CN112117434A - High-capacity electrode of solid sodium battery and preparation method and application thereof - Google Patents

High-capacity electrode of solid sodium battery and preparation method and application thereof Download PDF

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CN112117434A
CN112117434A CN202010926967.8A CN202010926967A CN112117434A CN 112117434 A CN112117434 A CN 112117434A CN 202010926967 A CN202010926967 A CN 202010926967A CN 112117434 A CN112117434 A CN 112117434A
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porous
sodium
solid electrolyte
electrode
solid
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CN112117434B (en
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温兆银
赖红健
吴相伟
王静宜
靳俊
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Shanghai Institute of Ceramics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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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Abstract

The invention discloses a high-capacity electrode of a solid-state sodium battery and a preparation method and application thereof. The high-load electrode of the solid-state sodium battery is porous/compact composite structure ceramic loaded with active substances, and comprises a porous/compact composite structure solid electrolyte and electrode active substances filled in pores of the porous/compact composite structure solid electrolyte; preferably, the porous/dense composite-structure solid electrolyte is a solid electrolyte having a vertical porous structure; more preferably, the electrode active material is synthesized in situ and filled in pores of the porous dense composite structure solid electrolyte. The high-capacity electrode of the solid sodium battery increases the contact area of the interface of the electrode and the solid electrolyte, reduces the interface impedance, and simultaneously improves the capacity of the active substances of the electrode, thereby improving the actual specific energy of the battery.

Description

High-capacity electrode of solid sodium battery and preparation method and application thereof
Technical Field
The invention relates to a high-load electrode of a solid sodium battery, a preparation method and application thereof, in particular to a method for loading an electrode active substance in a porous layer of a solid electrolyte with a porous/compact composite structure.
Background
The solid sodium battery has the advantages of excellent thermal stability, no leakage and volatilization, nonflammability, reduction of fire and the like. In addition, the sodium ion solid electrolyte has a higher electrochemical window, can be better matched with an electrode material, has good cycle performance and long service life, and can be used for a long time if being applied to the field of electric automobiles, thereby reducing the replacement cost of batteries. However, the contact interface between the electrode and the electrolyte of the solid-state sodium battery is solid-solid contact, the contact area is small, so that a large interface impedance is formed, and the electrode material loading is small, so that the practical energy density of the battery is low, and the commercial application of the battery is seriously hindered.
Increasing the interfacial contact area and increasing the electrode material loading is one of the key research items in solid-state sodium batteries. The Journal of Power Sources 247: 975-. The document ACS Cent Sci 3(1):52-57(Rechargeable Sodium All-Solid-State Battery) reports that the method of attaching the positive electrode to the Solid electrolyte by heating and pressurizing is used to increase the interfacial contact area. The literature Nano Lett 17(9): 5653-Organic Coating via Molecular Deposition Enable Long Life Sodium Metal Anode) reports an improvement in the wettability of the interface by means of a Coating of the electrolyte surface. The chinese patent CN106129350A uses sodium ion conductive material to modify the electrode in thin layer, so as to reduce the interface impedance and improve the battery performance. Chinese patent CN105374980A improves the interface problem by an interface wetting additive. The methods improve the problem of interface contact between the solid electrolyte and the electrode to a certain extent, but have the problems of complex process and high equipment requirement. Moreover, the above research mainly improves the interface, and does not change the design of the electrolyte structure, and the purpose of reducing the interface impedance and increasing the electrode material loading capacity cannot be realized.
Disclosure of Invention
In order to solve the problems, the invention provides a high-load electrode of a solid sodium battery and a preparation method and application thereof, which can increase the contact area (reduce the interface impedance) of the interface of the electrode and a solid electrolyte and simultaneously improve the load of active substances of the electrode, thereby improving the actual specific energy of the battery.
In a first aspect, the invention provides a high-load electrode of a solid sodium battery, which is a porous/dense composite structure ceramic loaded with an active material, and comprises a porous/dense composite structure solid electrolyte and an electrode active material filled in pores of the porous/dense composite structure solid electrolyte. Preferably, the porous/dense composite structure solid electrolyte is a solid electrolyte having a vertical porous structure. The design of the vertical porous structure is beneficial to the loading of active substances, and compared with disordered holes prepared by a pore-forming agent, the vertical porous structure can obviously shorten the migration path of sodium ions and reduce the tortuosity coefficient of diffusion, thereby increasing the dynamic effective diffusion coefficient and meeting the requirement of improving the performance of the battery.
Preferably, the electrode active material is synthesized in situ and filled in the pores of the solid electrolyte with the porous dense composite structure. By introducing the electrode active substance into the pores of the porous layer of the solid electrolyte with the porous/compact composite structure in an in-situ synthesis manner, the problem that the pores are easily blocked when the active particulate substance is injected into the porous layer can be effectively solved, and the loading capacity of the active substance is further improved.
Preferably, the solid electrolyte is a sodium solid electrolyte (a solid electrolyte of a sodium ion conductor). Preferably beta-Al2O3、Na3Zr2Si2PO12、Na3SbS4And Na3PS4One or a mixture of several of them. The solid electrolyte has high ionic conductivity and excellent thermal stability.
Preferably, the porous/dense composite structure solid electrolyte includes a porous layer near the positive electrode side and a dense layer near the negative electrode side. The design of the porous layer can improve the loading of active substances and increase the contact area to reduce the interface impedance, and the design of the dense layer can improve the overall mechanical strength of the electrolyte.
Wherein the thickness of the porous layer is 0.5-5mm, the diameter of the pores is 5-20 μm, and the porosity is 30-60%; the thickness of the compact layer is 20-200 μm, and the density is more than 95%. According to the invention, the electrode active substance is loaded in the porous electrolyte, and the porous layer has high porosity, so that the loading capacity of the active substance can be improved, the energy density of the battery can be improved, the contact area of the active substance and the electrolyte can be increased, and the volume expansion of the electrode substance can be relieved in the battery circulation process, thereby improving the circulation stability of the battery.
Preferably, the electrode active material is a positive electrode active material, preferably a polyanion compound of a sodium fast ion conductor structure. The phosphate anode material has a stable structure, and the volume of the phosphate anode material does not change obviously in the charge-discharge cycle process. Specifically, the polyanion compound with a sodium fast ion conductor (NASICON) structure has an open framework structure, can rapidly conduct sodium ions, has a very stable structure in a sodium ion deintercalation process, and is not easy to change in volume in a charge-discharge cycle process. The polyanion compound of the sodium fast ion conductor structure comprises one or more of sodium vanadium phosphate, sodium ferric phosphate and sodium titanium phosphate. The vanadium sodium phosphate has a typical NASICON structure, good Na ion conductivity, small volume change in the embedding and de-embedding processes, high voltage platform (3.4V), high theoretical specific energy (400Wh/kg), good thermal stability and is a sodium ion battery anode material with a good prospect.
Preferably, the unit area loading capacity of the positive electrode active material is 1-20mg/cm2. When the load is excessive, the active material is agglomerated, reducing the ion electron conductivity, resulting in a significant increase in the polarization of the battery, thereby affecting the battery performance.
Preferably, the positive electrode active material is infiltrated in the form of a sol into the pores of the porous layer of the porous/dense composite structure solid electrolyte and the active material is generated in situ in the porous layer by sintering. By in-situ synthesis of the active substance in the porous layer by permeating the active substance sol, the pore of the porous layer can be prevented from being blocked, the loading capacity of the active substance can be improved, the contact property of the active substance and the pore wall of the electrolyte can be improved, and the interface impedance can be reduced.
Preferably, the electrode active material is molten metal sodium as a negative electrode active material, which is infiltrated in the form of a melt into the pores of the porous layer of the porous/dense composite-structure solid electrolyte. Therefore, the stress concentration caused by the uneven deposition of sodium in the charge-discharge cycle process of the battery can be relieved to damage the electrolyte compact layer, and the generation of sodium dendrite can be effectively prevented.
Preferably, the high-load electrode of the solid-state sodium battery further comprises an elastic and adaptable system-change ionic liquid or polymer electrolyte which is positioned between the pore wall of the porous layer and the electrode active material. The interfacial wettability can be increased by adding a small amount of an ionic liquid or a polymer electrolyte to the pores of the porous layer supporting the active material; and the introduction of the ionic liquid can prevent the active substances from falling off from the pore walls and further reduce the interface impedance.
In a second aspect, the present invention provides a method for preparing a high-capacity electrode of a solid-state sodium battery, comprising the following steps:
(1) preparing a solid electrolyte with a vertical porous structure by an ice template method;
(2) impregnating the vertical porous structure solid electrolyte with the compact layer slurry to form a compact layer on one side of the porous layer, and then sintering to obtain a porous/compact composite structure solid electrolyte with the porous layer and the compact layer in layered distribution;
(3) introducing an electrode active substance into pores of a porous layer of the solid electrolyte with the porous/compact composite structure to obtain a high-load electrode of the solid sodium battery; preferably, the method of introducing the active material includes any one of a dipping method, a dropping method, and an in-situ sol-gel method.
Aiming at the solid sodium battery, the invention adopts an ice template method to prepare the porous structure of the electrolyte, and utilizes the gradient temperature difference under the vacuum environment to lead the ice crystal to vertically grow to obtain the electrolyte with the vertical porous structure. In some embodiments, the invention introduces an elastic ionic liquid transition layer into the vertical hole layer, which can prevent the active material from falling off from the pore wall during the circulation process, and wet the positive electrode interface, further reducing the interface impedance.
In a third aspect, the invention also discloses the application of the high-load electrode of the solid-state sodium battery in a flat-plate solid-state sodium battery.
In a fourth aspect, the present invention provides a method for simultaneously increasing the interfacial contact area and increasing the loading of electrode active material, comprising: preparing a porous/compact composite structure solid electrolyte with a porous layer and a compact layer which are distributed in a layered manner, and injecting electrode active substances into pores of the porous layer. The method can fill the electrode active material into the electrolyte porous layer as much as possible, thereby increasing the loading of the electrode active material.
Drawings
FIG. 1 is a schematic view of a porous/dense composite structure electrolyte according to the present invention;
FIG. 2 shows beta-Al prepared by an ice template method in example 3 of the present invention2O3The electrolyte porous layer is subjected to scanning electron microscopy, wherein (a) and (b) are surface topography maps of the porous layer, and (c) and (d) are cross-sectional topography maps of the porous layer;
FIG. 3 shows the preparation of beta-Al by the slurry dipping method in example 3 of the present invention2O3Electrolyte scanning electron microscope picture;
FIG. 4 shows active material-loaded beta-Al of example 9 of the present invention2O3A porous layer picture; wherein (a) is a cross-sectional scanning electron micrograph of the vanadium sodium phosphate loaded porous layer, and (b) is an EDS element distribution diagram of the corresponding region;
FIG. 5 shows the present invention in comparative example 1 with fully dense beta-Al2O3Impedance spectra of high-load (6mg) cells of electrolyte assembly;
FIG. 6 shows example 9 of the present invention in which beta-Al is a porous/dense composite structure2O3Height of electrolyte assemblyImpedance spectra of load (6mg) cells;
FIG. 7 shows example 9 of the present invention in which beta-Al is a porous/dense composite structure2O3Cycling performance profile of high loading (6mg) cells with electrolyte assembly.
Detailed Description
The invention is further illustrated with reference to the following description and with reference to the accompanying drawings. It is to be understood that the drawings and/or detailed description are only illustrative of the invention and are not restrictive thereof.
In the solid-state sodium battery, the electrode active material and the solid electrolyte are in solid-solid plane contact, the contact area is small, the interface resistance is large, the loading amount of the active material is small, and the actual energy density of the battery is low. Therefore, the porous/compact composite structure sodium solid electrolyte is prepared, and the active substance is loaded in the pores of the porous layer, so that the contact area between the positive active substance and the electrolyte can be increased, the interface problem can be improved, the loading capacity of the active substance can be improved, and the energy density of the battery can be further improved.
The following is an exemplary illustration of the method of making the high capacity electrode of the solid state sodium battery of the present invention.
And (4) preparing the porous layer slurry. The porous layer slurry includes a sodium solid electrolyte, a binder, and a solvent. The sodium solid electrolyte includes, but is not limited to, beta-Al2O3(also known as beta-Al)2O3”)、Na3Zr2Si2PO12、Na3SbS4And Na3PS4One or more of them. Preferably beta-Al2O3It has high ion conductivity (up to 3.2 × 10 at 60 deg.C)-3S cm-2. Binders include, but are not limited to, PVB, PVA, PEG, and like polymers. The porous layer slurry selects a solvent with a higher freezing point, which is beneficial to the icing of the solvent and the manufacture of vertical pores. For example, t-butanol, ethylene glycol, DMSO, etc. can be used as the solvent. The solid content of the sodium solid electrolyte in the porous layer slurry may be 20 to 70%, preferably 30 to 50%.
And preparing the vertical porous structure sodium solid electrolyte. The design of the vertical porous layer facilitates the penetration of active species. The vertical porous structure sodium solid electrolyte can be prepared by an ice template method. For example, sponge template is adopted to adsorb porous layer slurry, and freeze drying and sintering are carried out to obtain the vertical porous structure sodium solid electrolyte. The purpose of sintering is to remove the template and shrink and shape the vertical bore layer. As an example, sponge is used for absorbing the porous layer slurry, and the sponge after absorbing the porous layer slurry is vertically frozen by using a semiconductor refrigeration sheet. The freezing temperature can be 0-50 deg.C, and the freezing time can be 20-200min, preferably 60-80 min. Then putting the mixture into a freeze dryer for freeze drying. The freeze-drying time can be 5-20h, preferably 10-12 h. And sintering the freeze-dried sponge to obtain the vertical porous structure sodium solid electrolyte. The sintering temperature may be 800-1400 deg.C, preferably 1000-1200 deg.C. The sintering time may be from 1 to 5 hours, preferably from 2 to 3 hours. The rate of temperature rise may be 1-5 deg.C/min, preferably 2-3 deg.C/min.
And (5) configuring the dense layer slurry. The dense layer slurry includes a solvent, an additive, and a sodium solid electrolyte. The sodium solid electrolyte includes, but is not limited to, beta-Al2O3、Na3Zr2Si2PO12、Na3SbS4And Na3PS4Preferably beta-Al2O3. The additive can be selected from triethanolamine, PVB, PEG and the like, and can be used as a binder to make the slurry have certain viscosity. The solvent of the dense layer slurry can be selected from ethanol, butanone, isopropanol and the like. The solid content of the sodium solid electrolyte in the slurry of the dense layer may be 5 to 40%, preferably 10 to 20%. The solid content of the slurry of the compact layer is lower than that of the slurry of the porous layer, because the solid content of the slurry of the compact layer is low, and the slurry is repeatedly dipped for many times, which is favorable for improving the compactness.
And repeatedly dipping the vertical porous structure sodium solid electrolyte into the compact layer slurry and then sintering to obtain the porous/compact composite structure solid electrolyte with the layered distribution of the porous layer and the compact layer. The sintering is sodium-rich atmosphere sintering, and aims to prevent the volatilization of sodium element in the powder and facilitate the formation of beta-Al2O3Pure phase. The sintering temperature can be 1500-1600 ℃, and the sintering time can be 5-15 min. The purpose of the co-sintering is to bond the porous layer and theThe dense layers are in phase and provide intimate contact between the bilayers.
In the solid electrolyte with a porous/compact composite structure, the thickness of the porous layer can be 0.5-5mm, the diameter of the pores is 5-20 μm, and the porosity can be 30-60%. The porous layer is preferably a vertical porous layer. The thickness of the dense layer may be 20 to 200. mu.m, preferably 50 to 100. mu.m. In the porous/dense composite structure, the dense layer is continuous with the surface of at least one side of the porous layer. In some embodiments, the dense layer has a density of 95% or greater. It is understood that although some pores are inevitably contained in the dense layer, the electrode active material is mostly introduced into the pores of the porous layer of the porous/dense composite structure solid electrolyte in practical experiments due to the small loading amount of the electrode active material, that is, the electrode active material is hardly present in the dense layer. In this regard, it can be selected from beta-Al2O3No confirmation of the electrode active material particles was observed in the scanning electron micrograph of the solid electrolyte dense layer.
In some embodiments, the ratio of the thicknesses of the porous layer and the dense layer is 10: 1-5: 1, the electrolyte thus obtained has a high ionic conductivity and a high mechanical strength.
Then, an active material is introduced into the pores of the porous layer of the porous/dense composite structure solid electrolyte. The present invention provides different methods of synthesizing and injecting active species. First, active material particles are prepared, and then, an active material is injected into a porous electrolyte (method one, method two). Or the active material is synthesized in situ in the porous layer by a sol-gel method (method three). The above method is suitable for introduction of a positive electrode active material. The positive active material includes, but is not limited to, sodium vanadium phosphate, sodium iron phosphate, sodium titanium phosphate, and the like.
In an alternative embodiment, the first mode includes: at least one active substance is first synthesized by a solid-phase method, an electrostatic spinning method, a sol-gel method or a hydrothermal method. Then, the active material is dissolved in a solvent (e.g., NMP), the porous layer is immersed in a solution containing the active material, and the solvent is evaporated (e.g., the solvent is evaporated at 100 ℃), so that the active material is successfully supported in the electrolyte porous layer.
In an alternative embodiment, the second method includes: at least one active substance is first synthesized by a solid-phase method, an electrostatic spinning method, a sol-gel method or a hydrothermal method. Then, the active material is dissolved in a solvent (e.g., NMP), a solution containing the active material is dropped into the porous layer, and the solvent is evaporated, so that the active material is successfully supported in the electrolyte porous layer.
In an alternative embodiment, the third method includes: electrode active substance sols such as sodium vanadium phosphate sol, sodium ferric phosphate sol and sodium titanium phosphate sol are synthesized by a sol-gel method, and electrode active substance particles are synthesized in situ in an electrolyte porous layer through high-temperature reaction and calcination. As an example, an electrode active material sol is dropped into an electrolyte porous layer, and then the solvent is evaporated, repeating many times until the active material in the porous layer reaches a certain loading amount. And then putting the porous electrolyte into a drying oven at 150 ℃ for reaction for 12 hours to form gel, and finally co-firing the gel to form the electrode active substance in the porous electrolyte.
The electrode active material in the present invention is preferably a polyanion compound having a sodium fast ion conductor structure. The polyanionic compounds incorporated in the present invention have a distinct ion conduction mechanism compared to the layered oxide. When the layered oxide is used as an electrode active material, sodium ions are transmitted between layers of the active material; each protocell of a polyanionic compound such as sodium vanadium phosphate is composed of 6 unit cells, each unit cell is composed of 2 VOs6Octahedron and 3 POs4The tetrahedron shares angles. Wherein, VO is in z-axis6Octahedron and PO4The tetrahedrons are connected with each other through oxygen atoms on a common angle to form polyanion units, which respectively occupy two different positions of Na (1) and Na (2), wherein Na (1) is positioned at [ V ]2(PO4)3]In the structural unit, and Na (2) is located in two adjacent [ V ]2(PO4)3]Between the belts. The sodium removed is from Na (2), the Na at Na (1) is kept unchanged, the framework structure is not changed, and the three-dimensional ion diffusion channels are 2, so that the ion transmission is facilitated, and the volume change of the sodium-ion battery in the circulating process is relieved.
Preparation of high-capacity electrode of solid sodium batteryThe method allows the electrode active material to be filled into the electrolyte porous layer as much as possible, thereby increasing the loading amount of the electrode active material. The unit area load capacity of the positive active material is 1-20mg/cm2. The area refers to the area of the ceramic pole piece. In particular, in the embodiment, the loading amount of the electrode active material may be 1 to 20mg, preferably 4 to 8 mg.
Also provided in the present invention is a method of supporting an anode active material. The metal sodium is melted and permeates into the electrolyte porous layer to be used as a negative electrode, so that the damage to the electrolyte compact layer caused by stress concentration due to the uneven deposition of the sodium in the charge-discharge cycle process of the battery is relieved, the generation of sodium dendrite is effectively prevented, and the performance of the battery is further improved.
It is noteworthy that sodium ion battery and lithium ion battery systems need to overcome different technical hurdles when faced with the difficult problems of increasing interfacial contact area and increasing electrode material loading. Firstly, the charge carriers in the batteries are different, the lithium ion battery realizes charge and discharge through the movement and conversion of lithium ions between the positive electrode and the negative electrode, and the sodium ion battery realizes charge transfer through the insertion and the separation of sodium ions between the positive electrode and the negative electrode. And secondly, the two ions have different radiuses, the radius of the sodium ions is larger than that of the lithium ions, and the intercalation/deintercalation resistance of the sodium ions in the positive electrode and the negative electrode is larger. Based on the above two points, the sodium ion battery needs to overcome the difficulty of ion conduction and the easy expansion or contraction (large volume change) of volume caused by the intercalation/deintercalation of sodium ions with large radius. The polyanion compound with the vertical porous design and the sodium fast ion conductor structure is beneficial to ion transmission and relieves the volume change of the sodium ion battery in the circulating process, which is firstly proposed and used by the invention.
The present invention is further illustrated by the following examples. However, the scope of the present invention should not be limited to the scope described in examples and comparative examples, and any modification that does not depart from the subject matter of the present invention will be understood by those skilled in the art to be within the scope of the present invention. The specific process parameters and the like of the following examples are also only one example of suitable ranges and are not intended to be limited to the specific values of the following examples.
The area of the ceramic pole piece (positive electrode) in the above embodiment was 1cm2Left and right.
Comparative example 1
beta-Al is mixed2O3Pressing the powder into a fully compact sheet with the diameter of 16mm through a die, embedding the powder for sintering, and sintering at 1550 ℃ for 10min to obtain fully compact beta-Al2O3An electrolyte. Then preparing vanadium sodium phosphate active substance by sol-gel method, coating 6mg vanadium sodium phosphate on compact beta-Al2O3The electrolyte was used as the positive electrode, and the sodium sheet was used as the negative electrode, to assemble the battery. The battery performance is tested, and the impedance spectrum is shown in fig. 5, so that the impedance is very large, and the battery can hardly be normally cycled.
Example 1
Firstly, 6g of beta-Al2O3The powder was dissolved in 10g of t-butanol (solid content: 35% by mass)), and 1g of a polymerization agent PEG was added thereto, and stirred on a heating stage at 40 ℃ for 4 hours to form a porous layer slurry. Then, sponge templates with the diameter of 16mm are used for adsorbing the porous layer slurry, the porous layer slurry is placed on a semiconductor refrigerating sheet with the temperature of 50 ℃ below zero for vertical freeze drying, and the porous layer slurry is placed in a freeze dryer for freeze drying for 12 hours. And finally, sintering the porous material at 1000 ℃ for 2h at the heating rate of 2 ℃/min to obtain the vertical porous structure. Repeatedly dipping the dense layer slurry on one surface of the vertical porous structure, sintering for 10min at 1550 ℃ by adopting a powder embedding sintering method to obtain beta-Al with a porous/dense composite structure2O3An electrolyte (a schematic of which is shown in figure 1). The porosity of the porous layer was 54% as measured by archimedes' method. Synthesizing sodium vanadium phosphate by a sol-gel method, dissolving the sodium vanadium phosphate in NMP to form a solution, then dropping the solution into the porous layer, and evaporating the solvent at 100 ℃ to successfully load the active substance sodium vanadium phosphate in the porous pores of the electrolyte to form the active substance-loaded porous/dense composite structure ceramic. The obtained porous/compact composite structure ceramic loaded with active substances is used as a positive electrode and an electrolyte, a sodium sheet is used as a negative electrode, a small amount of electrolyte wets an interface to assemble a full cell, and all operations for assembling the cell are carried out in a glove box.
Example 2
beta-Al for preparing porous compact composite structure2O3Electrolyte, detailed description steps referring to example 1, only beta-Al in porous layer slurry was changed2O3The addition amount of the powder achieves the aim of adjusting the solid content, so that the solid content is 40%. The porosity of the porous layer was measured to be 50% by archimedes' method. Synthesizing sodium vanadium phosphate by a sol-gel method, dissolving the sodium vanadium phosphate in NMP to form a solution, then dropping the solution into the porous layer, and evaporating the solvent at 100 ℃ to successfully load the active substance sodium vanadium phosphate in the porous pores of the electrolyte to form the active substance-loaded porous/dense composite structure ceramic. The obtained porous/compact composite structure ceramic loaded with active substances is used as a positive electrode and an electrolyte, a sodium sheet is used as a negative electrode, a small amount of electrolyte wets an interface to assemble a full cell, and all operations for assembling the cell are carried out in a glove box.
Example 3
beta-Al for preparing porous compact composite structure2O3Electrolyte, detailed description steps referring to example 1, only beta-Al in porous layer slurry was changed2O3The addition amount of the powder achieves the aim of adjusting the solid content, so that the solid content is 45 percent. The porosity of the porous layer was 47% as measured by the archimedes method. Synthesizing sodium vanadium phosphate by a sol-gel method, dissolving the sodium vanadium phosphate in NMP to form a solution, then dropping the solution into the porous layer, evaporating the solvent at 100 ℃, and successfully loading the active substance sodium vanadium phosphate in the porous pores of the electrolyte to form the active substance-loaded porous/dense composite structure ceramic. The obtained porous/compact composite structure ceramic loaded with active substances is used as a positive electrode and an electrolyte, a sodium sheet is used as a negative electrode, a small amount of electrolyte wets an interface to assemble a full cell, and all operations for assembling the cell are carried out in a glove box.
Example 4
beta-Al for preparing porous compact composite structure2O3Electrolyte, detailed description steps referring to example 1, only beta-Al in porous layer slurry was changed2O3The addition amount of the powder is adjustedThe solid content was adjusted to 50%. The porosity of the porous layer was 40% as measured by the archimedes method. Synthesizing sodium vanadium phosphate by a sol-gel method, dissolving the sodium vanadium phosphate in NMP to form a solution, then dropping the solution into the porous layer, and evaporating the solvent at 100 ℃ to successfully load the active substance sodium vanadium phosphate in the porous pores of the electrolyte to form the active substance-loaded porous/dense composite structure ceramic. The obtained porous/compact composite structure ceramic loaded with active substances is used as a positive electrode and an electrolyte, a sodium sheet is used as a negative electrode, a small amount of electrolyte wets an interface to assemble a full cell, and all operations for assembling the cell are carried out in a glove box.
By analyzing the above porous structure with different porosities, it was found that beta-Al is present when the porous layer slurry is subjected to the above-mentioned treatment2O3When the solid content of the powder is 45%, the surface and section profile of the obtained electrolyte porous layer is shown in figure 2, and the electrolyte has an obvious vertical porous structure, and the pores of the porous layer are uniformly distributed. The diameter of the pores is 10-20 μm. The porosity, determined by the Archimedes method, was 47%. From fig. 3, it can be seen that the contact between the vertical pore layer (porous layer) and the dense layer is tight and the layered distribution is presented, and from fig. 4, it can be seen that the vanadium sodium phosphate is successfully loaded in the vertical pore layer, and the battery performance of the electrolyte loaded active material assembly of the porous dense structure is more excellent.
Example 5
beta-Al for preparing porous compact composite structure2O3Electrolyte, the concrete implementation steps refer to example 1, and beta-Al in the porous layer slurry2O3The solid content of the powder is 45 percent, and the purpose of further increasing the contact area of the active substance and the porous layer is achieved only by changing the method of synthesizing and injecting the active substance. Synthesizing sodium vanadium phosphate by a solid phase method, dissolving the sodium vanadium phosphate in NMP to form a solution, then soaking the porous layer in the solution, evaporating the solvent at 100 ℃, and successfully loading the active substance sodium vanadium phosphate in the porous pores of the electrolyte to form the active substance-loaded porous/dense composite structure ceramic. The obtained porous/compact composite structure ceramic loaded with active substances is used as a positive electrode and an electrolyte, and sodium is usedThe sheet was the negative electrode and the whole cell was assembled with a small amount of electrolyte wetting interface, all the operations for assembling the cell were performed in a glove box. The assembled battery can be stably cycled.
Example 6
beta-Al for preparing porous compact composite structure2O3Electrolyte, the concrete implementation steps refer to example 1, and beta-Al in the porous layer slurry2O3The solid content of the powder is 45 percent, and the purpose of further increasing the contact area of the active substance and the porous layer is achieved only by changing the method of synthesizing and injecting the active substance. Synthesizing sodium vanadium phosphate sol by a sol-gel method, infiltrating the sol into a porous layer, putting the porous layer into a vacuum oven to evaporate water, repeating the steps for many times until the load capacity of the active substance reaches 4mg, and in-situ generating the sodium vanadium phosphate active substance in pores through drying and sintering to form the active substance-loaded porous/compact composite structure ceramic. The obtained porous/compact composite structure ceramic loaded with active substances is used as a positive electrode and an electrolyte, a sodium sheet is used as a negative electrode, a small amount of electrolyte wets an interface to assemble a full cell, and all operations for assembling the cell are carried out in a glove box. The assembled cell has a small interfacial impedance and can be cycled stably for 100 cycles, and the coulombic efficiency for the first 50 cycles can be as high as 99%.
When active substance particles are injected by adopting an impregnation method and a dripping method, the active substances are positioned in pores and are in contact with the solid point of the pore walls, the contact area is small, the ionic conduction capability is poor, and the electrochemical performance of the battery is influenced. The sol is injected into the porous layer by adopting a sol-gel method to synthesize the active substance in situ, so that the problem can be effectively solved, the active substance grows on the pore wall in situ, the contact area is increased, the ion conduction capability is improved, and the battery performance is improved.
Example 7
beta-Al for preparing porous/compact composite structure2O3Electrolyte, the concrete implementation steps refer to example 1, and beta-Al in the porous layer slurry2O3The solid content of the powder is 45%, and only the types of active substances are changed. Synthesizing sodium titanium phosphate sol by sol-gel method, and infiltrating the sol into the porous layerAnd putting the ceramic into a vacuum oven to evaporate water, repeating for many times until the loading capacity of the active substance sodium titanium phosphate reaches 4mg, and generating the sodium titanium phosphate active substance in situ in pores through drying and sintering to form the active substance-loaded porous/compact composite structure ceramic. The obtained porous/compact composite structure ceramic loaded with active substances is used as a positive electrode and an electrolyte, a sodium sheet is used as a negative electrode, a small amount of electrolyte wets an interface to assemble a full cell, and all operations for assembling the cell are carried out in a glove box.
Example 8
beta-Al for preparing porous compact composite structure2O3Electrolyte, the concrete implementation steps refer to example 1, and beta-Al in the porous layer slurry2O3The solid content of the powder is 45%, and only the types of active substances are changed. Synthesizing sodium ferric phosphate sol by a sol-gel method, infiltrating the sol into the porous layer, putting the porous layer into a vacuum oven to evaporate water, repeating the steps for many times until the load capacity of the active substance reaches 4mg, and generating the sodium ferric phosphate active substance in the pores in situ through drying and sintering to form the active substance-loaded porous/compact composite structure ceramic. The obtained porous/compact composite structure ceramic loaded with active substances is used as a positive electrode and an electrolyte, a sodium sheet is used as a negative electrode, a small amount of electrolyte wets an interface to assemble a full cell, and all operations for assembling the cell are carried out in a glove box.
Comparing batteries assembled by different positive active materials, the battery assembled by loading the vanadium sodium phosphate active material in the porous layer has the best cycle performance, because the vanadium sodium phosphate positive electrode material has a more stable structure and is not easy to change in volume in the cycle process.
Example 9
beta-Al for preparing porous/compact composite structure2O3Electrolyte, the concrete implementation steps refer to example 1, and beta-Al in the porous layer slurry2O3The solid content of the powder is 45%, and the purpose of further increasing the energy density of the battery is achieved only by changing the loading amount of the active substances. Synthesizing sodium vanadium phosphate sol by a sol-gel method, infiltrating the sol into the porous layer, putting the porous layer into a vacuum oven, and evaporating the water to dryness. Repeatedly infiltrating the sol for many times, and generating the sodium vanadium phosphate active substance in situ in the pores through drying and sintering to form the porous/compact composite structure ceramic loaded with the active substance. The loading of the active substance sodium vanadium phosphate reaches 6 mg. The obtained porous/compact composite structure ceramic loaded with active substances is used as a positive electrode and an electrolyte, a sodium sheet is used as a negative electrode, a small amount of electrolyte wets an interface to assemble a full cell, and all operations for assembling the cell are carried out in a glove box. Compared with the battery assembled by the sodium vanadium phosphate with the loading of 4mg, the battery capacity is increased, and the energy density is also improved. It can be seen from fig. 6 and 7 that the assembled battery has less resistance and stable cycle performance.
Example 10
beta-Al for preparing porous/compact composite structure2O3Electrolyte, the concrete implementation steps refer to example 1, and beta-Al in the porous layer slurry2O3The solid content of the powder is 45%, and the purpose of further increasing the energy density of the battery is achieved only by changing the loading amount of the active substances. And synthesizing sodium vanadium phosphate sol by a sol-gel method, infiltrating the sol into the porous layer, and putting the porous layer into a vacuum oven to evaporate water. Repeatedly infiltrating the sol for many times, and generating the sodium vanadium phosphate active substance in situ in the pores through drying and sintering to form the porous/compact composite structure ceramic loaded with the active substance. The loading of the active substance sodium vanadium phosphate reaches 8 mg. The obtained porous/compact composite structure ceramic loaded with active substances is used as a positive electrode and an electrolyte, a sodium sheet is used as a negative electrode, a small amount of electrolyte wets an interface to assemble a full cell, and all operations for assembling the cell are carried out in a glove box.
The capacity of the battery with 8mg of sodium vanadium phosphate loading was improved compared to the battery assembled with 4mg and 6mg of sodium vanadium phosphate loading. However, the electronic conductivity of the battery is poor due to the excessive loading of the active material, and the polarization of the battery is remarkably increased, thereby causing the performance of the battery to be poor.
The analysis of the above embodiment can lead to: the energy density can be further increased by appropriately increasing the amount of the electrode active material to be supported, but too much amount of the electrode active material to be supported results in increased polarization of the battery and deterioration of the battery performance. Among them, when the active material loading amount is 6mg, the assembled battery has the best performance. As shown in fig. 7, the assembled all-solid battery can be cycled for 100 cycles with relative stability.
Example 11
Firstly 8g of beta-Al2O3The powder was dissolved in 10g of t-butanol, and 1g of binder PEG was added thereto, and stirred on a heating stage at 40 ℃ for 4 hours to form a porous layer slurry. Then, sponge templates with the diameter of 16mm are used for adsorbing the porous layer slurry, the porous layer slurry is placed on a semiconductor refrigerating sheet with the temperature of 50 ℃ below zero for vertical freeze drying, and the porous layer slurry is placed in a freeze dryer for freeze drying for 12 hours. And finally, sintering at 1000 ℃ for 2h at the heating rate of 2 ℃/min to obtain the solid electrolyte with the vertical porous structure. Polishing one surface of the solid electrolyte vertical to the porous structure, repeatedly soaking compact layer slurry, and sintering at 1550 ℃ for 10min by adopting a powder embedding sintering method to obtain beta-Al with a porous/compact composite structure2O3An electrolyte. The metallic sodium is melted at a high temperature of 300 c and then infiltrated into the porous layer of the electrolyte as a negative electrode. And (3) taking the aluminum foil coated with the sodium vanadium phosphate on the surface as a positive electrode, and wetting the interface with a small amount of electrolyte to assemble the battery. All operations for assembling the battery are performed in a glove box.

Claims (10)

1. The high-load electrode of the solid sodium battery is characterized in that the high-load electrode of the solid sodium battery is porous/compact composite structure ceramic loaded with active substances, and comprises a porous/compact composite structure solid electrolyte and electrode active substances filled in pores of the porous/compact composite structure solid electrolyte; preferably, the porous/dense composite-structure solid electrolyte is a solid electrolyte having a vertical porous structure; more preferably, the electrode active material is synthesized in situ and filled in pores of the porous dense composite structure solid electrolyte.
2. A solid state sodium battery high load electrode as claimed in claim 1, wherein the solid electrolyte is sodium solid electrolyte, preferably beta-Al2O3、Na3Zr2Si2PO12、Na3SbS4And Na3PS4One or a mixture of several of them.
3. A solid state sodium battery high load electrode as claimed in claim 1 or 2, wherein the porous/dense composite structure solid electrolyte comprises a porous layer near the positive side and a dense layer near the negative side; wherein the thickness of the porous layer is 0.5-5mm, the diameter of the pores is 5-20 μm, and the porosity is 30-60%; the thickness of the compact layer is 20-200 μm, and the density is more than 95%.
4. A solid state sodium battery high load electrode according to any one of claims 1 to 3, wherein the electrode active material is a positive electrode active material, preferably a polyanionic compound of sodium fast ion conductor structure including one or more of sodium vanadium phosphate, sodium ferric phosphate and sodium titanium phosphate.
5. The high-load electrode for solid-state sodium batteries according to any one of claims 1 to 4, characterized in that the loading per unit area of the positive active material is 1-20mg/cm2。
6. A solid state sodium battery high load electrode as claimed in any one of claims 1 to 5, characterized in that the positive electrode active substance is infiltrated in the form of a sol into the pores of the porous layer of the porous/dense composite structure solid electrolyte and the active substance is generated in situ in the porous layer by sintering.
7. A solid state sodium battery high load electrode as claimed in any one of claims 1 to 6, wherein the electrode active material is molten metallic sodium as a negative electrode active material which is infiltrated in molten form into the pores of the porous layer of the porous/dense composite structure solid electrolyte.
8. A solid state sodium battery high load electrode as claimed in any one of claims 1 to 7, characterized in that the solid state sodium battery high load electrode further comprises an elastic, adaptable system-change ionic liquid or polymer electrolyte between the pore walls of the porous layer and the electrode active material.
9. Method for the preparation of a high load electrode for a solid state sodium battery according to any of claims 1 to 8, characterized in that it comprises the following steps:
(1) preparing a solid electrolyte with a vertical porous structure by an ice template method;
(2) impregnating the vertical porous structure solid electrolyte with the compact layer slurry to form a compact layer on one side of the porous layer, and then sintering to obtain a porous/compact composite structure solid electrolyte with the porous layer and the compact layer in layered distribution;
(3) introducing an electrode active substance into pores of a porous layer of the solid electrolyte with the porous/compact composite structure to obtain a high-load electrode of the solid sodium battery; preferably, the method of introducing the active material includes any one of a dipping method, a dropping method, and an in-situ sol-gel method.
10. Use of the solid state sodium battery high load electrode of any one of claims 1 to 8 in a flat panel solid state sodium battery.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN114267876A (en) * 2021-12-20 2022-04-01 上海科技大学 Integrated electrode-electrolyte structure, preparation method thereof and all-solid-state battery
CN114975860A (en) * 2022-06-28 2022-08-30 重庆冠宇电池有限公司 Negative plate and battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104272518A (en) * 2012-04-27 2015-01-07 株式会社丰田自动织机 Solid electrolyte and secondary battery
CN104282867A (en) * 2013-07-12 2015-01-14 中国科学院上海硅酸盐研究所 Electrolyte ceramic membrane for sodium battery and preparation method of electrolyte ceramic membrane
CN108666613A (en) * 2017-03-27 2018-10-16 华为技术有限公司 A kind of solid electrolyte structure, secondary cell and preparation method
CN110957477A (en) * 2019-10-30 2020-04-03 苏州大学 Porous ceramic composite lithium metal cathode and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104272518A (en) * 2012-04-27 2015-01-07 株式会社丰田自动织机 Solid electrolyte and secondary battery
CN104282867A (en) * 2013-07-12 2015-01-14 中国科学院上海硅酸盐研究所 Electrolyte ceramic membrane for sodium battery and preparation method of electrolyte ceramic membrane
CN108666613A (en) * 2017-03-27 2018-10-16 华为技术有限公司 A kind of solid electrolyte structure, secondary cell and preparation method
CN110957477A (en) * 2019-10-30 2020-04-03 苏州大学 Porous ceramic composite lithium metal cathode and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HAOWEI ZHAI等: ""A Flexible Solid Composite Electrolyte with Vertically Aligned and Connected Ion-Conducting Nanoparticles for Lithium Batteries"", 《NANO LETTERS》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN114267876A (en) * 2021-12-20 2022-04-01 上海科技大学 Integrated electrode-electrolyte structure, preparation method thereof and all-solid-state battery
CN114975860A (en) * 2022-06-28 2022-08-30 重庆冠宇电池有限公司 Negative plate and battery
CN114975860B (en) * 2022-06-28 2024-05-07 重庆冠宇电池有限公司 Negative plate and battery

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