CN115395092A - All-solid-state rechargeable battery and method for manufacturing electrolyte thereof - Google Patents

All-solid-state rechargeable battery and method for manufacturing electrolyte thereof Download PDF

Info

Publication number
CN115395092A
CN115395092A CN202110565215.8A CN202110565215A CN115395092A CN 115395092 A CN115395092 A CN 115395092A CN 202110565215 A CN202110565215 A CN 202110565215A CN 115395092 A CN115395092 A CN 115395092A
Authority
CN
China
Prior art keywords
sodium
modification layer
solid
rechargeable battery
electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110565215.8A
Other languages
Chinese (zh)
Inventor
吕力
王玉美
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chongqing New National University Research Institute
National University of Singapore
Original Assignee
Chongqing New National University Research Institute
National University of Singapore
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chongqing New National University Research Institute, National University of Singapore filed Critical Chongqing New National University Research Institute
Priority to CN202110565215.8A priority Critical patent/CN115395092A/en
Priority to PCT/CN2022/094582 priority patent/WO2022247809A1/en
Publication of CN115395092A publication Critical patent/CN115395092A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to an all-solid-state rechargeable battery and a method for manufacturing an electrolyte thereof. An all-solid-state rechargeable battery according to the present invention includes a high potential positive electrode material having the ability to store sodium ions, a metallic sodium negative electrode, and an all-solid-state electrolyte between the positive electrode and the negative electrode. The electrolyte comprises an inorganic porous framework, a ferroelectric material modification layer attached to the surface of the porous framework, and organic polymers filled in pores of the porous framework and pores of the modification layer. The all-solid-state rechargeable battery with the ferroelectric material modification layer has lower interface impedance and higher room temperature cycling stability.

Description

All-solid-state rechargeable battery and method for manufacturing electrolyte thereof
Technical Field
The present invention relates to electrochemical energy storage devices and methods for making electrolytes therefor, and more particularly to an all-solid-state rechargeable battery and methods for making electrolytes therefor.
Background
All-solid-state rechargeable batteries employ solid-state electrolytes to provide a safer rechargeable battery. Among many solid electrolyte systems, polymer composite electrolytes are of interest because of their ability to maintain intimate contact with the electrodes. However, the current solid-state rechargeable battery adopting the polymer composite electrolyte is difficult to recycle at room temperature, and particularly when metal sodium is used as a battery cathode, the capacity of the battery is seriously attenuated, so that the application of the current polymer all-solid-state rechargeable battery is greatly limited.
Disclosure of Invention
According to one aspect, the invention provides an all-solid-state rechargeable battery comprising a positive electrode, a negative electrode, and an electrolyte between the positive and negative electrodes. The positive electrode includes a high potential positive electrode material having the ability to store sodium ions. The cathode is metallic sodium. The electrolyte comprises a NASICON sodium ion material with a porous framework, a modification layer attached to the surface of the porous framework, and a polymer filled in pores of the porous framework and pores of the modification layer.
Preferably, the modification layer is a ferroelectric material with a perovskite structure. Further preferably, the perovskite structure ferroelectric material is one of the following materials: potassium sodium niobate, lead zirconate titanate, bismuth sodium titanate.
Preferably, the porous scaffold comprises Na3Zr2Si2PO12 of NASICON structure.
Preferably, the polymer comprises an organic polymer and a sodium salt, wherein the organic polymer is one or a combination of the following: polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile; the sodium salt is one of the following or a combination thereof: sodium bistrifluoromethylsulfonyl imide, sodium perchlorate, sodium bisfluorosulfonyl imide, sodium trifluoromethanesulfonate and sodium hexafluorophosphate.
Preferably, the mass ratio of the modifying layer to the porous framework is 2.4.
Preferably, the porous skeleton has a porosity of 18vol% or more and 56vol% or less.
According to another aspect, the present invention provides a method of making an all-solid-state rechargeable battery electrolyte, the method comprising:
a. coating a precursor solution of a modification layer material on the surface of the porous framework;
b. sintering the precursor solution and the porous framework to form a crystal modification layer containing pores on the surface of the porous framework;
c. filling molten polymer material into pores of the porous skeleton attached with the modification layer; and
d. and solidifying the molten polymer to form the composite electrolyte, wherein the composite electrolyte comprises a porous framework, a modification layer attached to the surface of the porous framework and a polymer filled in pores of the porous framework and pores of the modification layer.
Brief description of the drawings
Fig. 1 is a flowchart of a method of manufacturing an all-solid rechargeable battery according to an embodiment of the invention.
Fig. 2 shows an X-ray diffraction pattern of an electrolyte of an all-solid rechargeable battery according to an embodiment of the present invention.
Fig. 3 is a partially enlarged view of fig. 2.
Fig. 4 is FE-SEM images (a 1, a2, a 3) and TEM images (a 4) of the ferroelectric material modified inorganic porous framework and FE-SEM images (b 1, b2, and b 3) of the ferroelectric material modified polymer composite electrolyte according to an embodiment of the present invention.
Fig. 5 is a graph of electrochemical resistance of a polymer composite electrolyte with a ferroelectric material modification layer of an all-solid rechargeable battery according to an embodiment of the present invention at room temperature.
Fig. 6 is a graph of discharge capacity as a function of cycle number for an all-solid-state sodium metal battery having a ferroelectric material modification layer for an all-solid-state rechargeable battery according to an embodiment of the present invention.
Fig. 7 is a graph of discharge capacity as a function of cycle number for an all-solid-state sodium metal battery without a ferroelectric material modification layer.
Fig. 8 is a graph of electrochemical resistance test results after long cycling at room temperature showing the electrochemical resistance of an all-solid-state sodium metal battery with a ferroelectric material modification layer and an all-solid-state sodium metal battery without a ferroelectric material modification layer of an all-solid-state rechargeable battery according to an embodiment of the present invention.
Fig. 9 is a schematic diagram showing the results of the interface resistance test after long cycling at room temperature, and shows the interface resistance of each of the all-solid-state sodium metal battery with the ferroelectric material modification layer and the all-solid-state sodium metal battery without the ferroelectric material modification layer of the all-solid-state rechargeable battery according to the embodiment of the present invention.
Detailed Description
An all-solid-state rechargeable battery includes a positive electrode, a negative electrode, and an electrolyte between the positive and negative electrodes. The positive electrode is made of a high-potential positive electrode material with the capacity of storing sodium ions. The negative electrode is metallic sodium. The electrolyte comprises a NASICON sodium ion material with a porous framework, a modification layer attached to the surface of the porous framework, and a polymer filled in pores of the porous framework and pores of the modification layer.
According to one embodiment, the all-solid-state rechargeable battery of the invention is an all-solid-state sodium metal battery, and the modification layer of the all-solid-state sodium metal battery is a perovskite structure ferroelectric material with a relatively high curie temperature, for example, the modification layer can be a perovskite structure ferroelectric material with a curie temperature higher than 300 ℃. The perovskite structure ferroelectric material is a material comprising potassium sodium niobate, lead zirconate titanate or sodium bismuth titanate. The porous framework may be made of an inorganic electrolyte, which may be an oxide of, for example, sodium fast ion conductor (NASICON) structure.
The polymer includes organic polymers and sodium salts. The organic polymer may be, for example, one of polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, or a combination thereof; the sodium salt can be selected from one or a combination of sodium bistrifluoromethylsulfonyl imide, sodium perchlorate, sodium bisfluorosulfonyl imide, sodium triflate and sodium hexafluorophosphate.
In one embodiment, the inorganic electrolyte is Na3Zr2Si2PO12 of NASICON structure and its dopant; and the polymer is a mixture of polyethylene oxide and bis-trifluoromethylsulfonyl imide sodium salt. Preferably, the polymer electrolyte consists of polyethylene oxide and sodium bistrifluoromethylsulfonyl imide in an EO to Na molar ratio of 12.
The polymer composite all-solid-state electrolyte having a ferroelectric material modification layer as described above may be fabricated according to the method 100 shown in fig. 1. As shown in fig. 1, the method 100 applies a ferroelectric material precursor solution to the surface of an inorganic electrolyte framework of NASICON structure at step 110. The coating step may be performed by a drop coating method, a spin coating method, a spray coating method, or the like. In one embodiment, the k0.5na0.5nbo3 precursor solution can be uniformly coated on both side surfaces of the Na3Zr2Si2PO12 skeleton of NASICON structure in air.
In step 120, the method performs high temperature sintering on the porous skeleton coated with the ferroelectric material precursor solution, which is prepared in step 110, to form a ferroelectric material modification layer on the surface of the porous skeleton. The porous scaffold coated with the k0.5na0.5nbo3 precursor solution in step 110 may be dried at 100 ℃, pyrolyzed at 550 ℃, and sintered at 750 ℃ in air to form a firmly bonded porous crystal layer of k0.5na0.5nbo3 on the surface of the Na3Zr2Si2PO12 porous scaffold, thereby obtaining a Na3Zr2Si2PO12 porous scaffold of NASICON structure to which a k0.5na0.5nbo3 modification layer is attached. Preferably, in the porous skeleton after sintering, the mass ratio of k0.5na0.5nbo3 to Na3Zr2Si2PO12 is 2.4.
In step 130, the method fills the molten polymer in the pores of the porous skeleton with the modification layer on the surface, which is made in step 120. In step 140, the method solidifies the molten polymer after step 130 to obtain a porous skeleton with a ferroelectric modification layer attached and pores filled with the polymer, thereby obtaining the polymer composite all-solid-state electrolyte with the ferroelectric modification layer. For example, the polymer in a molten state may be filled in the pores of the porous skeleton having the ferroelectric material modification layer formed on the surface thereof by a vacuum infiltration method.
In one example, a polymer in a molten state is filled and solidified in a Na3Zr2Si2PO12 skeleton of a porous NASICON structure of a k0.5na0.5nbo3 modification layer in a vacuum oven at 80 to 130 ℃, for example, in a vacuum oven at 110 ℃ by a vacuum infiltration method to prepare a k0.5na0.5nbo3-modified polymer composite electrolyte. Preferably, the polymer electrolyte may be filled from one side of the Na3Zr2Si2PO12 porous skeleton of NASICON structure, and the filling may be repeated several times until both side surfaces of the porous skeleton are wet-filled with the molten polymer electrolyte. And then, wetting the filled porous skeleton with the modification layer on the surface by using the molten polymer electrolyte, and curing to obtain the K0.5Na0.5NbO3 modified layer polymer composite electrolyte fully filled by the polymer electrolyte.
The polymer composite all-solid-state electrolyte with the ferroelectric material modification layer obtained after the step 140 is pressed into a thin film, and the thin film can be used as the electrolyte of the all-solid-state sodium metal battery according to the embodiment of the invention. For example, the all-solid-state rechargeable battery according to the present invention can be manufactured by pressing the polymer composite electrolyte of the k0.5na0.5nbo3 modification layer into a dense film having a thickness of 300 to 600 μm and pressing the positive and negative electrode sheets against the dense film electrolyte, respectively.
The inorganic electrolyte backbone of the NASICON structure used in step 110 may be prepared by, for example, a sol-gel method. In one example, the Na3Zr2Si2PO12 skeleton of NASICON structure can be prepared by a sol-gel method in an air atmosphere.
Specifically, zirconium butoxide solution, tetraethyl silicate, nitrilotris (methylene) triphosphonic acid solution and sodium acetate can be dissolved in an ethanol solvent according to the stoichiometric ratio and uniformly mixed to prepare a clear sol solution. Wherein, sodium acetate with 10 percent excess can be added into the sol solution to compensate the loss of sodium ions in the subsequent heat treatment process. Then, two chemical stabilizers, polyvinylpyrrolidone and ethanolamine, were mixed at a molar ratio of 1. The sol solution was heated at 50 ℃ for 4 hours to convert it to a wet gel. Then, the above wet gel was heated at 200 ℃ for 24 hours to completely convert it into a dry gel powder, and then the above dry gel powder was pressed into a dense dry gel sheet. The above-mentioned dried gel sheet can be sintered at a high temperature ranging from 1025 ℃ to 1050 ℃ (preferably 1025 ℃) for 8 hours while controlling the temperature rise rate of 5 ℃/minute, to be completely crystallized to form an inorganic electrolyte skeleton of porous NASICON structure. Wherein the porosity of the finally produced porous skeleton can be controlled by controlling the molar ratio of the mixed chemical stabilizer to Na3Zr2Si2PO12. For example, when the ratio of the stabilizer to Na3Zr2Si2PO12 is 1, the porosity of the porous skeleton is 18vol% (volume percent). When the ratio of the stabilizer to Na3Zr2Si2PO12 is 2. According to a preferred embodiment, the NASICON-structured inorganic electrolyte porous skeleton of the present invention has a porosity of 18vol% or more and 56vol% or less.
The ferroelectric material precursor solution used in step 110 may also be prepared by a sol-gel method. In one embodiment, the ferroelectric material precursor solution of k0.5na0.5nbo3 can be prepared by a sol-gel method under dry nitrogen at room temperature.
Specifically, potassium acetate, sodium acetate, and niobium ethoxide may be uniformly mixed and dissolved in a 2-methoxyethanol solvent in a K: na: nb molar ratio of 0.6. Subsequently, a mixed chemical stabilizer of monoethanolamine, ethanolamine and ethylenediaminetetraacetic acid was added to the above solution in a molar ratio to k0.5na0.5nbo3 of 0.84. Wherein, the loss of the two elements in the subsequent heat treatment process can be supplemented by adding a small amount of potassium and sodium raw materials. And the addition of chemical stabilizers such as monoethanolamine, ethanolamine and ethylenediamine tetraacetic acid can effectively reduce further loss of potassium and sodium in the subsequent heat treatment process.
The polymer electrolyte used in step 130 may be prepared in air. In one example, polyethylene oxide (Mv 600,000) was uniformly dissolved in an ethanol solvent with heating at 45 ℃ in a molar ratio of EO to Na of 12. Subsequently, the above solution was coated on a glass substrate and heated at 60 ℃ for 24 hours to be completely dried, and a polymer electrolyte, such as the polymer electrolyte of polyethylene oxide and sodium bistrifluoromethylsulfonyl imide obtained in this exemplary embodiment, was obtained.
As described above, the polymer composite all-solid-state electrolyte with ferroelectric material modification layer obtained after completion of step 140 may be pressed into a thin film as an electrolyte of an all-solid rechargeable battery according to the present invention. The all-solid-state sodium metal battery can be manufactured by cold pressing and packaging the anode, the polymer composite electrolyte film with the ferroelectric material modification layer and the metal sodium cathode at room temperature.
In one embodiment, the positive electrode tab, the ferroelectric-modified polymer composite electrolyte film, and the sodium metal negative electrode tab may be cold-pressed and packaged in a battery case, such as a button cell, at room temperature in a glove box filled with argon gas, thereby obtaining an all-solid-state rechargeable battery having a positive | ferroelectric modification layer-polymer composite electrolyte-ferroelectric modification layer | sodium metal negative electrode structure.
In one embodiment, the positive electrode comprises a mixture of a positive electrode active material, a conductive carbon material, and a polymer binder. The positive electrode active material may be polyanion, prussian blue, or layered oxide. Preferably, the positive electrode active material is polyanionic Na3V2 (PO 4) 3 and a dopant thereof. For example, the positive active material may be na3v1.85fe0.15 (PO 4) 3.
In one embodiment, the positive electrode may be manufactured by:
first, a positive electrode active material powder, conductive carbon black super-P, and a binder polyvinylidene fluoride were mixed and dissolved in a 1-methyl-2-pyrrolidone solvent in a mass ratio of 7. Wherein, the positive active material is Na3V1.85Fe0.15 (PO 4) 3.
Then, the above-mentioned positive electrode material slurry was uniformly coated on an aluminum foil current collector, and dried for 8 hours by heating to 120 ℃ in a vacuum oven to prepare a positive electrode of an all-solid rechargeable battery according to the present invention.
In one embodiment, an all-solid-state rechargeable battery (positive electrode/ferroelectric-modified polymer composite electrolyte/negative electrode) according to the present invention has a na3v1.85fe0.15 (PO 4) 3 rd charge k0.5na0.5nbo3-Na3Zr2Si2PO12-k0.5na0.5nbo3| Na structure. Wherein the electrolyte with the ferroelectric modification layer is bonded into a whole by the polymer electrolyte.
The all-solid-state rechargeable battery according to the invention has effectively reduced interfacial resistance of the battery, and higher room temperature cycle stability. The above advantageous effects are presented in detail in the following examples.
Example 1
Example 1 is intended to test and present the crystal structure, micro-topography and electrochemical impedance spectra of the electrolyte of an all-solid rechargeable battery according to the present invention. In example 1, the experimental method may include testing the porous framework of the ferroelectric-modified inorganic electrolyte and the crystal structure of the ferroelectric-modified polymer composite electrolyte using an X-ray diffractometer (XRD). The X-ray diffractometer may be, for example, an XRD-6000 type X-ray diffractometer by Shimadzu corporation (Shimadzu).
The experimental method may further include a test analysis of the micro-morphology and elemental distribution of the electrolyte of the all-solid rechargeable battery according to the present invention using a field emission scanning electron microscope (FE-SEM) and a Transmission Electron Microscope (TEM). The field emission scanning electron microscope may be, for example, a model S-4300 field emission scanning electron microscope of Hitachi (HITACHI). The transmission electron microscope may be, for example, tecnai of FEI corporation TM G2 Transmission electron microscope model F30.
The experimental method may further comprise testing the electrochemical resistance spectrum of the electrolyte of an all-solid-state rechargeable battery according to the present invention using an impedance analyzer. The resistance analyzer may be, for example, an enhanced input (Solartron) model 1260-1287 resistance analyzer.
The prepared electrolyte has higher flexibility, and aluminum foils can be directly attached to the two surfaces of the electrolyte to be used as electrodes during testing. In one example, the test voltage is 10mV and the frequency is 1MHz to 1Hz.
The ionic conductivity σ of the electrolyte can be calculated by the following formula (1).
σ＝t/(RA) (1)
Wherein t is the thickness of the sample to be tested, A is the test area, and R is the total resistance measured from electrochemical resistance spectroscopy.
Fig. 2 shows an experimentally measured X-ray diffraction pattern. As shown in fig. 2, the inorganic electrolyte framework with the ferroelectric material modification layer only contains sodium fast ion conductor (NASICON) and perovskite (perovskite) structures, which indicates that the ferroelectric material in the surface modification layer of the inorganic electrolyte framework does not affect the crystal structure of the inorganic electrolyte framework. In addition, the XRD result of the polymer composite electrolyte modified by the ferroelectric material has main peaks consistent with the structures of polyethylene oxide crystals (PDF 00-067-1538), perovskites (PDF 04-007-9793) and sodium fast ion conductors (PDF 01-076-1449), and no obvious impurity phase is observed. This is more clearly seen in fig. 3, which is a partial enlargement of the part of the frame a in fig. 2.
Fig. 4 shows experimentally measured FE-SEM and TEM images (a 1, a2, a3, and a 4) of the inorganic porous skeleton having the ferroelectric material modification layer and FE-SEM images (b 1, b2, and b 3) of the ferroelectric material modified polymer composite electrolyte. Wherein a1 is the surface topography of the inorganic material porous framework with the ferroelectric material modification layer under low magnification, wherein the ferroelectric material modification layer presents a porous island-shaped region 410; a2 is a distribution diagram of the Nb element 420 on the surface of the inorganic material porous framework with the ferroelectric material modification layer; a3 is a distribution diagram of Si element 430 on the surface of the inorganic porous skeleton with the ferroelectric material modification layer; a4 is the micro-morphology of the inorganic porous framework with the ferroelectric material modification layer under high magnification; b1 is the cross-sectional shape of the polymer composite electrolyte with the ferroelectric material modification layer with low magnification; b2 is the surface appearance of the polymer composite electrolyte with the ferroelectric material modification layer with high magnification; b3 is the high magnification cross section shape of the polymer composite electrolyte with the ferroelectric material modification layer.
In fig. 4, as shown in a1-a3, the ferroelectric material modification layer is in a porous island region 410 on the surface of the porous skeleton of Na3Zr2Si2PO12, and the pores of the inorganic porous skeleton having the ferroelectric material modification layer are in the nanometer scale (see a 4); and as shown in b1-b3, in the finally prepared polymer composite electrolyte with the ferroelectric material modification layer with higher flexibility, the polymer is fully filled in the pores of the porous framework, and the coating layer is formed on the outer surface of the inorganic ceramic particles.
Fig. 5 is a graph of the electrochemical resistance value of the polymer composite electrolyte having a ferroelectric material modification layer at room temperature, which is experimentally measured. As shown in fig. 5, the room temperature electrochemical resistance spectrum of the polymer composite electrolyte with the ferroelectric material modification layer exhibits a typical Nyquist curve. The intercept of the slope in the resistance spectrum on the solid axis is the total resistance of the electrolyte. From the intercept of fig. 5, it can be calculated by using equation (1) that the total ionic conductivity of the ferroelectric-modified polymer composite electrolyte at room temperature is high, about 7.0 x 10-5 siemens/cm (S/cm).
Example 2
Example 2 is intended to test and present the galvanostatic long-cycle charge-discharge performance of all-solid-state sodium metal battery electrolytes with ferroelectric material modification layers fabricated according to the methods of the present invention.
In example 2, the experimental method included a constant current long cycle charge-discharge comparative test at room temperature using a bond cell test system on all-solid sodium metal cells with interfacial ferroelectric modification layers and all-solid sodium metal cells without ferroelectric modification, where the test voltage was 2.5 to 4.0 volts (V) and the test current was 11.8 milliamps/gram (mA/g).
Fig. 6 is a graph showing the discharge capacity of the all-solid-state sodium metal battery with the ferroelectric material modification layer according to the cycle number. Fig. 7 is a graph showing the discharge capacity of the all-solid-state sodium metal battery without the modification layer of the ferroelectric material, which is measured by the experiment, as a function of the cycle number. As shown in fig. 6, the first cycle discharge capacity of the all-solid-state sodium metal battery with the ferroelectric material modification layer was 79.9 milliampere-hour/gram (mAh/g) at room temperature. After 170 cycles of charge and discharge, the battery exhibited a capacity retention rate as high as 71.7%. In contrast, the all-solid-state sodium metal battery without the ferroelectric material modification layer shown in fig. 7 has a low discharge capacity of only 57 ma-hr/g at room temperature in the first cycle. Moreover, the capacity of the battery is quickly attenuated in the circulating process. After 170 cycles of charge and discharge, the capacity retention rate is only 13.0%.
Example 3
Example 3 is intended to test the electrochemical impedance spectrum and the interfacial resistance of an all-solid-state sodium metal battery with a ferroelectric material modification layer fabricated according to the method of the present invention after completion of long-cycle charge and discharge. In example 3, the experimental method includes testing electrochemical resistance spectra of all-solid-state sodium metal batteries with and without ferroelectric material modification layers using a resistance analyzer at room temperature after completing long-cycle charge and discharge. The impedance analyzer is, for example, a 1260-1287 type impedance analyzer available from Solartron. The test voltage may be set at 10 millivolts (mV) with a frequency of 1MHz to 1Hz.
Fig. 8 is a graph of electrochemical resistance values after long cycles at room temperature, which shows electrochemical resistance values of the all-solid-state sodium metal battery having the ferroelectric material modification layer and the all-solid-state sodium metal battery having no ferroelectric material modification layer at the interface. As shown in fig. 8, the resistance spectrum X of the all-solid-state sodium metal battery without the ferroelectric material modification layer at the interface and the resistance spectrum Y of the all-solid-state sodium metal battery with the ferroelectric material modification at the interface both include two semicircles (a high-frequency semicircle and a medium-frequency semicircle) and a low-frequency straight line. Wherein, the high frequency semicircle represents the interface resistance of the anode-electrolyte, and the medium frequency semicircle is provided with the cathode-electrolyte. As can be seen from fig. 8, the interface resistance of the all-solid-state sodium metal battery with the ferroelectric material modification layer at the interface is significantly lower than that of the all-solid-state sodium metal battery without the ferroelectric material modification layer. Experiments show that the electrolyte with the ferroelectric modification layer can effectively improve the conduction of ions of the all-solid-state sodium metal battery on an electrode-electrolyte interface, thereby improving the cycling stability of the battery.
Fig. 9 is a schematic view of the experimentally measured interface resistance values after long cycles at room temperature, showing the interface resistance values of the all-solid-state sodium metal battery with ferroelectric material modification and the all-solid-state sodium metal battery without ferroelectric material modification layers, respectively. As shown in fig. 9, at room temperature, the positive electrode-electrolyte interface resistance (e.g., about 2 kohms as shown by 820) and the negative electrode-electrolyte interface resistance (e.g., about 33.8 kohms as shown by 840) of the all-solid-state sodium metal battery with the ferroelectric material modification layer are much lower than the positive electrode-electrolyte interface resistance (e.g., about 9.3 kohms as shown by 810) and the negative electrode-electrolyte interface resistance (e.g., about 205 kohms as shown by 830), respectively, of the all-solid-state sodium metal battery without the ferroelectric material modification layer. Experiments show that the ferroelectric material modification layer can effectively improve the conduction of ions at an electrode-electrolyte interface and improve the cycling stability of the battery.
As can be understood from the above experimental examples, the polymer composite electrolyte having a ferroelectric material modification layer according to the present invention has a high room temperature ionic conductivity (e.g., about 7.0 x 10 "5 siemens/cm); the ferroelectric material modification can effectively reduce the interface resistance of the anode-electrolyte and the interface resistance of the cathode-electrolyte in the all-solid-state battery. The all-solid-state sodium metal battery with the ferroelectric material modification layer can run stably at room temperature. For example, the first-cycle discharge capacity of constant-current charge and discharge (current of about 11.8 milliampere/g) at room temperature is about 79.9 milliampere hour/g, and the capacity retention rate is as high as about 71.7% after 170 cycles.
The foregoing description of embodiments, specific examples and application scenarios of the present invention have been presented for purposes of illustration and description, but are not intended to be exhaustive or limiting. Many modifications and variations will be apparent to practitioners skilled in this art. The examples and embodiments were chosen and described in order to explain the principles of the invention and its practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
Thus, although the illustrative example embodiments have been described herein with reference to the accompanying drawings, it is to be understood that the description is not limiting, and that various other changes and modifications may be affected therein by one skilled in the art without departing from the scope or spirit of the disclosure and the embodiments.

Claims (10)

1. An all-solid rechargeable battery, comprising:
a positive electrode comprising a high potential positive electrode material having the ability to store sodium ions;
a negative electrode, the negative electrode being metallic sodium; and
the electrolyte is arranged between the positive electrode and the negative electrode and comprises an NASICON sodium ion material with a porous framework, a modification layer attached to the surface of the porous framework and a polymer filled in pores of the porous framework and pores of the modification layer.
2. The all-solid rechargeable battery of claim 1 wherein the modification layer is a ferroelectric material of perovskite structure.
3. The all-solid rechargeable battery according to claim 2, wherein the perovskite structure ferroelectric material is one of: potassium sodium niobate, lead zirconate titanate and bismuth sodium titanate.
4. The all-solid rechargeable battery according to claim 1, wherein the porous scaffold comprises Na3Zr2Si2PO12 of NASICON structure.
5. The all-solid rechargeable battery according to claim 1, wherein the polymer comprises an organic polymer and a sodium salt, wherein the organic polymer is one or a combination of: polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile; the sodium salt is one of the following or a combination thereof: sodium bistrifluoromethylsulfonyl imide, sodium perchlorate, sodium bistrifluorosulfonimide, sodium trifluoromethanesulfonate and sodium hexafluorophosphate.
6. The all-solid rechargeable battery of claim 1, wherein the mass ratio of the modification layer to the porous scaffold is 2.4.
7. The all-solid rechargeable battery according to claim 1, wherein the porous skeleton has a porosity of 18vol% or more and 56vol% or less.
8. A method of making an all-solid rechargeable battery electrolyte, the method comprising the steps of:
a. coating a precursor solution of a modification layer material on the surface of the porous framework;
b. sintering the precursor solution and the porous framework to form a crystal modification layer containing pores on the surface of the porous framework;
c. filling molten polymer material in the pores of the porous framework attached with the modification layer; and
d. and solidifying the molten polymer to form the composite electrolyte, wherein the composite electrolyte comprises a porous framework, a modification layer attached to the surface of the porous framework and a polymer filled in pores of the porous framework and pores of the modification layer.
9. The method of claim 8, wherein the modifying layer is a perovskite-structured ferroelectric material.
10. The method according to claim 8, wherein the perovskite structure ferroelectric material is one of: potassium sodium niobate, lead zirconate titanate and bismuth sodium titanate.
CN202110565215.8A 2021-05-24 2021-05-24 All-solid-state rechargeable battery and method for manufacturing electrolyte thereof Pending CN115395092A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202110565215.8A CN115395092A (en) 2021-05-24 2021-05-24 All-solid-state rechargeable battery and method for manufacturing electrolyte thereof
PCT/CN2022/094582 WO2022247809A1 (en) 2021-05-24 2022-05-24 All-solid-state rechargeable battery and method for preparing electrolyte thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110565215.8A CN115395092A (en) 2021-05-24 2021-05-24 All-solid-state rechargeable battery and method for manufacturing electrolyte thereof

Publications (1)

Publication Number Publication Date
CN115395092A true CN115395092A (en) 2022-11-25

Family

ID=84114700

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110565215.8A Pending CN115395092A (en) 2021-05-24 2021-05-24 All-solid-state rechargeable battery and method for manufacturing electrolyte thereof

Country Status (2)

Country Link
CN (1) CN115395092A (en)
WO (1) WO2022247809A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117423829B (en) * 2023-12-19 2024-04-23 湖南长远锂科新能源有限公司 Lithium ion battery anode material and preparation method and application thereof
CN117727938B (en) * 2024-02-07 2024-04-19 湖南先钠科技有限公司 Sodium ion battery positive electrode material capable of being used for quick charge and preparation method thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5556797B2 (en) * 2010-12-17 2014-07-23 トヨタ自動車株式会社 Secondary battery
EP3772125A1 (en) * 2019-07-29 2021-02-03 Fundación Centro De Investigación Cooperativa De Energías Alternativas Cic Energigune Fundazioa Solid-state sodium battery
CN111584940A (en) * 2020-05-25 2020-08-25 山东大学 Method for improving interface stability of solid electrolyte and metal cathode
CN111799504B (en) * 2020-08-06 2021-07-02 南方科技大学 Solid electrolyte, preparation method thereof and all-solid-state battery
CN112531206B (en) * 2020-12-03 2021-11-23 北京大学 Solid electrolyte material, preparation method thereof, solid electrolyte sheet and all-solid-state battery

Also Published As

Publication number Publication date
WO2022247809A1 (en) 2022-12-01

Similar Documents

Publication Publication Date Title
US20200365862A1 (en) Membranes for electrochemical cells
JP7273513B2 (en) Solid state Li-S battery and method of making same
KR102699849B1 (en) Solid-state hybrid electrolyte, method for preparing the same and uses thereof
US11043696B2 (en) Metal alloy layers on substrates, methods of making same, and uses thereof
JP4465492B2 (en) Rechargeable hybrid battery / supercapacitor system
TWI418077B (en) Lithium secondary battery
EP2903060B1 (en) Manufacturing method of electrode assembly, electrode assembly, and battery
US20210257658A1 (en) Solid-state li-s batteries and methods of making same
KR101876861B1 (en) Hybrid solid electrolyte for all solid lithium secondary battery and method for preparing the same
US11276880B2 (en) Solid-state electrolytes based on lithium halides for all-solid-state lithium-ion battery operating at elevated temperatures
KR20200084008A (en) Solid-state battery electrolyte with increased stability to cathode materials
US20190027724A1 (en) Electrochemical Energy Storage Devices and Methods of Making and Using the Same
WO2022247809A1 (en) All-solid-state rechargeable battery and method for preparing electrolyte thereof
JP5487719B2 (en) Manufacturing method of all-solid lithium secondary battery, and all-solid lithium secondary battery obtained by the manufacturing method
US20170263980A1 (en) Method for producing electrochemical cells of a solid-state battery
WO2015157339A1 (en) Membranes for electrochemical cells
JP2020514948A (en) ALL-SOLID LITHIUM-ION BATTERY AND MANUFACTURING METHOD THEREOF
JP2015088437A (en) Pre-doping method of nonaqueous secondary battery and battery obtained by pre-doping method
JP5849543B2 (en) Electrode body for lithium ion secondary battery, method for producing electrode body for lithium ion secondary battery, and lithium ion secondary battery
He et al. Synthesis and interface modification of oxide solid-state electrolyte-based all-solid-state lithium-ion batteries: Advances and perspectives
US20200153038A1 (en) Rechargeable lithium-ion battery
JP6102615B2 (en) Negative electrode active material and secondary battery using the same
KR101417282B1 (en) sulfur electrode of lithium sulfur battery and manufacturing method for the same, and lithium sulfur battery appling the same
JP2019091525A (en) Method for manufacturing lithium ion secondary battery
US20220131181A1 (en) Method for manufacturing solid secondary battery including composite electrolyte film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination