CN113113593A - Room temperature solid sodium ion battery based on liquid alloy - Google Patents

Room temperature solid sodium ion battery based on liquid alloy Download PDF

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Publication number
CN113113593A
CN113113593A CN202110220007.4A CN202110220007A CN113113593A CN 113113593 A CN113113593 A CN 113113593A CN 202110220007 A CN202110220007 A CN 202110220007A CN 113113593 A CN113113593 A CN 113113593A
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sodium
alloy
ion battery
liquid
sodium ion
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刘山
赵乾乾
王岭
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North China University of Science and Technology
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North China University of Science and Technology
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C24/00—Alloys based on an alkali or an alkaline earth metal
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a room temperature solid sodium ion battery based on liquid alloy, belonging to the technical field of batteries, wherein a cathode material is liquid sodium-potassium alloy (9.2to 58.2 wt% of Na), a supporting framework is redox graphene, a sodium-potassium alloy cathode is obtained by combining the liquid sodium-potassium alloy and the redox graphene, compared with pure metal sodium as a solid sodium ion battery cathode, the sodium-potassium alloy cathode can effectively improve the wettability of a cathode and an electrolyte interface, and simultaneously can provide more active sites for the deposition of the metal sodium, so that the distribution of metal ions is more uniform, meanwhile, the three-dimensional porous structure of the redox graphene can relieve the volume change of the metal sodium in the circulating process, the sodium-potassium alloy cathode is applied to the solid sodium ion battery, the performance of the sodium-potassium alloy cathode is obviously improved and enhanced, more importantly, the solid sodium ion battery is tested at normal temperature, the realization of the room temperature solid-state sodium ion battery based on the liquid alloy is possible.

Description

Room temperature solid sodium ion battery based on liquid alloy
Technical Field
The invention relates to the technical field of batteries, in particular to a room-temperature solid sodium ion battery based on liquid alloy.
Background
As the energy crisis has increased and the demand for electronic products has increased, the demand for new high energy density rechargeable batteries has also increased. Lithium ion batteries have been widely studied due to their high cycle stability, but development of lithium batteries is limited due to shortage of lithium metal resources. Among the elements of the lithium congener, sodium metal is of great interest due to the abundant reserves in the earth's crust. In addition, the high specific capacity of the metallic sodium (1166 mAhg)-1) And a low electrode potential (-2.714Vvs standard hydrogen electrode) is considered an ideal negative electrode material for sodium ion batteries. And, the metallic sodium cathode is in a high energy sodium metal battery (Na-O)2Battery, Na-S battery and Na-CO2Batteries) play a significant role.
However, since lithium organic liquid electrolyte is used, like lithium metal, sodium metal also has fire and even explosion safety hazards during deposition and dissolution, which greatly limits the practical application of the electrolyte in sodium batteries.
The method is an effective solution to replace the traditional organic electrolyte with the nonflammable solid electrolyte, the solid sodium ion battery is considered to be one of the ideal candidates for the next generation of energy storage devices due to high energy density and good safety, however, the development of the solid sodium ion battery is also difficult at present, the application of the solid sodium ion battery is limited by poor contact between the metal sodium cathode and the solid electrolyte interface due to the use of the metal sodium as the cathode, and the wettability of the metal sodium on the electrolyte is poor, so that the uneven deposition of charges and the growth penetration of dendrites are caused, and the early failure of the battery is finally caused.
Disclosure of Invention
1. Technical problem to be solved
The invention aims to provide a room temperature solid sodium ion battery based on liquid alloy, which adopts sodium-potassium alloy to replace common metal sodium as a cathode material of the solid sodium ion battery, the sodium-potassium alloy exists in a liquid state at normal temperature, the wettability of a cathode on a solid electrolyte interface can be increased by the method, the effect of stabilizing the solid-liquid interface is achieved, the deposition of the metal sodium is more uniform, the generation of sodium dendrite can be prevented, the service life of the battery is prolonged, the solid sodium ion battery can be realized at normal temperature, and the room temperature solid sodium ion battery based on the liquid alloy is simple and feasible, the cost is low, the preparation process steps are few, the operation is simple, and the room temperature solid sodium ion battery based on the liquid alloy is suitable for large-scale popularization and production.
2. Technical scheme
In order to solve the problems, the invention adopts the following technical scheme:
the utility model provides a room temperature solid-state sodium ion battery based on liquid alloy, includes positive plate, negative pole piece and solid electrolyte, positive plate surface coating has anodal active material, the negative pole piece contains liquid alloy and support skeleton, solid electrolyte is NASICON type compound.
As a preferable scheme of the invention, the positive active material of the positive plate is one or more of sodium vanadium phosphate, NaMnO2, Prussian blue compounds and sulfur positive electrodes.
As a preferable scheme of the invention, the liquid alloy is one or more of a liquid sodium-potassium alloy, a sodium-cesium alloy and a sodium-rubidium alloy.
As a preferable scheme of the invention, the preparation method of the negative plate material comprises the following steps: the alloy is prepared by directly and physically stacking metal sodium and metal potassium, under the protection of argon atmosphere, a certain amount of metal sodium and metal potassium are weighed according to the mass percentage of 9.2-58.2% of sodium, and are physically stacked together and kept stand for 1-3 hours to obtain the uniformly mixed sodium-potassium liquid alloy.
As a preferable scheme of the invention, the support framework material is redox graphene.
As a preferred scheme of the invention, the support framework is prepared by the following specific steps: measuring a graphene oxide aqueous solution, carrying out suction filtration to obtain a graphene oxide film, drying in a drying oven, stripping the dried graphene oxide film from filter paper, and carrying out high-temperature thermal reduction under the protection of argon atmosphere to obtain the redox graphene film.
As a preferable scheme of the invention, the processing technology of the negative plate is as follows: sucking a certain amount of liquid sodium-potassium alloy to directly drip on the redox graphene film, sucking the sodium-potassium alloy into the redox graphene film immediately, and after the sodium-potassium alloy is completely absorbed by the redox graphene film, punching the sodium-potassium alloy into a negative plate with the diameter of 1cm by using a mold for later use.
As a preferable mode of the present invention, the solid electrolyte is Na of NASICON type1+xM2SixP3-xO12(M ═ Zr, Hf) solid electrolyte.
In a preferable embodiment of the present invention, the solid electrolyte is prepared by a high temperature solid phase reaction method, and Na is added2CO3、ZrO2Or HfO2、MgO、SiO2、NH4H2PO4Ball milling and mixing according to the stoichiometric ratio, pressing into a wafer by using a die after high-temperature firing, carrying out cold isostatic pressing, and finally sintering at high temperature to obtain the catalyst, wherein the reaction temperature is 1250 ℃, and the reaction time is 16 hours.
As a preferable scheme of the invention, the working current density between the negative plate and the solid electrolyte is 0.5-65 mAcm-2。
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
the liquid alloy exists in a liquid state at normal temperature, the contact mode between the sodium metal cathode and the solid electrolyte can be changed into liquid-solid contact, the method is favorable for improving the interface wettability of the cathode and the solid electrolyte, sodium ions are more distributed, the uniform growth of metal sodium is better realized, the growth of dendritic crystals can be inhibited, the wettability of the metal sodium on the solid electrolyte can be improved by adopting the liquid sodium metal alloy cathode, more active sites are provided for the deposition of the metal sodium, and the distribution of the metal ions is more uniform.
Based on the advantages, the liquid sodium alloy is adopted as the cathode of the solid sodium ion battery, so that the energy density and the cycling stability of the solid sodium ion battery can be greatly improved, and the solid sodium ion battery is tested at normal temperature, so that the normal-temperature solid sodium ion battery based on the liquid sodium-potassium alloy is possible.
Drawings
FIG. 1 is a schematic diagram of a solid state sodium ion battery and its negative electrode and electrolyte interface contacts;
FIG. 2 is a photograph and a section electron microscope picture of a sodium-potassium alloy cathode; (a) an optical photo of the prepared sodium-potassium alloy cathode; (b) is a scanning electron microscope photo of the sodium-potassium alloy cathode section;
FIG. 3 is an electron microscope image of the interface of the cathode and electrolyte after cycling; (a) scanning electron microscope photographs of the interface contact condition after circulation by taking pure metal sodium as a negative electrode: (b) is a scanning electron microscope picture of the interface contact condition after circulation by taking the sodium-potassium alloy as a negative electrode.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
Referring to fig. 1-3, a room temperature solid sodium ion battery based on liquid alloy comprises a positive plate, a negative plate and a solid electrolyte, wherein the surface of the positive plate is coated with a positive active material, the negative plate comprises liquid alloy and a supporting framework, and the solid electrolyte is an NASICON type compound.
Specifically, the positive active material of the positive plate is sodium vanadium phosphate and NaMnO2Prussian blue compounds and sulfur positive electrodeThe sodium vanadium phosphate belongs to a sodium ion superconductor material, a stable sodium containing position is formed by an NASICON structure framework, an open three-dimensional ion migration channel is favorable for improving the diffusion of sodium ions, and the sodium vanadium phosphate is used as a battery anode material, has ideal specific capacity, voltage platform and circulation stability and is convenient to popularize and utilize.
The method is favorable for improving the wettability of the interface of the cathode and the solid electrolyte, so that sodium ions are distributed more, uniform growth of metal sodium is better realized, generation of dendritic crystals is inhibited, and the performance of the battery is improved.
Specifically, the preparation method of the negative plate comprises the following steps: the liquid alloy is prepared by directly and physically stacking metal sodium and metal potassium, under the protection of argon atmosphere, a certain amount of metal sodium and metal potassium are weighed according to the mass percentage of 9.2-58.2% of sodium, and are physically stacked together and kept stand for 1-3 hours to obtain the uniformly mixed sodium-potassium liquid alloy.
The solid-state sodium ion battery has the advantages that the redox graphene is selected for use as the support framework material, the sodium-potassium liquid alloy can be uniformly dispersed on the surface of the solid electrolyte through the support framework, the practicability and the using effect of the electrolyte can be further guaranteed, the three-dimensional porous structure of the redox graphene can relieve the volume change of metal sodium in the circulating process, the sodium-potassium alloy negative electrode is applied to the solid-state sodium ion battery, and the performance of the negative electrode is obviously improved.
Specifically, the support framework is prepared by the following steps: measuring a graphene oxide aqueous solution, carrying out suction filtration to obtain a graphene oxide film, drying in a drying oven, stripping the dried graphene oxide film from filter paper, and carrying out high-temperature thermal reduction under the protection of argon atmosphere to obtain a redox graphene film.
Specifically, the processing technology of the negative plate is as follows: a certain amount of liquid sodium-potassium alloy is directly dripped on the redox graphene film, the sodium-potassium alloy can be immediately sucked into the redox graphene film, and after the sodium-potassium alloy is completely absorbed by the redox graphene film, the sodium-potassium alloy is punched into a negative plate with the diameter of 1cm by a mould for standby application.
Specifically, the solid electrolyte is NASICON type Na1+xM2SixP3-xO12The solid sodium ion battery has the characteristics of high energy density and good cycle performance and safety performance, and can be stably cycled at normal temperature.
Specifically, the solid electrolyte is prepared by high-temperature solid-phase reaction method, and Na is added2CO3、ZrO2Or HfO2、MgO、SiO2、NH4H2PO4Ball milling and mixing according to stoichiometric ratio, after high temperature firing, pressing into a wafer by a mould, cold isostatic pressing, and finally sintering at high temperature to obtain the product, wherein the reaction temperature is 1250 ℃, the reaction time is 16 hours, and the process is simple and is beneficial to popularization.
Specifically, the working current density between the negative plate and the solid electrolyte is 0.5-65 mAcm-2The method can obviously improve the problem of interface wettability of the metal sodium cathode and the solid electrolyte, provides more active sites for the deposition of the metal sodium, enables the distribution of metal ions to be more uniform, effectively prevents the generation of sodium dendrites, improves the cycling stability of the metal sodium cathode, and improves the performance of the solid sodium ion battery.
Example 1:
the invention provides a room-temperature solid sodium-ion battery based on liquid alloy, which comprises the following operations: the solid sodium ion battery cathode is the sodium-potassium alloy cathode prepared in the above way, the cathode sheet material is liquid sodium-potassium alloy which exists in a liquid state at normal temperature, the contact mode between the sodium metal cathode and the solid electrolyte can be changed into liquid-solid contact, the method is favorable for improving the interface wettability of the cathode and the solid electrolyte, more distributes sodium ions, better realizes the uniform growth of metal sodium, inhibits the generation of dendrites, improves the battery performance, in order to explore the morphological characteristics of the prepared alloy negative electrode, the morphology of the sodium-potassium alloy negative electrode prepared above was characterized by a Scanning Electron Microscope (SEM), as shown in fig. 1, the cathode shows a layered porous structure, and metal sodium and metal potassium are uniformly distributed in the cathode, so that the generation of sodium dendrite is effectively prevented, the cycling stability of the metal sodium cathode is improved, and the performance of a solid sodium ion battery is improved.
Example 2:
different from the embodiment 1, in the embodiment, the redox graphene is adopted, the three-dimensional porous structure of the redox graphene can relieve the volume change of the metal sodium in the circulation process, in order to explore the existence form of the sodium-potassium alloy in the redox graphene film, the sodium-potassium alloy cathode is placed in glycol dimethyl ether, as the known sodium-potassium alloy can be dissolved in ethylene glycol dimethyl ether, the sodium-potassium alloy pellets can be observed to be separated from the negative electrode plate, which shows that the liquid state of the sodium-potassium alloy pellets in the electrode is always kept, the sodium-potassium alloy exists in a liquid state at normal temperature, the method can change the contact mode between the sodium metal cathode and the solid electrolyte into liquid-solid contact, is favorable for improving the interface wettability of the cathode and the solid electrolyte, enables sodium ions to be more distributed, better realizes the uniform growth of metal sodium, inhibits the generation of dendrites and improves the performance of the battery.
Example 3:
the embodiment provides a room temperature solid sodium ion battery based on liquid alloy, which comprises the following operations: the following operations were carried out in a glove box filled with argon (water content < 0.01ppm, oxygen content < 0.01ppm), with the sodium-potassium liquid alloy and the comparative common sodium foil as the negative electrodes, respectively, and the solid electrolyte was Na of NASICON type3.2Hf1.9Mg0.1Si2PO4Solid electrolyte, assembling button symmetrical cell, electroplating and stripping with blue test system at current density of 25mAcm-2The symmetrical battery assembled by taking the sodium-potassium alloy as the cathode still has small overpotential after being cycled for 220 hours, and when the current density is increased to 40mAcm-2Can still be stably circulated, the overpotential is only 10mV, and the battery assembled by the common sodium cathode is as low as 0.1mAcm-2The current density of the solid-state sodium ion battery can not be stably circulated, and the solid-state sodium ion battery still has stable circulation performance at normal temperature, strong practicability and convenient popularization and utilization.
Example 4:
the difference from example 3 is:
the current density applied in this example was from 0.1mAcm-2Increasing to 65mAcm-2When the limit current which can be borne by the symmetrical battery is tested, the limit current density which can be borne between the negative plate and the solid electrolyte can reach 65mAcm-2That is, the limiting current of a solid-state symmetrical battery using a liquid sodium-potassium alloy as a negative electrode is as high as 65mAcm-2Much larger than most of the current solid-state sodium ion batteries, the limiting current of the solid-state symmetrical battery taking pure sodium as the cathode is only 1mAcm-2The utility model has the advantages of strong practicability, wide application range, long service life and easy popularization and utilization.
Example 5:
the difference from example 3 is:
the electrolyte used in this example was liquid sodium ion battery electrolyte (1M NaClO)4in EC: DMC EMC 1:1:1 (5% FEC)), sodium-potassium alloy was still used as a negative electrode to assemble a button-type symmetrical battery, and the battery was subjected to plating and peeling tests with a blue test system at a current density of 25mAcm-2The symmetric battery can stably circulate for 320 hours without short circuit, which shows that the prepared sodium-potassium alloy cathode has the advantages in the liquid battery, long service life, easy popularization and utilization and strong practicability.
Example 6:
in contrast to example 3:
the battery after the circulation is disassembled in the glove box, the negative electrode is washed and dried, the appearance of the interface between the negative electrode and the solid electrolyte is observed by using a Scanning Electron Microscope (SEM), as shown in figure 2, compared with the common pure sodium negative electrode, the wettability of the sodium-potassium alloy on the solid electrolyte is better, the interface contact is tighter, the wettability is better and the interface contact is tighter in the actual use process, so that sodium ions in the solid sodium ion battery can be more distributed, the uniform growth of metal sodium is better realized, the generation of dendritic crystals is inhibited, the battery performance is improved, the service life is prolonged, and the use cost is reduced.
Example 7:
the difference from example 3 is:
according to the embodiment, after the symmetrical battery is assembled, alternating current impedance test is carried out by using more Princeton workstations, so that the effects of sodium-potassium alloy on improving interface contact and reducing interface resistance are reflected, the test frequency range is 0.01-105Hz, the amplitude is 10mV, and the result shows that compared with the solid-state symmetrical battery with pure sodium as the cathode, the interface impedance of the battery with the sodium-potassium alloy as the cathode is obviously reduced, the service life of the battery can be effectively prolonged, the use cost is reduced and the practicability is strong.
Example 8:
the difference from example 3 is:
in the embodiment, sodium-potassium alloy is used as a negative electrode, sodium vanadium phosphate is used as a positive electrode, the button type full-cell is assembled, the test current rate is 5 ℃, the test temperature is 25 ℃, and the discharge specific capacity after 100 cycles of circulation is 111.2mAhg-1The coulombic efficiency was 99.9%, and when the current rate was increased to 10C, the specific discharge capacity was 105.4mAhg-1And the capacity is not obviously attenuated after 100 cycles, which shows that the solid sodium ion battery has very good cycling stability, is small in limited degree in the actual use process, can effectively improve the use effect of the solid sodium ion battery and prolong the service life, is beneficial to popularization and utilization, has few preparation process steps, is simple to operate, and is suitable for large-scale popularization and production.
In conclusion, by adopting the sodium-potassium alloy as the cathode of the solid sodium ion battery, the problem of interface wettability between the metal sodium cathode and the solid electrolyte can be obviously improved, generation of sodium dendrite is effectively prevented, the cycling stability of the metal sodium cathode is improved, and the performance of the solid sodium ion battery is improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the equivalent replacement or change according to the technical solution and the modified concept of the present invention should be covered by the scope of the present invention.

Claims (10)

1. The utility model provides a room temperature solid-state sodium ion battery based on liquid alloy, includes positive plate, negative pole piece and solid electrolyte, its characterized in that: the surface of the positive plate is coated with a positive active substance, the negative plate comprises a liquid alloy and a supporting framework, and the solid electrolyte is an NASICON type compound.
2. The room temperature solid-state sodium ion battery based on the liquid alloy as claimed in claim 1, wherein the positive active material of the positive plate is one or more of sodium vanadium phosphate, NaMnO2, Prussian blue compounds and sulfur positive electrode.
3. The room temperature solid state sodium ion battery of claim 1, wherein the liquid alloy is one or more of a liquid sodium potassium alloy, a sodium cesium alloy and a sodium rubidium alloy.
4. A room temperature solid state sodium ion battery based on liquid alloy according to claim 3, characterized in that the negative plate is made of the following materials: the alloy is prepared by directly and physically stacking metal sodium and metal potassium, under the protection of argon atmosphere, a certain amount of metal sodium and metal potassium are weighed according to the mass percentage of 9.2-58.2% of sodium, and are physically stacked together and kept stand for 1-3 hours to obtain the uniformly mixed sodium-potassium liquid alloy.
5. The liquid alloy-based room temperature solid state sodium ion battery of claim 1, wherein the support framework material is redox graphene.
6. A room temperature solid state sodium ion battery based on liquid alloy as claimed in claim 5, characterized in that the support frame is prepared by the following steps: measuring a graphene oxide aqueous solution, carrying out suction filtration to obtain a graphene oxide film, drying in a drying oven, stripping the dried graphene oxide film from filter paper, and carrying out high-temperature thermal reduction under the protection of argon atmosphere to obtain the redox graphene film.
7. The liquid alloy-based room temperature solid state sodium ion battery according to claim 1, wherein the negative plate is processed by the following process: sucking a certain amount of liquid sodium-potassium alloy to directly drip on the redox graphene film, sucking the sodium-potassium alloy into the redox graphene film immediately, and after the sodium-potassium alloy is completely absorbed by the redox graphene film, punching the sodium-potassium alloy into a negative plate with the diameter of 1cm by using a mold for later use.
8. A liquid alloy based room temperature solid state sodium ion battery as claimed in claim 1 wherein the solid electrolyte is Na of NASICON type1+xM2SixP3-xO12(M ═ Zr, Hf) solid electrolyte.
9. The room temperature solid-state sodium ion battery based on liquid alloy as claimed in claim 1, wherein the solid electrolyte is prepared by high temperature solid phase reaction method and Na is added2CO3、ZrO2Or HfO2、MgO、SiO2、NH4H2PO4Ball milling and mixing according to stoichiometric ratio, firing at high temperature, pressing into round piece with a mould, cold isostatic pressing, and finally high-temperature sinteringAnd (3) sintering at a high temperature of 1250 ℃ for 16 hours.
10. The liquid alloy-based room temperature solid state sodium ion battery according to claim 1, wherein the operating current density between the negative electrode sheet and the solid electrolyte is 0.5-65 mAcm-2。
CN202110220007.4A 2021-02-26 2021-02-26 Room temperature solid sodium ion battery based on liquid alloy Pending CN113113593A (en)

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CN113659193A (en) * 2021-08-27 2021-11-16 西北工业大学 All-solid-state sodium ion battery cell structure, preparation method and battery
CN113659193B (en) * 2021-08-27 2023-09-01 西北工业大学 All-solid-state sodium ion battery cell structure, preparation method and battery
CN114975892A (en) * 2022-05-15 2022-08-30 北京化工大学 Preparation method of self-supporting liquid alloy electrode

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