383A (en) * | 2021-11-29 | 2022-03-01 | 复旦大学 | Oxygen valence-variable sodium ion battery positive electrode material containing transition metal vacancy and preparation method thereof |
| CN114566632A (en) * | 2022-03-04 | 2022-05-31 | 上海交通大学 | Positive electrode material for sodium ion battery and preparation method thereof |
| CN114678520A (en) * | 2022-02-17 | 2022-06-28 | 扬州大学 | Positive electrode material for sodium ion battery and preparation method thereof |
| CN114725346A (en) * | 2022-03-31 | 2022-07-08 | 钠远新材科技(无锡)有限公司 | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
-
2017
- 2017-11-29 CN CN201711228974.5A patent/CN107946581A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| GURPREET SINGH ET AL.: "《High Voltage Mg-Doped Na0.67Ni0.3–xMgxMn0.7O2 (x=0.05, 0.1) Na-Ion Cathodes with Enhanced Stability and Rate Capability》", 《CHEMISTRY OF MATERIALS》 * |
| PENGFEI WANG ET AL.: "《Suppressing the P2–O2 Phase Transition of Na0.67Mn0.67Ni0.33O2 by Magnesium Substitution for Improved Sodium‐Ion Batteries》", 《ANGEW. CHEM. INT. ED.》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109742365A (en) * | 2019-01-09 | 2019-05-10 | 东北大学秦皇岛分校 | A kind of sodium-ion battery positive material, preparation method and a kind of sodium-ion battery |
| KR102457600B1 (en) | 2019-01-11 | 2022-10-20 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | Positive electrode active material, manufacturing method thereof, sodium ion battery, and apparatus provided with sodium ion battery |
| KR20210092775A (en) * | 2019-01-11 | 2021-07-26 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | Positive electrode active material, manufacturing method thereof, sodium ion battery, and apparatus provided with sodium ion battery |
| US20210408541A1 (en) * | 2019-08-07 | 2021-12-30 | Panasonic Intellectual Property Management Co., Ltd. | Positive-electrode active material and battery |
| CN111933943A (en) * | 2020-08-10 | 2020-11-13 | 苏州科技大学 | Sodium ion battery Na with high energy density0.67Mn0.65Fe0.2Ni0.15O2Efficient and stable preparation method of anode material |
| CN111864200A (en) * | 2020-08-25 | 2020-10-30 | 南开大学 | High-capacity sodium ion battery positive electrode material |
| CN114122383A (en) * | 2021-11-29 | 2022-03-01 | 复旦大学 | Oxygen valence-variable sodium ion battery positive electrode material containing transition metal vacancy and preparation method thereof |
| CN114122383B (en) * | 2021-11-29 | 2023-11-24 | 复旦大学 | Oxygen-valence-changing sodium ion battery positive electrode material containing transition metal vacancy and preparation method thereof |
| CN114678520A (en) * | 2022-02-17 | 2022-06-28 | 扬州大学 | Positive electrode material for sodium ion battery and preparation method thereof |
| CN114678520B (en) * | 2022-02-17 | 2023-08-22 | 扬州大学 | Positive electrode material for sodium ion battery and preparation method thereof |
| CN114566632A (en) * | 2022-03-04 | 2022-05-31 | 上海交通大学 | Positive electrode material for sodium ion battery and preparation method thereof |
| CN114566632B (en) * | 2022-03-04 | 2024-02-06 | 上海苏迪恩新能源科技有限责任公司 | Positive electrode material for sodium ion battery and preparation method thereof |
| CN114725346A (en) * | 2022-03-31 | 2022-07-08 | 钠远新材科技(无锡)有限公司 | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
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