CN110112375A - The double transition metal manganese base layered cathode materials of sodium-ion battery - Google Patents
The double transition metal manganese base layered cathode materials of sodium-ion battery Download PDFInfo
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- CN110112375A CN110112375A CN201910221196.XA CN201910221196A CN110112375A CN 110112375 A CN110112375 A CN 110112375A CN 201910221196 A CN201910221196 A CN 201910221196A CN 110112375 A CN110112375 A CN 110112375A
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- ion battery
- transition metal
- cathode materials
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- 239000011572 manganese Substances 0.000 title claims abstract description 82
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 68
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 56
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 50
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 50
- 239000010406 cathode material Substances 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000011734 sodium Substances 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 3
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 10
- 150000002696 manganese Chemical class 0.000 claims description 10
- 239000011656 manganese carbonate Substances 0.000 claims description 10
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 10
- 159000000000 sodium salts Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 2
- 230000009466 transformation Effects 0.000 abstract description 4
- 238000009831 deintercalation Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000001354 calcination Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000007600 charging Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000000155 in situ X-ray diffraction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- H01M4/362—Composites
-
- 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
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to a kind of double transition metal manganese base layered cathode materials of sodium-ion battery, it is characterised in that: its general formula is NaxMn1‑ yMyO2, wherein M is Ru, Ir, Nb, Bi, Sn, Ta or Sb, and 0.3≤x≤1,0 < y≤0.5.Material preparation method of the invention is simple, there is stronger practicability, and the material being synthesized improves the electronic conductivity and Na ~+Mobility of material, the phase transformation under high voltage during sodium ion deintercalation is inhibited, so that the specific capacity, high rate performance and cycle performance when the positive electrode is assembled into sodium-ion battery have all obtained effective raising.This method to advanced optimize sodium-ion battery performance and sodium-ion battery future commercialization be all of great significance.
Description
Technical field
The present invention relates to electrochemical field more particularly to a kind of double transition metal manganese base layered cathode materials of sodium-ion battery
Material.
Background technique
Sodium element is the 6th element abundant in the earth's crust, low with the physicochemical properties and price similar with elemental lithium
Honest and clean feature, thus sodium-ion battery is considered as one of the novel energy-storing equipment for being most hopeful to substitute lithium ion battery.However
Sodium-ion battery is there is the migration of sodium ion difficulty, the problems such as stability is poor, and energy density is relatively low.
In recent years, stratiform transition metal oxide has a systems such as height ratio capacity, preparation method be simple and environmental-friendly
Column advantage and paid close attention to by researcher.Especially manganese base stratified material has the characteristics that low price, high capacity are considered as most having
Wish one of commercialized positive electrode.But manganese base stratified material also has the shortcomings that its is intrinsic, this kind of material is in electrochemistry mistake
There is complicated phase transition process in journey, Phase-change Problems especially under high voltages will cause the huge volume change of material and
Structural aberration, so as to cause the decaying of battery cycle life.
There is not yet a kind of sodium-ion battery stratiform for meeting the environmental stability that sodium-ion battery commercialization requires at present
Positive electrode, so that being widely popularized for sodium-ion battery is restricted.
Application No. is 2017105709588 Chinese patents to disclose the manganese-based anode material of sodium-ion battery, in manganese base
The surface of layered cathode material constructs one layer of several nanometers of titanium-based oxide, and the partial size of prepared positive electrode is 2-10 μm,
Specific discharge capacity needs to be further increased.
Summary of the invention
In order to solve the above technical problems, the object of the present invention is to provide a kind of double transition metal manganese base shapes of sodium-ion battery
Positive electrode, the present invention provides a kind of internal stratified material adulterated, positive electrode of the invention holds in charge and discharge process
It measures bigger, high rate performance and cycle performance is more preferable.
The present invention provides a kind of double transition metal manganese base layered cathode materials of sodium-ion battery, general formula NaxMn1- yMyO2, wherein M is Ru, Ir, Nb, Bi, Sn, Ta or Sb, and 0.3≤x≤1,0 < y≤0.5.
Preferably, M Ru.
Preferably, 0.5≤x≤0.9,0.02 < y≤0.3.
It is highly preferred that the general formula of the double transition metal manganese base layered cathode materials of sodium-ion battery is Na0.6Mn0.93Ru0.07O2。
The double transition metal manganese-based anode materials of sodium-ion battery of the invention have layered crystal structure, anode of the invention
In material, Mn constituent content is higher, and main purpose is control battery cost and raising battery capacity.Sodium-ion battery of the invention
Double transition metal manganese base layered cathode materials excite more in cathode material structure by the uniform incorporation of a small amount of other metal M
Sodium ion active site, improve material electric conductivity and inhibit high voltage under material phase transformation, so that electrode material ratio be respectively increased
Capacity, material high rate performance and cycle performance, the final overall performance for improving sodium-ion battery.
Preferably, the positive electrode crystal structure belongs to P63/ mmc orSpace group.
Further, the positive electrode is in the single-size of stratiform packed structures, and the partial size of the positive electrode is
0.2-1μm。
Further, the preparation method of the double transition metal manganese base layered cathode materials of sodium-ion battery of the invention include with
Lower step:
Then tabletting after sodium salt, manganese salt and other metal oxides are mixed is calcined at 700-1100 DEG C, obtain after cooling
The double transition metal manganese base layered cathode materials of the sodium-ion battery；Wherein, other described metal oxides are selected from RuO2、IrO2、
SnO2、Ta2O5、Bi2O3、Nb2O5And Sb2O5One or more of.
Further, the sodium salt is Na2CO3、NaNO3One or more of with NaCl.
Further, the manganese salt is MnCO3And/or Mn (NO3)2.Preferably, manganese salt MnCO3.Manganese salt is calcined
Gas generation is had in journey, so that the particle of finally formed positive electrode is smaller.
Further, the sodium salt, manganese salt and sodium element, manganese element and other metallic elements in other metal oxides
Molar ratio be 0.3-1:0.5-1:0.01-0.5.
Preferably, sodium salt, manganese salt and sodium element, manganese element and other metallic elements in other metal oxides mole
Than for 0.5-0.9:0.6-0.9:0.02-0.3.
Further, it is mixed using ball-milling method, ball milling speed 100-300r/min, Ball-milling Time 2-20h.Ball-milling method
Enable to sodium salt, manganese salt and other metal oxide precursors to mix well, facilitate subsequent reaction, it is full and uniform into
Row.
Further, tabletting is carried out at 1-50MPa.Tabletting is carried out at this pressure, it can be by precursor mixture pressure
Closer, distance diminution between particle is obtained, reacts more abundant and equal between each section presoma when being conducive to subsequent heat treatment
It is even.
Further, when calcining, with the speed of 1-20 DEG C/min from room temperature to 700-1100 DEG C.
Further, it is carried out under oxygen atmosphere or air atmosphere when calcining.
The present invention uses solid sintering technology, makes manganese base stratified material equal by other metallic elements by controlling reaction condition
Even incorporation to obtain the stable base layered cathode material of manganese containing sodium, and has the structure in wide voltage range without phase-change
Characteristic.
According to the above aspect of the present invention, the present invention has at least the following advantages:
(1) raw material that the present invention uses is cheap and easy to get, and the preparation method of solid-phase sintering is simply easily realized, having can actually grasp
The property made and business replicability.
(2) positive electrode prepared by the present invention, is the single-size of stratiform packed structures, and partial size is 0.2-1 μm.
(3) positive electrode prepared by the present invention improves the electronic conductivity and Na ~+Mobility of material, it is suppressed that high
Phase transformation under voltage during sodium ion deintercalation, so that when the positive electrode is assembled into sodium-ion battery, charge and discharge process
High reversible has height ratio capacity, and due to the other metallic elements of incorporation, improves the sodium ion and electronic conduction of material,
And then the high rate performance of electrode material is improved, in addition, the metallic element of doping effectively inhibits under electrode material high voltage
Phase transformation, to improve cyclical stability of the electrode material in charge and discharge process.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention and the accompanying drawings.
Detailed description of the invention
Fig. 1 is the X-ray of the double transition metal manganese base layered cathode materials of sodium-ion battery prepared by the embodiment of the present invention 1
Powder diffractogram；
Fig. 2 is the scanning of the double transition metal manganese base layered cathode materials of sodium-ion battery prepared by the embodiment of the present invention 1
Electron microscope；
Fig. 3 is the transmission of the double transition metal manganese base layered cathode materials of sodium-ion battery prepared by the embodiment of the present invention 1
Electron microscope；
Fig. 4 is the transmission of the double transition metal manganese base layered cathode materials of sodium-ion battery prepared by the embodiment of the present invention 1
Electronic Speculum elemental scan spectrogram；
Fig. 5 is the double transition metal manganese base layered cathode material charge and discharge of sodium-ion battery prepared by the embodiment of the present invention 1
Curve and in situ X-ray diffraction powder diffractogram；
Fig. 6 is that the double transition metal manganese base layered cathode materials of sodium-ion battery prepared by the embodiment of the present invention 1 are typical
Charging and discharging curve；
Fig. 7 is the double transition metal manganese base layered cathode materials of sodium-ion battery prepared by the embodiment of the present invention 1 in difference
Multiplying power figure under circuit current density；
Fig. 8 is the double transition metal manganese base layered cathode material 50mA/g of sodium-ion battery prepared by the embodiment of the present invention 1
Long circulating performance curve under current density；
Fig. 9 is that the double transition metal manganese base layered cathode materials of sodium-ion battery prepared by the embodiment of the present invention 1 are dressed up entirely
Charging and discharging curve figure when battery.
Specific embodiment
Following embodiment further illustrates the contents of the present invention, but should not be construed as limiting the invention.Without departing substantially from
In the case where spirit of that invention and essence, to modification made by the method for the present invention, step or condition and replaces, belong to the present invention
Range.
Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.
(1) it is 0.6:0.93:0.07 according to molar ratio, accurately weighs the NaNO of corrresponding quality3、MnCO3And RuO2, it is added
In ball grinder, then ball milling bead is added thereto, above-mentioned presoma is uniformly mixed by ball milling 5h under the conditions of 300r/min, is mixed
Close uniform presoma dry 12h in 100 DEG C of baking ovens.
(2) mixture after ball milling is depressed into the disk that diameter is 16mm in 10MPa pressure.
(3) step (2) is obtained sheet sample to be placed in tube furnace, is warming up to 900 under oxygen atmosphere with 5 DEG C/min
DEG C, it calcines 4 hours；It cools to room temperature with the furnace, then is ground into powdered, molecular formula Na0.6Mn0.93Ru0.07O2, material
The partial size of particle is 0.2-1 μm.
The double transition metal manganese-based anode materials of the sodium-ion battery of above-mentioned preparation are characterized, as a result picture 1-4, Fig. 1
The indicatrix for showing layered oxide shows that sample has the space P63/mmc group structure.Fig. 2 shows that material is stratiform heap
The single-size of product structure, the size of particle are 0.2-1 μm.Fig. 3 shows that material is lamellar pattern.Fig. 4 can be seen that four kinds
Element is evenly distributed in material.Fig. 5 can be seen that the progress with charge and discharge, and the X-ray powder diffraction spectrogram of material does not have
New peak generates, and shows material in the structural evolution mechanism that wide-voltage range is without phase-change.
Electrochemical property test, knot are carried out to the double transition metal manganese base layered cathode materials of the sodium-ion battery of above-mentioned preparation
Fruit such as Fig. 6-9.As can be seen from Figure 6, the material is in 50mA g-1, the first discharge specific capacity under 1.5-4.5 V voltage conditions be
209.3mAh g-1, 3 charge-discharge tests are made to material, charging and discharging curve essentially coincides, and illustrates the charge and discharge process of the material
High reversible.Fig. 7 shows multiplying power of the material under different current densities, in 5000mA g-1Under the conditions of, specific capacity is still
There is 97.3mAh g-1.In Fig. 8, top curve represents charge and discharge coulombic efficiency, and lower curve represents the specific capacity of material, shows
By the specific capacity still also original 75.3% of battery in the long-time charge and discharge cycles of 200 circles, and battery herein fill by length
The coulombic efficiency of battery is held in 98% or more in discharge cycles.After Fig. 9 shows that material and hard carbon cathode are assembled into full battery
In 50mA g-1, the first discharge specific capacity under 1.5-4.5 V voltage conditions be 101.0mAh g-1, 3 charge and discharge are made to material
Test, charging and discharging curve essentially coincides, and illustrates charge and discharge process high reversible after the material is assembled into full battery.
Embodiment 2
The molar ratio for changing each substance is 0.6:0.99:0.01 according to molar ratio, accurately weighs the NaNO of corrresponding quality3、
MnCO3And RuO2, according to step (1)-(3) method in embodiment 1, prepare the double transition metal manganese base shapes of sodium-ion battery
Positive electrode, molecular formula Na0.6Mn0.99Ru0.01O2。
Embodiment 3
The molar ratio for changing each substance is 0.6:0.9:0.1 according to molar ratio, accurately weighs the NaNO of corrresponding quality3、
MnCO3And RuO2, according to step (1)-(3) method in embodiment 1, prepare the double transition metal manganese base shapes of sodium-ion battery
Positive electrode, molecular formula Na0.6Mn0.9Ru0.1O2。
Embodiment 4
The molar ratio for changing each substance is 0.6:0.8:0.2 according to molar ratio, accurately weighs the NaNO of corrresponding quality3、
MnCO3And RuO2, according to step (1)-(3) method in embodiment 1, prepare the double transition metal manganese base shapes of sodium-ion battery
Positive electrode, molecular formula Na0.6Mn0.8Ru0.2O2。
Embodiment 5
The molar ratio for changing each substance is 0.6:0.5:0.5 according to molar ratio, accurately weighs the NaNO of corrresponding quality3、
MnCO3And RuO2, according to step (1)-(3) method in embodiment 1, prepare the double transition metal manganese base shapes of sodium-ion battery
Positive electrode, molecular formula Na0.6Mn0.5Ru0.5O2。
Embodiment 6
The molar ratio for changing each substance is 0.3:0.93:0.07 according to molar ratio, accurately weighs the NaNO of corrresponding quality3、
MnCO3And RuO2, according to step (1)-(3) method in embodiment 1, prepare the double transition metal manganese base shapes of sodium-ion battery
Positive electrode, molecular formula Na0.3Mn0.0.93Ru0.07O2。
Embodiment 7
The molar ratio for changing each substance is 1:0.93:0.07 according to molar ratio, accurately weighs the NaNO of corrresponding quality3、
MnCO3And RuO2, according to step (1)-(3) method in embodiment 1, prepare the double transition metal manganese base shapes of sodium-ion battery
Positive electrode, molecular formula Na1Mn0.0.93Ru0.07O2。
Embodiment 8
By the RuO in embodiment 12Change the IrO of equimolar amounts into2, according to step (1)-(3) method in embodiment 1, system
The standby double transition metal manganese base layered cathode materials of sodium-ion battery out, molecular formula Na0.6Mn0.93Ir0.07O2。
Embodiment 9
By the RuO in embodiment 12Change the Sb of 0.5 mole into2O5, according to step (1)-(3) method in embodiment 1,
Prepare the double transition metal manganese-based anode materials of sodium-ion battery, molecular formula Na0.6Mn0.93Sb0.07O2。
Embodiment 10
By the RuO in embodiment 12Change the Nb of 0.5 mole into2O5, according to step (1)-(3) method in embodiment 1,
Prepare the double transition metal manganese-based anode materials of sodium-ion battery, molecular formula Na0.6Mn0.93Nb0.07O2。
Embodiment 11
By the RuO in embodiment 12Change the SnO of equimolar amounts into2, according to step (1)-(3) method in embodiment 1, system
The standby double transition metal manganese base layered cathode materials of sodium-ion battery out, molecular formula Na0.6Mn0.93Sn0.07O2。
Embodiment 12
By the RuO in embodiment 12Change the Ta of 0.5 mole into2O5, according to step (1)-(3) method in embodiment 1,
Prepare the double transition metal manganese base layered cathode materials of sodium-ion battery, molecular formula Na0.6Mn0.93Ta0.07O2。
Embodiment 13
By the RuO in embodiment 12Change the Bi of 0.5 mole into2O3, according to step (1)-(3) method in embodiment 1,
Prepare the double transition metal manganese base layered cathode materials of sodium-ion battery, molecular formula Na0.6Mn0.93Bi0.07O2。
Embodiment 14
By the MnCO in embodiment 13Change the Mn (NO of equimolar amounts into3)2, according to step (1)-(3) side in embodiment 1
Method prepares the double transition metal manganese base layered cathode materials of sodium-ion battery, molecular formula Na0.6Mn0.93Ru0.07O2。
Embodiment 15
By the NaNO in embodiment 13The NaCl for changing equimolar amounts into, according to step (1)-(3) method in embodiment 1,
Prepare the double transition metal manganese base layered cathode materials of sodium-ion battery, molecular formula Na0.6Mn0.93Ru0.07O2。
Embodiment 16
900 DEG C of calcination temperature in embodiment 1 are changed into 700 DEG C, according to step (1)-(3) method in embodiment 1, system
The standby double transition metal manganese base layered cathode materials of sodium-ion battery out, molecular formula Na0.6Mn0.93Ru0.07O2。
Embodiment 17
Change 900 DEG C of calcination temperature in embodiment 1 into 1100 DEG C, according to step (1)-(3) method in embodiment 1,
Prepare the double transition metal manganese base layered cathode materials of sodium-ion battery, molecular formula Na0.6Mn0.93Ru0.07O2。
Embodiment 18
The calcination atmosphere oxygen in embodiment 1 is changed into air, according to step (1)-(3) method in embodiment 1, preparation
The double transition metal manganese base layered cathode materials of sodium-ion battery out, molecular formula Na0.6Mn0.93Ru0.07O2。
In conclusion material preparation method of the invention is simple, abundant raw material is cheap, and degree of being practical is high, synthesis
Positive electrode uniform particle diameter out is the single-size of stratiform packed structures, occurs without phase-change in wide-voltage range.It is this
Material can greatly improve the structural stability in material charge and discharge process when assembling sodium-ion battery, to improve battery entirety
Cycle performance also improves the high rate performance and specific capacity of material to a certain extent.In addition, material of the invention is assembled into
Full battery also has very excellent chemical property in charge and discharge process.Therefore, material of the invention and preparation method exist
It has a good application prospect in optimization sodium-ion battery energy storage device performance.
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of double transition metal manganese base layered cathode materials of sodium-ion battery, it is characterised in that: its general formula is NaxMn1-yMyO2,
Wherein M is Ru, Ir, Nb, Bi, Sn, Ta or Sb, and 0.3≤x≤1,0 < y≤0.5.
2. the double transition metal manganese base layered cathode materials of sodium-ion battery according to claim 1, it is characterised in that: anode
The crystal structure of material belongs to P63/ mmc orSpace group.
3. the double transition metal manganese base layered cathode materials of sodium-ion battery according to claim 1, it is characterised in that: anode
Material is in granular form, and the partial size of positive electrode is 0.2-1 μm.
4. the double transition metal manganese base layered cathode materials of sodium-ion battery according to any one of claim 1-3, special
Sign is that preparation method includes the following steps:
Then tabletting after sodium salt, manganese salt and other metal oxides are mixed is calcined at 700-1100 DEG C, obtain after cooling described
The double transition metal manganese base layered cathode materials of sodium-ion battery；Wherein, other described metal oxides are selected from RuO2、IrO2、
SnO2、Ta2O5、Bi2O3、Nb2O5And Sb2O5One or more of.
5. the double transition metal manganese base layered cathode materials of sodium-ion battery according to claim 4, it is characterised in that: described
Sodium salt is Na2CO3、NaNO3One or more of with NaCl.
6. the double transition metal manganese base layered cathode materials of sodium-ion battery according to claim 4, it is characterised in that: described
Manganese salt is MnCO3And/or Mn (NO3)2。
7. the double transition metal manganese base layered cathode materials of sodium-ion battery according to claim 4, it is characterised in that: described
The molar ratio of sodium salt, manganese salt and sodium element in other metal oxides, manganese element and other metallic elements is 0.3-1:0.5-
1:0.01-0.5。
8. the double transition metal manganese base layered cathode materials of sodium-ion battery according to claim 4, it is characterised in that: use
Ball-milling method mixes, ball milling speed 100-300r/min, Ball-milling Time 2-20h.
9. the double transition metal manganese base layered cathode materials of sodium-ion battery according to claim 4, it is characterised in that: in 1-
Tabletting is carried out under 50MPa.
10. the double transition metal manganese base layered cathode materials of sodium-ion battery according to claim 4, it is characterised in that: forge
The burning time is 1-50h, and heating rate is 1-20 DEG C/min.
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