CN111129493B - Transition metal sulfide positive electrode material of sodium ion battery and preparation method and application thereof - Google Patents
Transition metal sulfide positive electrode material of sodium ion battery and preparation method and application thereof Download PDFInfo
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- CN111129493B CN111129493B CN201911369268.1A CN201911369268A CN111129493B CN 111129493 B CN111129493 B CN 111129493B CN 201911369268 A CN201911369268 A CN 201911369268A CN 111129493 B CN111129493 B CN 111129493B
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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 provides a transition metal sulfide positive electrode material of a sodium ion battery, and a preparation method and application thereof, wherein the chemical composition of the transition metal sulfide positive electrode material of the sodium ion battery is NaCrxV1‑xS2Wherein 0 is<x<1. The transition metal sulfide positive electrode material of the sodium ion battery is used in the sodium ion battery, the reversible charging specific capacity can reach 190mAh/g at a multiplying power of 20mA/g to the maximum extent, the average voltage is 2.4V vs. Na +/Na to the maximum extent, the specific energy can reach 456Wh/kg, and for NaCr2/3V1/3S2The reversible capacity of the material is still 160mAh/g under the multiplying power of 1000mA/g, and the capacity is higher than 90mAh/g after 100 cycles of circulation. NaCrxV1‑xS2The lithium ion battery positive electrode material has the advantages of good rate performance, high average discharge voltage, high specific capacity and simple preparation, and is suitable for being used as a positive electrode material of a sodium ion battery.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a transition metal sulfide positive electrode material for a sodium ion battery, and a preparation method and application thereof.
Background
With the continuous development of global economy, the requirements on various energy sources and energy source materials are increasingly raised, and a clean and environment-friendly new energy system is urgently needed to be found in order to save fossil fuels and protect the environment. Wind energy, solar energy and the like are ideal clean energy sources, but are influenced by climate and geographical positions, and if the generated electric energy can be stored into chemical energy in an electrochemical form, peaks and valleys can be regulated and controlled, and grid-connected transmission is facilitated. The traditional lead-acid storage batteries in the current market have heavier pollution and low performance and are gradually replaced, the lithium ion batteries are influenced by low abundance and high price of lithium elements, and the sodium ion batteries with high abundance and low price have no advantages in the aspect of cost. With the increasing market demand of electric vehicles, the research and development of the anode material with high charging speed and large charging current becomes urgent. Therefore, the development of electrode materials with large capacity and high rate performance has a considerable practical significance.
Disclosure of Invention
In view of the above, the present invention is directed to a transition metal sulfide positive electrode material for a sodium ion battery, which overcomes the defects of the prior art and has high rate capability.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the chemical composition of the transition metal sulfide anode material of the sodium ion battery is NaCrxV1-xS2Wherein 0 is<x<1. The material is binary layered transition metal sulfide containing transition metals Cr and V.
Preferably, the material crystals belong to the R-3m space group structure.
Preferably, the invention provides NaCr as a positive electrode material of a sodium-ion batteryxV1-xS2In the form of amorphous powder, obtained by grinding or ball milling of a sintered block, the particle size of which depends on the fineness of grinding, should be ground to a particle size in the range of 0.1 to 5 μm for easy coating.
Another objective of the present invention is to provide a method for preparing the transition metal sulfide positive electrode material of the sodium ion battery, so as to prepare the positive electrode material.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a transition metal sulfide positive electrode material of a sodium ion battery comprises the step of carrying out sintering reaction on a chromium source and a vanadium source in a stoichiometric ratio, a sodium source in a stoichiometric ratio and a sulfur source in a stoichiometric ratio of 100-110% under the condition of inert gas atmosphere.
Preferably, the method further comprises the step of grinding the sintering reaction product into powder by using a mortar or a ball mill to obtain the transition metal sulfide cathode material of the sodium-ion battery.
Preferably, the chromium source is metal chromium powder, the vanadium source is metal vanadium powder, the sodium source is sodium sulfide, and the sulfur source is sulfur powder;
preferably, before the chromium source, the vanadium source, the sodium source and the sulfur source are subjected to a sintering reaction, the chromium source, the vanadium source, the sodium source and the sulfur source are uniformly mixed and compacted in a glove box under an inert gas atmosphere, and then the mixture is sealed;
preferably, the sintering reaction temperature is between 700 and 1000 ℃, and the reaction time is between 3 and 72 hours;
preferably, the sintering reaction is carried out in an electric furnace; the inert gas is one or more than two of nitrogen, argon and helium.
The invention also relates to the application of the transition metal sulfide positive electrode material of the sodium-ion battery in the sodium-ion battery.
Another object of the present invention is to provide a positive electrode plate of a sodium ion battery, which comprises the positive electrode material as described above and has high rate capability due to the positive electrode material.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the positive pole piece of the sodium-ion battery contains the transition metal sulfide positive pole material of the sodium-ion battery.
The invention further aims to provide a preparation method of the positive pole piece of the sodium-ion battery, so as to prepare the positive pole piece.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a positive pole piece of a sodium-ion battery comprises the steps of mixing a transition metal sulfide positive pole material of the sodium-ion battery with a conductive agent and a binder, coating the mixture on an active material, and drying or airing the mixture in an inert gas atmosphere to obtain the positive pole piece of the sodium-ion battery.
Preferably, the mass ratio of the transition metal sulfide positive electrode material, the conductive agent and the binder of the sodium ion battery is (5-10): 0.5-5): 1.
Preferably, the conductive agent is one or more of ketjen black, carbon black and graphite, and the binder is Polytetrafluoroethylene (PTFE) or/and polyvinylidene fluoride (PVDF).
Preferably, the active material is aluminum foil, copper foil, or nickel foam.
Another object of the present invention is to provide a positive electrode plate sodium-ion battery containing the above sodium-ion battery, which also has high rate capability due to the inclusion of the above positive electrode material.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the utility model provides a sodium ion battery, includes positive pole piece, negative pole piece and diaphragm, its characterized in that: the positive pole piece is the positive pole piece.
Preferably, the negative pole piece is metal sodium.
Preferably, the membrane is one or more than two of Whatman, Celgrad and ENTEK.
The last objective of the present invention is to provide a method for preparing the above sodium-ion battery, so as to prepare the above sodium-ion battery.
A preparation method of a sodium ion battery comprises the step of assembling a positive pole piece, a negative pole piece, electrolyte and a diaphragm into the sodium ion battery.
In the invention, the electrolyte in the electrolyte is selected from sodium hexafluorophosphate (NaPF)6) Sodium perchlorate (NaClO)4) And sodium bis (trifluoromethylsulfonyl) imide (NaTFSI).
In the invention, the solvent in the electrolyte is any one or more of dimethyl ethylene glycol ether (DME), Tetraglyme (TEGDME), 1, 4-Dioxane (DOL), Ethylene Carbonate (EC), PC (propylene carbonate), dimethyl carbonate (DMC), fluoroethylene carbonate (FEC) and the like.
Compared with the prior art, the transition metal sulfide cathode material for the sodium-ion battery has the following advantages:
(1) through doping Cr and V elements, NaCr is changedxV1-xS2The valence band structure of the system, the 3d energy level of V is close to the 3p energy level of S, and the interaction between V-S and Cr-S is strong, so that the covalency of V-S and Cr-S is enhanced in the charging process, and electron holes which can exist stably and are highly reversible in the charging and discharging processes are formed, which is proved by X-ray absorption spectroscopy (XAS). V, Cr, the redox level of S is improved by the interaction with S, the overall charge-discharge voltage of the battery is improved, the stable and reversible electron holes have good conductivity, and the rate capability and the cycle performance of the anode material are improved.
(2)NaCrxV1-xS2Good electrode performance, wherein the NaCr2/3V1/3S2Reversible charge and discharge with highest capacityThe specific capacity reaches 190mAh/g, the average voltage is 2.4V vs. Na +/Na, the specific energy can reach 456Wh/kg, the reversible capacity still has 160mAh/g under the multiplying power of 1000mA/g, and the capacity is higher than 90mAh/g after 100 cycles of circulation.
(3) The results of experimental characterization and analysis show that the material has excellent electrochemical performance and can be used as a positive electrode material of a high-performance sodium-ion battery. No NaCr is found so farxV1-xS2The material is used as the positive electrode material of the sodium ion battery.
The preparation method of the transition metal sulfide cathode material of the sodium ion battery has the advantages of easily obtained raw materials, simple process and easy operation.
The positive pole piece of the sodium-ion battery, the sodium-ion battery and the transition metal sulfide positive material of the sodium-ion battery have the same advantages compared with the prior art, and the preparation method of the positive pole piece of the sodium-ion battery, the preparation method of the sodium-ion battery and the preparation method of the transition metal sulfide positive material of the sodium-ion battery have the same advantages compared with the prior art, and are not repeated herein.
Drawings
FIG. 1 shows NaCr in example 1 of the present invention2/3V1/3S2Scanning electron microscope photos of the electrode materials after sintering and grinding;
FIG. 2 shows NaCr in example 1 of the present invention2/3V1/3S2An X-ray powder diffraction pattern of the anode material and a Rietveld refinement result thereof, wherein a in the pattern is a comparison of an XRD curve measured by an experiment and a refined simulation XRD curve; b is the position of each diffraction peak determined by fine modification; c is the difference between the simulated value and the experimental value;
FIG. 3 shows NaCr in example 1 of the present invention2/3V1/3S2The electrode material has a first circle of charge-discharge curves under the current densities of 20mA/g and 1000 mA/g;
FIG. 4 shows NaCr in example 1 of the present invention2/3V1/3S2The discharge capacity and the coulombic efficiency of the electrode material are shown in a schematic diagram of 100 circles at the current density of 1000 mA/g;
FIG. 5 shows NaCr in example 1 of the present invention2/3V1/3S2An S element X-ray absorption spectrum (XAS) near-edge structure diagram of the electrode material in the original, fully charged and fully discharged states;
FIG. 6 shows NaCr2/3V1/3S2With NaCr1/3V2/3S2An X-ray powder diffraction pattern contrast diagram of the anode material;
FIG. 7 shows NaCr1/3V2/3S2The first and 10 th circles of charge-discharge curves of the electrode material under the current density of 20 mA/g;
FIG. 8 shows NaCr1/2V1/2S2The first and 10 th circles of the charging and discharging curves of the electrode material are under the current density of 20 mA/g.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
In the present invention, NaCrxV1-xS2The crystal structure of (a) was determined by an X-ray diffractometer (XRD, Bruker D8).
Example 1
The chemical composition of the transition metal sulfide anode material of the sodium ion battery is NaCr2/3V1/3S2。
The preparation method of the transition metal sulfide cathode material of the sodium ion battery comprises the following steps: metal chromium powder, metal vanadium powder, sodium sulfide and sulfur powder with the stoichiometric ratio of 100% are uniformly mixed in a glove box in argon atmosphere, compacted, sealed in a vacuum quartz tube, placed in an electric furnace in argon protective atmosphere for sintering reaction, slowly heated to 750 ℃ at the speed of 2 ℃ per minute, and kept for 70 hours. And cooling at the speed of 1 ℃ per minute, taking out, and grinding into powder by using a mortar in an argon atmosphere to obtain the transition metal sulfide positive electrode material of the sodium-ion battery.
The application of the transition metal sulfide positive electrode material of the sodium ion battery comprises the following steps:
the preparation method of the positive pole piece of the sodium-ion battery containing the transition metal sulfide positive pole material of the sodium-ion battery comprises the following steps: in an argon atmosphere, adding NaCr according to the mass ratio of 7:2:12/3V1/3S2The conductive carbon black and the PVDF binder are dissolved in the NMP and uniformly mixed, stirred into uniform slurry, coated on an aluminum foil, naturally dried in an argon atmosphere and cut into the positive pole piece.
The preparation method of the sodium ion battery containing the positive pole piece comprises the following steps: taking a high-purity metal lithium sheet as a cathode; a Whatman sodium electrical membrane was used; NaClO4 was dissolved in Ethylene Carbonate (EC), dimethyl carbonate (DMC) and fluoroethylene carbonate (FEC) at a concentration of 1mol/L electrolyte (19: 19:2 by volume). The positive pole piece, the negative pole, the Whatman sodium electric diaphragm and the electrolyte are assembled into a 2032 type button cell for testing, and the cell is assembled in an argon atmosphere of a glove box. Electrochemical testing was performed under a blue (Land) cell test system.
FIG. 1, NaCr2/3V1/3S2The scanning electron microscope photo of the sintered and ground electrode material shows that the material is powder material, and the particle size of the material is 0.1-3 μm in the example.
FIG. 2, NaCr2/3V1/3S2The X-ray powder diffraction pattern and the Rietveld refinement result of the anode material show that the material belongs to an R-3m space group, Cr and V atoms are randomly mixed and arranged, and the a axis length
Length of c axis
The material synthesized by the method is pure phase, and no other impure phase is seen.
FIG. 3, NaCr2/3V1/3S2The electrode material has a first-circle charge-discharge curve under the current densities of 20mA/g and 1000mA/g, and has larger polarization under high multiplying power, so that a wider electrochemical window is adopted for testing.The first discharge capacity was 190 and 160mAh/g, respectively.
FIG. 4 shows NaCr in example 1 of the present invention2/3V1/3S2The schematic diagram of the discharge capacity and the coulombic efficiency of the electrode material for the first 100 circles under the current density of 1000mA/g shows that the coulombic efficiency of the material is maintained at 100 percent, and the capacity of more than 90mAh/g can be still kept after the material is circulated for 100 times under the large multiplying power of 1000 mA/g.
FIG. 5 shows NaCr in example 1 of the present invention2/3V1/3S2The near edge structure diagram of the S element X-ray absorption spectrum (XAS) of the electrode material in the original, fully charged and fully discharged states. From the figure, it can be seen that the XAS spectra of the original and full discharge states are almost completely consistent, indicating that the reversibility of the material is very good, and the valence state and chemical environment of S are both returned to the original state. The fully charged state of the S-element XAS spectrum has an elevated shoulder corresponding to the electron hole that exists in the S atom as the S atom loses electrons during charging. While the main peak increases from 2469eV to 2470eV, indicating that the chemical valence of S increases overall.
Example 2
The chemical composition of the transition metal sulfide anode material of the sodium ion battery is NaCr1/3V2/3S2。
The preparation method of the transition metal sulfide cathode material of the sodium ion battery comprises the following steps: uniformly mixing metal chromium powder, metal vanadium powder, sodium sulfide and sulfur powder with a stoichiometric ratio of 105% in a glove box in an argon atmosphere, compacting, placing the mixture into a vacuum quartz tube for sealing, placing the vacuum quartz tube into an electric furnace in an argon protective atmosphere for sintering reaction, slowly heating to 1000 ℃ at a rate of 2 ℃ per minute, and keeping the temperature for 3 hours. And cooling at the speed of 1 ℃ per minute, taking out, and grinding into powder by using a mortar in an argon atmosphere to obtain the transition metal sulfide positive electrode material of the sodium-ion battery.
The application of the transition metal sulfide positive electrode material of the sodium ion battery comprises the following steps:
sodium-ion battery positive pole piece containing sodium-ion battery transition metal sulfide positive pole material and preparation method of positive pole pieceThe method comprises the following steps: in an argon atmosphere, adding NaCr according to the mass ratio of 6:3:11/3V2/3S2The Ketjen black and the binder PTFE are dissolved in NMP and uniformly mixed, stirred into uniform slurry, coated on an aluminum foil, naturally dried in an argon atmosphere, and cut into the positive pole piece.
The preparation method of the sodium ion battery containing the positive pole piece comprises the following steps: taking a high-purity metal lithium sheet as a cathode; adopting a Celgrad sodium electric diaphragm; electrolyte is 1mol/L NaPF6Dissolved in Ethylene Carbonate (EC), Propylene Carbonate (PC) and fluoroethylene carbonate (FEC) (volume ratio 19: 19: 2). The positive pole piece, the negative pole, the Celgrad sodium electric diaphragm and the electrolyte are assembled into a 2032 type button cell for testing, and the cell is assembled in an argon atmosphere of a glove box. Electrochemical testing was performed under a blue (Land) cell test system.
FIG. 6, NaCr2/3V1/3S2、NaCr1/2V1/2S2With NaCr1/3V2/3S2And comparing the X-ray powder diffraction patterns of the cathode materials. The three peaks are almost consistent in position and belong to the R-3m space group, and no obvious mixed peak is found. The modified conditions can still synthesize pure-phase NaCrxV1-xS2。
FIG. 7, NaCr1/3V2/3S2The first and 10 th circles of charge-discharge curves of the electrode material under the current density of 20mA/g have the first discharge capacity of 170mAh/g, which is higher than that of NaCr2/3V1/3S2Slightly lower, and the charging and discharging platform is at 2.3-2.5V, compared with NaCr1/3V2/3S2Slightly lower.
Example 3
The chemical composition of the transition metal sulfide anode material of the sodium ion battery is NaCr1/2V1/2S2。
The preparation method of the transition metal sulfide cathode material of the sodium ion battery comprises the following steps: uniformly mixing metal chromium powder, metal vanadium powder and sodium sulfide in a stoichiometric ratio and sulfur powder in a stoichiometric ratio of 110% in a glove box in an argon atmosphere, compacting, putting the mixture into a vacuum quartz tube for sealing, putting the vacuum quartz tube into an electric furnace in an argon protective atmosphere for sintering reaction, slowly heating to 850 ℃ at a rate of 2 ℃ per minute, and keeping the temperature for 30 hours. And cooling at the speed of 1 ℃ per minute, taking out, and grinding into powder by using a mortar in an argon atmosphere to obtain the transition metal sulfide positive electrode material of the sodium-ion battery.
The application of the transition metal sulfide positive electrode material of the sodium ion battery comprises the following steps:
the preparation method of the positive pole piece of the sodium-ion battery containing the transition metal sulfide positive pole material of the sodium-ion battery comprises the following steps: in an argon atmosphere, adding NaCr according to the mass ratio of 8:1:11/2V1/2S2Conductive carbon black and binder PTFE are dissolved in NMP and uniformly mixed, stirred into uniform slurry, coated on an aluminum foil, naturally dried in argon atmosphere and cut into a positive pole piece.
The preparation method of the sodium ion battery containing the positive pole piece comprises the following steps: taking a high-purity metal lithium sheet as a cathode; NETEK sodium electric diaphragm is adopted; 1mol/L NaTFSI electrolyte is dissolved in 1, 4-Dioxane (DOL) + dimethyl ethylene glycol ether (DME) (volume ratio is 1: 1). The positive pole piece, the negative pole, the NETEK sodium electric diaphragm and the electrolyte are assembled into a 2032 type button cell for testing, and the cell is assembled in an argon atmosphere of a glove box. Electrochemical testing was performed under a blue (Land) cell test system.
FIG. 6, NaCr2/3V1/3S2、NaCr1/2V1/2S2With NaCr1/3V2/3S2And comparing the X-ray powder diffraction patterns of the cathode materials. The three peaks have almost the same positions and belong to the R-3m space group, and no obvious mixed peak is found. The modified conditions can still synthesize pure-phase NaCrxV1-xS2。
FIG. 8, NaCr1/2V1/2S2The first and 10 th circles of charge-discharge curves of the electrode material under the current density of 20mA/g have the first discharge capacity of 114mAh/g, which is better than that of NaCr1/3V2/3S2Slightly lower, but less cyclic attenuation. At the same time, the charging and discharging platform is at 2.4-2.6V and is at NaCr1/3V2/3S2And NaCr2/3V1/3S2In the meantime.
In conclusion, the transition metal sulfide positive electrode material for the sodium-ion battery is synthesized in one step in an inert gas atmosphere by a solid phase method to obtain a single-phase positive electrode material product. The electrode material is used in a sodium ion battery, the reversible charging specific capacity can reach 190mAh/g maximally under the multiplying power of 20mA/g, the average voltage is 2.4V vs. Na +/Na maximally, the specific energy can reach 456Wh/kg, and for NaCr2/3V1/3S2The reversible capacity of the material is still 160mAh/g under the multiplying power of 1000mA/g, and the capacity is higher than 90mAh/g after circulation for 100 circles. NaCrxV1-xS2The lithium ion battery positive electrode material has the advantages of good rate performance, high average discharge voltage, high specific capacity and simple preparation, and is suitable for being used as a positive electrode material of a sodium ion battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (14)
1. The transition metal sulfide positive electrode material of the sodium ion battery is characterized in that: the chemical composition of the material is NaCrxV1-x S2, wherein x is more than 0 and less than 1, the material crystal belongs to an R-3m space group structure, the material is in an amorphous powder form, and the particle size is between 0.1 and 5 mu m.
2. A method of making the transition metal sulfide positive electrode material of a sodium ion battery of claim 1, wherein: comprises the step of sintering reaction by adopting a chromium source, a vanadium source, a sodium source and a sulfur source in a stoichiometric ratio of 100-110% under the inert gas atmosphere condition.
3. The method for preparing the transition metal sulfide positive electrode material of the sodium-ion battery according to claim 2, characterized in that: the chromium source is metal chromium powder, the vanadium source is metal vanadium powder, the sodium source is sodium sulfide, and the sulfur source is sulfur powder.
4. The method for preparing the transition metal sulfide positive electrode material of the sodium-ion battery according to claim 3, characterized in that: before the chromium source, the vanadium source, the sodium source and the sulfur source are subjected to sintering reaction, the chromium source, the vanadium source, the sodium source and the sulfur source need to be uniformly mixed and compacted in a glove box in inert gas atmosphere.
5. The method for preparing the transition metal sulfide positive electrode material of the sodium-ion battery according to claim 4, wherein: the sintering reaction temperature is between 700 ℃ and 1000 ℃, and the reaction time is between 3 and 72 hours.
6. The method for preparing the transition metal sulfide positive electrode material of the sodium-ion battery according to claim 5, wherein: the sintering reaction is carried out in an electric furnace; the inert gas is one or more than two of nitrogen, argon and helium.
7. The use of the transition metal sulfide positive electrode material of a sodium ion battery of claim 1 in a sodium ion battery.
8. The utility model provides a positive pole piece of sodium ion battery which characterized in that: a sodium ion battery transition metal sulfide positive electrode material as defined in claim 1.
9. The method for preparing the positive pole piece of the sodium-ion battery as claimed in claim 8, wherein the method comprises the following steps: and mixing the transition metal sulfide positive electrode material of the sodium-ion battery with a conductive agent and a binder, coating the mixture on an active material, and drying or airing the active material in an inert gas atmosphere to obtain the positive electrode piece of the sodium-ion battery.
10. The preparation method of the positive pole piece of the sodium-ion battery as claimed in claim 9, characterized in that: the mass ratio of the transition metal sulfide positive electrode material, the conductive agent and the binder of the sodium ion battery is (5-10): 0.5-5): 1.
11. The method for preparing the positive pole piece of the sodium-ion battery as claimed in claim 10, wherein the method comprises the following steps: the conductive agent is one or more of Ketjen black, carbon black and graphite conductor, and the binder is polytetrafluoroethylene or/and polyvinylidene fluoride.
12. The method for preparing the positive pole piece of the sodium-ion battery as recited in claim 11, characterized in that: the active material is aluminum foil, copper foil or foamed nickel.
13. The utility model provides a sodium ion battery, includes positive pole piece, negative pole piece and diaphragm, its characterized in that: the positive pole piece is the positive pole piece of claim 8;
and/or the negative pole piece is metal sodium;
and/or the diaphragm is one or more than two of Whatman, Celgrad and ENTEK.
14. The method of manufacturing a sodium-ion battery of claim 13, wherein: the method comprises the steps of assembling a positive pole piece, a negative pole piece, electrolyte and a diaphragm into a sodium-ion battery; the electrolyte in the electrolyte is selected from one or more of sodium hexafluorophosphate, sodium perchlorate and sodium bis (trifluoromethylsulfonyl) imide, and the solvent in the electrolyte is selected from one or more of dimethyl ethylene glycol diether, tetraglyme, 1, 4-dioxane, ethylene carbonate, propylene carbonate, dimethyl carbonate and fluoroethylene carbonate.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161703A (en) * | 2015-08-07 | 2015-12-16 | 复旦大学 | Quintuple layered oxide cathode material for sodium ion battery and preparation method of quintuple layered oxide cathode material |
| CN108155353A (en) * | 2017-11-20 | 2018-06-12 | 中南大学 | A kind of graphitized carbon jacketed electrode material and preparation method thereof and the application as energy storage device electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161703A (en) * | 2015-08-07 | 2015-12-16 | 复旦大学 | Quintuple layered oxide cathode material for sodium ion battery and preparation method of quintuple layered oxide cathode material |
| CN108155353A (en) * | 2017-11-20 | 2018-06-12 | 中南大学 | A kind of graphitized carbon jacketed electrode material and preparation method thereof and the application as energy storage device electrode material |
Non-Patent Citations (1)
| Title |
|---|
| "Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S–S";Tian Wang等;《NATURE COMMUNICATIONS》;20191001;第10卷;全文 * |
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