CN108695553B - All-solid-state sodium secondary battery electrolyte, preparation method and application thereof - Google Patents

All-solid-state sodium secondary battery electrolyte, preparation method and application thereof Download PDF

Info

Publication number
CN108695553B
CN108695553B CN201810757815.2A CN201810757815A CN108695553B CN 108695553 B CN108695553 B CN 108695553B CN 201810757815 A CN201810757815 A CN 201810757815A CN 108695553 B CN108695553 B CN 108695553B
Authority
CN
China
Prior art keywords
component
solid
secondary battery
sodium secondary
state sodium
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.)
Active
Application number
CN201810757815.2A
Other languages
Chinese (zh)
Other versions
CN108695553A (en
Inventor
姚霞银
万红利
刘高瞻
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.)
Ningbo Institute of Material Technology and Engineering of CAS
Original Assignee
Ningbo Institute of Material Technology and Engineering of CAS
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 Ningbo Institute of Material Technology and Engineering of CAS filed Critical Ningbo Institute of Material Technology and Engineering of CAS
Priority to CN201810757815.2A priority Critical patent/CN108695553B/en
Publication of CN108695553A publication Critical patent/CN108695553A/en
Application granted granted Critical
Publication of CN108695553B publication Critical patent/CN108695553B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • 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)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The invention provides an all-solid-state sodium secondary battery electrolyte, a method and application thereof, wherein the electrolyte is prepared from the following raw materials, wherein the raw materials comprise a first component and a second component; the first component is selected from Na2S and/or Na2Se; the second component is selected from Sb2S3、Sb2Se3、Sb2S5、Sb2Se5、P2S5、P2S3、As2S3、As2S5、S、Se、SnS2、SiS2、SnS、GeS2And GeS; the granularity of the electrolyte of the all-solid-state sodium secondary battery is 10 nm-10 mu m. The raw materials also comprise a dopant, and the dopant is selected from one or more of a third component, an oxide and a halide; the third component and the second component are not the same in composition. The electrolyte has higher sodium ion conductivity in the all-solid-state sodium secondary battery; but also has a wider electrochemical window. The all-solid-state sodium secondary battery prepared based on the electrolyte has good multiplying power and cycle performance.

Description

All-solid-state sodium secondary battery electrolyte, preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrolytes, and particularly relates to an all-solid-state sodium secondary battery electrolyte, and a preparation method and application thereof.
Background
The lithium secondary battery has the advantages of high energy density, high working voltage, long cycle life and the like, and is widely applied to large-scale energy storage. However, as the dependence of the development of large-scale consumer electronics and electric automobile industries on lithium secondary batteries is increased, the shortage of lithium resources becomes an obstacle to the development of large-scale application of lithium secondary batteries. The sodium secondary battery adopts metal sodium with low cost and abundant reserves as a negative electrode, the electrochemical working mechanism of the sodium secondary battery is similar to that of the lithium secondary battery, and the potential of the sodium secondary battery is only 0.3V higher than that of the lithium secondary battery, so that the sodium secondary battery is expected to replace the lithium secondary battery to become a next-generation low-cost and high-safety battery energy storage technology.
The traditional high-temperature sodium battery adopts molten elemental sulfur as a positive electrode and metal sodium as a negative electrode material, so that the high-temperature sodium-sulfur battery has great potential safety hazard. The room temperature sodium ion battery adopts the organic liquid electrolyte, and the battery system is inevitably introduced with volatile, inflammable and explosive organic liquid, which also brings safety problem to the battery system. The room-temperature all-solid-state sodium battery adopts the non-combustible solid electrolyte to replace the traditional electrolyte based on an organic solvent, is expected to fundamentally solve the safety of the battery, can further improve the energy density and the cycle life of the battery, and accords with the development direction of the high-safety energy density battery in the future.
At present, solid electrolytes used in all-solid-state sodium batteries are classified into oxide electrolytes, polymer electrolytes, and sulfide electrolytes. The oxide electrolyte has high ion conductivity, but has high interface resistance between the electrolyte and the electrode. Therefore, a polymer electrolyte is added to the oxide electrolyte layer to form a composite electrolyte to improve the interface between the electrode and the electrolyte. However, the polymer electrolyte has the disadvantages of low ionic conductivity and narrow electrochemical window, and the working temperature range of the battery and the use voltage range of the electrode material are limited. Sulfide electrolytes are of interest because of their high ionic conductivity, wide electrochemical window, and stable electrochemical performance. And the Young modulus of the sulfide electrolyte is low, so that the interface impedance can be reduced by a cold pressing mode to form a compact electrolyte sheet, and the assembly molding of the battery is facilitated. The reported performance of room temperature all-solid-state sodium batteries based on sulfide electrolytes is still poor.
Disclosure of Invention
In view of the above, the present invention is directed to an all-solid-state sodium secondary battery electrolyte, which has high ionic conductivity, a preparation method thereof, and applications thereof.
The invention provides an all-solid-state sodium secondary battery electrolyte, which is prepared from the following raw materials, wherein the raw materials comprise a first component and a second component;
the first component is selected from Na2S and/or Na2Se；
The second component is selected from Sb2S3、Sb2Se3、Sb2S5、Sb2Se5、P2S5、P2S3、As2S3、As2S5、S、Se、SnS2、SiS2、SnS、GeS2And GeSOr a plurality thereof;
the granularity of the electrolyte of the all-solid-state sodium secondary battery is 10 nm-10 mu m.
Preferably, the raw material further comprises a dopant;
the dopant is selected from one or more of a third component, an oxide and a halide;
the third component is selected from SiS2、GeS2、SnS2、SiS、GeS、SnS、TiS2、FeS、Sb2S3、Sb2Se3、Sb2S5、Sb2Se5、P2S5、P2S3、As2S3、As2S5、S、Se、FeS2、MoS2、B2S3、Al2S3、MnS、ZnS、NiS、Ni2S3、NiS2And MnS2One or more of; the third component and the second component are different in composition.
Preferably, the oxide is selected from P2O5、B2O3、SiO2、TiO2、ZnO、Al2O3、MnO、MnO2、GeO2、Sb2O3、Sb2O5、As2O3And As2O5One or more of;
the halide is selected from sodium halides.
Preferably, the all-solid-state sodium secondary battery electrolyte has the following composition: (100-m) C: mD;
0≤m≤50；
c is selected from electrolytes shown in formula I, formula II or formula III:
x1A1·y1B1formula I; said x1:y1＝2～3:1；
x2A2·y2B2·y3B3Formula II; said x2:y2:y3＝3～11:1～4:1～2；
x3A3·y4B4·y5B5·y6B6Formula III; said x3:y4:y5:y6＝5～11:1～4:1:2；
A is described1、A2And A3Independently selected from the first component;
b is1、B2、B3、B4、B5And B6Independently selected from the second component;
the D is selected from dopants.
Preferably, said C is selected from 3Na2S·Sb2S3·2S、11Na2S·4SnS2·P2S5、3Na2S·P2S5Or 3Na2S·Sb2S3·2Se。
The invention provides a preparation method of the electrolyte of the all-solid-state sodium secondary battery, which comprises the following steps:
mixing the first component, the second component and a solvent, and reacting to obtain a precursor solution; the first component is selected from Na2S and/or Na2Se; the second component is selected from Sb2S3、Sb2Se3、Sb2S5、Sb2Se5、P2S5、P2S3、As2S3、As2S5、S、Se、SnS2、SiS2、SnS、GeS2And GeS;
and drying and grinding the precursor solution, and carrying out heat treatment under a protective atmosphere to obtain the all-solid-state sodium secondary battery electrolyte, wherein the granularity of the all-solid-state sodium secondary battery electrolyte is 10 nm-10 mu m.
Preferably, the first component, the second component, the solvent are also mixed with the dopant;
the dopant is selected from one or more of a third component, an oxide and a halide;
the third component is selected from SiS2、GeS2、SnS2、SiS、GeS、SnS、TiS2、FeS、Sb2S3、Sb2Se3、Sb2S5、Sb2Se5、P2S5、P2S3、As2S3、As2S5、S、Se、FeS2、MoS2、B2S3、Al2S3、MnS、ZnS、NiS、Ni2S3、NiS2And MnS2One or more of; the third component and the second component are different in composition.
Preferably, the solvent is selected from one or more of water, acetonitrile, tetrahydrofuran, N-methylformamide, ethylene glycol dimethyl ether, dimethyl carbonate, ethyl acetate, chlorobenzene, N-hexane, ethanol, methanol and dimethylformamide.
Preferably, the temperature of the heat treatment is 150-1000 ℃, and the heat treatment time is 0.5-36 h.
The invention provides an all-solid-state sodium secondary battery, which comprises a positive electrode, a negative electrode and an all-solid-state sodium secondary battery electrolyte arranged between the positive electrode and the negative electrode;
the all-solid-state sodium secondary battery electrolyte is the all-solid-state sodium secondary battery electrolyte prepared by the preparation method in the technical scheme or the all-solid-state sodium secondary battery electrolyte prepared by the preparation method in the technical scheme.
The invention provides an all-solid-state sodium secondary battery electrolyte and a method thereof, wherein the electrolyte is prepared from the following raw materials, wherein the raw materials comprise a first component and a second component; the first component is selected from Na2S and/or Na2Se; the second component is selected from Sb2S3、Sb2Se3、Sb2S5、Sb2Se5、P2S5、P2S3、As2S3、As2S5、S、Se、SnS2、SiS2、SnS、GeS2And GeS; the granularity of the electrolyte of the all-solid-state sodium secondary battery is 10 nm-10 mu m.The preparation method comprises the steps of mixing a first component, a second component and a solvent, drying and grinding an obtained reaction product, and carrying out heat treatment to obtain the electrolyte, wherein the method can effectively regulate and control the particle size and the morphology of the electrolyte by a solvent liquid phase method to ensure that the electrolyte has higher sodium ion conductivity, and the electrolyte also has a wider electrochemical window-4～5.0×10-3S cm-1The particle size is 10 nm-10 mu m, and the electrochemical window is up to 5V.
Detailed Description
The invention provides an all-solid-state sodium secondary battery electrolyte, which is prepared from the following raw materials, wherein the raw materials comprise a first component and a second component;
the first component is selected from Na2S and/or Na2Se；
The second component is selected from Sb2S3、Sb2Se3、Sb2S5、Sb2Se5、P2S5、P2S3、As2S3、As2S5、S、Se、SnS2、SiS2、SnS、GeS2And GeS;
the granularity of the electrolyte of the all-solid-state sodium secondary battery is 10 nm-10 mu m.
The electrolyte provided by the invention has the particle size of 10 nm-10 mu m, so that the electrolyte has higher sodium ion conductivity.
The electrolyte of the all-solid-state sodium secondary battery is prepared from the following raw materials, wherein the raw materials comprise a first component; the first component is selected from Na2S and/or Na2Se; preferably selected from Na2S。
The raw material comprises a second component selected from Sb2S3、Sb2Se3、Sb2S5、Sb2Se5、P2S5、P2S3、As2S3、As2S5、S、Se、SnS2、SiS2、SnS、GeS2And GeS, preferably selected from Sb2S3、S、P2S5、SnS2And Se.
In the present invention, the raw materials preferably further include a dopant; the dopant is selected from one or more of a third component, an oxide, and a halide. In the invention, vacancy or interstitial sodium ions are introduced into the electrolyte system by adding the dopant, so that a sodium ion transmission channel is widened, the acting force between the framework and the sodium ions is weakened, and the purposes of improving the conductivity of the sodium ions of the system and improving the electrochemical stability of the electrolyte are achieved.
The third component is preferably selected from SiS2、GeS2、SnS2、SiS、GeS、SnS、TiS2、FeS、Sb2S3、Sb2Se3、Sb2S5、Sb2Se5、P2S5、P2S3、As2S3、As2S5、S、Se、FeS2、MoS2、B2S3、Al2S3、MnS、ZnS、NiS、Ni2S3、NiS2And MnS2One or more of; the third component and the second component are different in composition.
The oxide is preferably selected from P2O5、B2O3、SiO2、TiO2、ZnO、Al2O3、MnO、MnO2、GeO2、Sb2O3、Sb2O5、As2O3And As2O5One or more of; more preferably from P2O5、Sb2O5And As2O5Most preferably selected from Sb2O5。
The halide is preferably selected from sodium halides; more preferably one or more selected from NaCl, NaF, NaBr and NaI, most preferably NaCl.
In the present invention, the all-solid-state sodium secondary battery electrolyte preferably has the following composition: (100-m) C: mD;
0≤m≤50；
c is selected from electrolytes shown in formula I, formula II or formula III:
x1A1·y1B1formula I; said x1:y1＝2～3:1；
x2A2·y2B2·y3B3Formula II; said x2:y2:y3＝3～11:1～4:1～2；
x3A3·y4B4·y5B5·y6B6Formula III; said x3:y4:y5:y6＝5～11:1～4:1:2；
A is described1、A2And A3Independently selected from the first component;
b is1、B2、B3、B4、B5And B6Independently selected from the second component;
the D is selected from dopants.
In the present invention, the first component and the second component can form a bulk C of the multi-element all-solid secondary electrolyte. C is preferably selected from the group consisting of electrolytes of formula I, formula II or formula III:
x1A1·y1B1formula I; said x1:y1＝2～3:1；
x2A2·y2B2·y3B3Formula II; said x2:y2:y3＝3～11:1～4:1～2；
x3A3·y4B4·y5B5·y6B6Formula III; said x3:y4:y5:y6＝5～11:1～4:1:2。
In the formula I, A1Selected from the first component; in a molar ratio of x1:y12-3: 1; preferably, x1：y13:1 or 2: 1.
In the formula II, A2Selected from the first component; in a molar ratio of x2:y2:y33-11: 1-4: 1-2; preferably, x2:y2:y33:1:2, 5:1:1 or 11:4: 1.
In the formula III, A3Selected from the first component; in a molar ratio of x3:y4:y5:y65-11: 1-4: 1: 2; preferably, x3:y4:y5:y6Either 5:1:1:2 or 11:4:1: 2.
More preferably, the electrolyte host C is selected from Na3PS4、Na3PSe4、Na3SbS4、Na3AsS4、Na3SbSe4、Na3AsSe4、Na10GeP2S12、Na10SiP2S12、Na10SnP2S12、Na11Sn2PS12、Na11Sn2PSe12、Na11.1Sn2.1P0.9Se12、Na10.8Sn1.9PS11.8、Na4-x4Sn1-x4Sbx4S4(0.02≤x4≤0.33)，94Na3PS4·6Na4SiS4，Na2.9375PS3.9375Cl0.0625，Na3+x5Mx5P1-x5S4(M＝Ge4+,Ti4+,Sn4+；0＜x5≤0.1)，Na3P0.62As0.38S4And Na3PSx6Se4-x6(0. ltoreq. x 6. ltoreq.4); most preferably selected from Na3PS4、Na3SbS4And Na11Sn2PS12One or more ofAnd (4) a plurality of.
In the present invention, D is selected from dopants. The kind of the dopant is the same as that of the dopant in the above technical solution, and is not described herein again.
M is the molar content of the dopant; m is more than or equal to 0 and less than or equal to 50; preferably, 0. ltoreq. m.ltoreq.30; more preferably, 0. ltoreq. m.ltoreq.10.
In a particular embodiment of the invention, the electrolyte host C is preferably selected from 3Na2S·Sb2S3·2S、11Na2S·4SnS2·P2S5、3Na2S·P2S5Or 3Na2S·Sb2S3·2Se。
In the present invention, the electrolyte of the all-solid-state sodium secondary battery is specifically Na3SbS4；Na3SbS3Se；90Na3SbS4·10Sb2O5；95Na3PS4·5NaCl；Na3PS4Or Na11Sn2PS12。
The invention provides a preparation method of the electrolyte of the all-solid-state sodium secondary battery, which comprises the following steps:
mixing the first component, the second component and a solvent, and reacting to obtain a precursor solution; the first component is selected from Na2S and/or Na2Se; the second component is selected from Sb2S3、Sb2Se3、Sb2S5、Sb2Se5、P2S5、P2S3、As2S3、As2S5、S、Se、SnS2、SiS2、SnS、GeS2And GeS;
and drying and grinding the precursor solution, and carrying out heat treatment under a protective atmosphere to obtain the all-solid-state sodium secondary battery electrolyte, wherein the granularity of the all-solid-state sodium secondary battery electrolyte is 10 nm-10 mu m.
The method mixes and reacts a first component, a second component and a solvent to obtain a precursor solution. The types of the first component and the second component are the same as those of the first component and the second component in the above technical solution, and are not described herein again.
In the present invention, the solvent is preferably selected from one or more of water, acetonitrile, tetrahydrofuran, N-methylformamide, ethylene glycol dimethyl ether, dimethyl carbonate, ethyl acetate, chlorobenzene, N-hexane, ethanol, methanol, and dimethylformamide, and more preferably from one or more of acetonitrile, ethylene glycol dimethyl ether, and tetrahydrofuran. The volume of the solvent and the mass ratio of the electrolyte obtained by the reaction are preferably (5-40) ml: (0.005-2) mol.
In the present invention, the first component, the second component, the solvent are preferably further mixed with a dopant; the dopant is selected from one or more of a third component, an oxide, and a halide. The types of the third component, the oxide and the halide are the same as those of the third component, the oxide and the halide in the above technical scheme, and are not described again here. When the third component is doped, it is of a different species than the second component.
In the present invention, the mixing is preferably mechanical mixing. The reaction temperature of the first component, the second component and the solvent is preferably 25-110 ℃, and more preferably 25-60 ℃; the reaction time is preferably 30min to 120 hours, more preferably 6 hours to 48 hours.
After the precursor solution is obtained, the precursor solution is dried, ground and subjected to heat treatment under a protective atmosphere to obtain the all-solid-state sodium secondary battery electrolyte, wherein the granularity of the all-solid-state sodium secondary battery electrolyte is 10 nm-10 mu m.
After the precursor solution is obtained in the present invention, it is preferably dried after suction filtration. In the present invention, the drying temperature is preferably 40 to 200 ℃. The grinding mode is preferably one or more selected from high-energy ball milling, low-speed tumbling and hand milling, and more preferably high-energy ball milling. The grinding time is preferably 30min to 72 hours, and more preferably 4 to 24 hours.
The protective atmosphere is preferably selected from nitrogen and/or argon. The heat treatment is also called annealing. The temperature of the heat treatment is preferably 150-1000 ℃, and more preferably 230-800 ℃; the time for the heat treatment is preferably 0.5 to 36 hours, more preferably 2 to 20 hours.
In the sintering heat treatment process, the sintering mode, the sintering temperature rise rate and the cooling mode after sintering are not particularly limited, the sintering mode can be sealed sintering or sintering in an open inert atmosphere, and the cooling mode after sintering can be quenching or furnace cooling.
The preparation method provided by the invention can control the particle size and the morphology of the prepared electrolyte by selecting the solvent and adjusting the reaction time; the sodium ion conductivity of the prepared all-solid-state sodium secondary battery electrolyte material can be further adjusted by adjusting the grinding time, the heat treatment temperature and the heat treatment time. The preparation method has simple operation and short preparation period.
The invention provides an all-solid-state sodium secondary battery, which comprises a positive electrode, a negative electrode and an all-solid-state sodium secondary battery electrolyte arranged between the positive electrode and the negative electrode;
the all-solid-state sodium secondary battery electrolyte is prepared by the preparation method in the technical scheme or the technical scheme.
In the present invention, the material of the positive electrode is preferably selected from FeS2、NaCrO2And VS4One or more of; the positive electrode is a composite positive electrode. The material of the negative electrode is preferably metallic sodium.
The secondary battery has excellent electrochemical performance, particularly good multiplying power and cycle performance.
In order to further illustrate the present invention, the following examples are provided to describe the electrolyte of all-solid-state sodium secondary battery, the preparation method and the application thereof in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Under the protection of argon atmosphere, (1) adding Na2S、Sb2S3Mixing with S according to the molar ratio of 3:1:2 and acetonitrile 20ml as a solvent, and reacting at 50 ℃ for 36 hours to obtain the all-solid-state sodium secondary battery electrolyte material Na3SbS4The precursor solution of (1); (2) carrying out suction filtration and drying on the precursor solution obtained in the step 1) to obtain an all-solid-state sodium secondary battery electrolyte material precursor; (3) performing high-energy ball milling on the precursor obtained in the step 2) for 24 hours to obtain precursor powder; (4) annealing the precursor powder obtained in the step 3) at 480 ℃ for 12h to obtain the all-solid-state sodium secondary battery electrolyte material Na3SbS4. The scanning electron microscope test result shows that the Na prepared in the example 13SbS4The particle size of the electrolyte material is 10 nm-200 nm, the prepared all-solid-state sodium secondary battery electrolyte material is subjected to electrochemical alternating current impedance spectroscopy (EIS) test (taking a carbon sheet as a blocking electrode) and cyclic voltammetry test (taking metallic sodium as a reference electrode and stainless steel as a counter electrode) at room temperature, and the result shows that the room-temperature sodium ion conductivity is 3.0 × 10-3S cm-1And the electrochemical window is-0.5V-5V, which shows that the obtained material has good conductivity and electrochemical stability. Mixing the above all-solid-state electrolyte material with sodium metal cathode, FeS2The mixed positive electrode is assembled into the all-solid-state sodium secondary battery. The assembled all-solid-state sodium secondary battery is subjected to charge and discharge tests at a current density of 50mA/g, and the test results show that: the obtained all-solid-state sodium secondary battery has specific discharge capacity of 410.5mAh g-1The first efficiency was 72.4%. And after circulating for 100 circles, the capacity of the product is kept at 250.6mAhg-1。
Example 2
Under the protection of argon atmosphere, (1) adding Na2S、Sb2S3Mixing Se with 20ml of glycol dimethyl ether serving as a solvent according to the molar ratio of 3:1:2, and reacting at 25 ℃ for 48 hours to obtain the all-solid-state sodium secondary battery electrolyte material Na3SbS3A precursor solution of Se; (2) carrying out suction filtration and drying on the precursor solution obtained in the step 1) to obtain an all-solid-state sodium secondary battery electrolyte material precursor; (3) carrying out high-energy ball milling on the precursor obtained in the step 2) for 4h to obtain precursor powder; (4) annealing the precursor powder obtained in the step 3) for 2 hours at 500 ℃ to obtain the all-solid-state sodium secondary battery electrolyte material Na3SbS3And (5) Se. Scanning Electron Microscope (SEM) test of the structure shows that Na prepared in example 23SbS3The particle size of Se is 30-500 nm, the prepared all-solid-state sodium secondary battery electrolyte material is subjected to electrochemical alternating current impedance spectroscopy (EIS) test (a carbon sheet is used as a blocking electrode) and cyclic voltammetry test (metallic sodium is used as a reference electrode and stainless steel is used as a counter electrode) at room temperature, and the result shows that the room-temperature sodium ion conductivity is 3.4 × 10-3S cm-1And the electrochemical window is-0.5V-5V, which shows that the obtained material has good conductivity and electrochemical stability. Mixing the above all-solid-state electrolyte material with sodium metal cathode, NaCrO2The mixed positive electrode is assembled into the all-solid-state sodium secondary battery. The assembled all-solid-state sodium secondary battery is subjected to charge and discharge tests at a current density of 50mA/g, and the test results show that: the first discharge specific capacity of the obtained all-solid-state sodium secondary battery is 120.6mAh g-1The first efficiency was 72.8%. And after circulating for 100 circles, the capacity of the solution is kept at 75.2mAh g-1。
Example 3
Under the protection of argon atmosphere, (1) adding Na2S、Sb2S3And S are weighed according to the molar ratio of 3:1:2 and then (3 Na)2S·Sb2S3·2S):Sb2O5Sb was weighed at a molar ratio of 90:102O5Mixing with 30ml of tetrahydrofuran solvent, and reacting for 48 hours at 25 ℃ to obtain a precursor solution of the electrolyte material of the all-solid-state sodium secondary battery; (2) carrying out suction filtration and drying on the precursor solution obtained in the step 1) to obtain an all-solid-state sodium secondary battery electrolyte material precursor; (3) performing high-energy ball milling on the precursor obtained in the step 2) for 8 hours to obtain precursor powder; (4) annealing the precursor powder obtained in the step 3) at 480 ℃ for 8h to obtain the all-solid-state sodium secondary battery electrolyte material 90Na3SbS4·10Sb2O5. Scanning Electron Microscope (SEM) test of the structure shows that 90Na prepared in example 33SbS4·10Sb2O5The particle size of (A) is 20nm to 300 nm. The prepared all-solid-state sodium secondary battery electrolyte material is subjected to electrochemical alternating current impedance spectroscopy (EIS) test (taking a carbon sheet as a blocking electrode) and cyclic voltammetry test (taking metallic sodium as a reference electrode and stainless steel as a counter electrode) at room temperature, and the result is thatThe room temperature sodium ion conductivity was found to be 3.9 × 10-3S cm-1And the electrochemical window is-0.5V-5V, which shows that the obtained material has good conductivity and electrochemical stability. Mixing the above all-solid-state electrolyte material with sodium metal cathode, VS4The mixed positive electrode is assembled into the all-solid-state sodium secondary battery. The assembled all-solid-state sodium secondary battery is subjected to charge and discharge tests at a current density of 100mA/g, and the test results show that: the first discharge specific capacity of the obtained all-solid-state sodium secondary battery is 440.3mAh g-1The first efficiency is 75.6 percent, and the capacity is kept to be 300.5mAh g after 100 circles of circulation-1。
Example 4
Under the protection of argon atmosphere, (1) adding Na2S、P2S5Weighing according to the molar ratio of 3:1, and then pressing according to (3 Na)2S·P2S5) Weighing NaCl according to the molar ratio of 95:5, mixing the NaCl with 20ml of acetonitrile serving as a solvent, and reacting at 60 ℃ for 6 hours to obtain a precursor solution of the electrolyte material of the all-solid-state sodium secondary battery; (2) carrying out suction filtration and drying on the precursor solution obtained in the step 1) to obtain an all-solid-state sodium secondary battery electrolyte material precursor; (3) performing high-energy ball milling on the precursor obtained in the step 2) for 20 hours to obtain precursor powder; (4) annealing the precursor powder obtained in the step 3) at 230 ℃ for 8h to obtain the all-solid-state sodium secondary battery electrolyte material 95Na3PS45 NaCl. Scanning Electron Microscope (SEM) test of the structure shows that 95Na prepared in example 43PS4The particle size of 5NaCl is 100 nm-1 mu m, and the prepared electrolyte material of the all-solid-state sodium secondary battery is subjected to an electrochemical alternating current impedance spectroscopy (EIS) test (a carbon sheet is used as a blocking electrode) and a cyclic voltammetry test (metallic sodium is used as a reference electrode and stainless steel is used as a counter electrode) under the room temperature condition, so that the room temperature sodium ion conductivity is 9.5 × 10-4S cm-1And the electrochemical window is-0.5V-5V, which shows that the obtained material has good conductivity and electrochemical stability. Mixing the above all-solid-state electrolyte material with sodium metal cathode, VS4The mixed positive electrode is assembled into the all-solid-state sodium secondary battery. The assembled all-solid-state sodium secondary battery is subjected to charge and discharge tests at a current density of 100mA/gThe results show that: the first discharge specific capacity of the obtained all-solid-state sodium secondary battery is 419.7mAh g-1The first efficiency is 75.1%, and after 100 cycles, the capacity is maintained at 280.6mAh g-1。
Example 5
Under the protection of argon atmosphere, (1) adding Na2S、P2S5Weighing according to the molar ratio of 3:1, mixing with 20ml of acetonitrile serving as a solvent, and reacting at 50 ℃ for 24 hours to obtain a precursor solution of the electrolyte material of the all-solid-state sodium secondary battery; (2) carrying out suction filtration and drying on the precursor solution obtained in the step 1) to obtain an all-solid-state sodium secondary battery electrolyte material precursor; (3) performing high-energy ball milling on the precursor obtained in the step 2) for 13h to obtain precursor powder; (4) annealing the precursor powder obtained in the step 3) at 260 ℃ for 4h to obtain Na of the all-solid-state sodium secondary battery electrolyte material3PS4. Scanning Electron Microscope (SEM) test of the structure shows that Na prepared in example 53PS4The particle size of the electrolyte material is 200 nm-1 mu m, and the prepared electrolyte material of the all-solid-state sodium secondary battery is subjected to electrochemical alternating current impedance spectroscopy (EIS) test (taking a carbon sheet as a blocking electrode) and cyclic voltammetry test (taking metallic sodium as a reference electrode and stainless steel as a counter electrode) at room temperature, and the result shows that the room-temperature sodium ion conductivity is 2 × 10-4S cm-1And the electrochemical window is-0.5V-5V, which shows that the obtained material has good conductivity and electrochemical stability. Mixing the above all-solid-state electrolyte material with sodium metal cathode, FeS2The mixed positive electrode is assembled into the all-solid-state sodium secondary battery. The assembled all-solid-state sodium secondary battery is subjected to charge and discharge tests at a current density of 50mA/g, and the test results show that: the first discharge specific capacity of the obtained all-solid-state sodium secondary battery is 405.6mAh g-1The first efficiency is 70.6 percent, and the capacity is kept to be 200.4mAh g after 100 cycles of circulation-1。
Example 6
Under the protection of argon atmosphere, (1) adding Na2S、SnS2、P2S5Weighing according to the mol ratio of 11:4:1, mixing with acetonitrile 40ml solvent, reacting for 12h at 50 ℃ to obtain the all-solid-state sodium secondary battery electrolyte materialNa11Sn2PS12Precursor solution; (2) carrying out suction filtration and drying on the precursor solution obtained in the step 1) to obtain an all-solid-state sodium secondary battery electrolyte material precursor; (3) performing high-energy ball milling on the precursor obtained in the step 2) for 20 hours to obtain precursor powder; (4) annealing the precursor powder obtained in the step 3) at 800 ℃ for 20h to obtain the all-solid-state sodium secondary battery electrolyte material Na11Sn2PS12. Scanning Electron Microscope (SEM) test of the structure shows that Na prepared in example 611Sn2PS12The particle size of the electrolyte material is 500 nm-5 mu m, and the prepared electrolyte material of the all-solid-state sodium secondary battery is subjected to electrochemical alternating current impedance spectroscopy (EIS) test (taking a carbon sheet as a blocking electrode) and cyclic voltammetry test (taking metallic sodium as a reference electrode and stainless steel as a counter electrode) at room temperature, and the result shows that the room-temperature sodium ion conductivity is 5 × 10-3S cm-1And the electrochemical window is-0.5V-5V, which shows that the obtained material has good conductivity and electrochemical stability. Mixing the above all-solid-state electrolyte material with sodium metal cathode, VS4The mixed positive electrode is assembled into the all-solid-state sodium secondary battery. The assembled all-solid-state sodium secondary battery is subjected to charge and discharge tests at a current density of 100mA/g, and the test results show that: the first discharge specific capacity of the obtained all-solid-state sodium secondary battery is 450.5mAh g-1The first efficiency is 80.2 percent, and the capacity is maintained to be 342.1mAh g after 100 circles of circulation-1。
As can be seen from the above examples, the present invention provides an all-solid-state sodium secondary battery electrolyte and a method thereof, the electrolyte being prepared from a starting material comprising a first component and a second component; the first component is selected from Na2S and/or Na2Se; the second component is selected from Sb2S3、Sb2Se3、Sb2S5、Sb2Se5、P2S5、P2S3、As2S3、As2S5、S、Se、SnS2、SiS2、SnS、GeS2And GeS; the granularity of the electrolyte of the all-solid-state sodium secondary battery is 10nmThe preparation method comprises the steps of mixing a first component, a second component and a solvent, drying and grinding an obtained reaction product, and carrying out heat treatment to obtain the electrolyte, wherein the method can effectively regulate and control the particle size and the morphology of the electrolyte by a solvent liquid phase method, so that the electrolyte has higher sodium ion conductivity, and also has a wider electrochemical window-4～5.0×10-3S cm-1The particle size is 10 nm-10 mu m, and the electrochemical window is up to 5V.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. An all-solid-state sodium secondary battery electrolyte is prepared from raw materials including a first component and a second component;
the first component is selected from Na2S and/or Na2Se；
The second component is selected from Sb2S3、Sb2Se3、Sb2S5、Sb2Se5、P2S5、P2S3、As2S3、As2S5、S、Se、SnS2、SiS2、SnS、GeS2And GeS;
the granularity of the electrolyte of the all-solid-state sodium secondary battery is 10 nm-10 mu m;
the raw materials also comprise dopants;
the dopant is selected from one or more of a third component, an oxide and a halide;
the third component is selected from SiS2、GeS2、SnS2、SiS、GeS、SnS、TiS2、FeS、Sb2S3、Sb2Se3、Sb2S5、Sb2Se5、P2S5、P2S3、As2S3、As2S5、S、Se、FeS2、MoS2、B2S3、Al2S3、MnS、ZnS、NiS、Ni2S3、NiS2And MnS2One or more of; the third component and the second component are different in composition;
the oxide is selected from P2O5、B2O3、SiO2、TiO2、ZnO、Al2O3、MnO、MnO2、GeO2、Sb2O3、Sb2O5、As2O3And As2O5One or more of;
the halide is selected from sodium halide;
the all-solid-state sodium secondary battery electrolyte has the following composition: (100-m) C: mD;
0≤m≤50；
c is selected from electrolytes shown in formula II or formula III:
x2A2·y2B2·y3B3formula II; said x2: y2: y3=3~11:1~4:1~2；
x3A3·y4B4·y5B5·y6B6Formula III; said x3: y4: y5: y6=5~11:1~4:1:2；
A is described2And A3Independently selected from the first component;
b is2、B3、B4、B5And B6Independently selected from the second component;
the D is selected from dopants.
2. The all-solid-state sodium secondary battery electrolyte according to claim 1, wherein the C is selected from 3Na2S·Sb2S3·2S、11Na2S·4SnS2·P2S5Or 3Na2S·Sb2S3·2Se。
3. A method for preparing the electrolyte of the all-solid-state sodium secondary battery according to any one of claims 1 to 2, comprising the steps of:
mixing the first component, the second component and a solvent, and reacting to obtain a precursor solution; the first component is selected from Na2S and/or Na2Se; the second component is selected from Sb2S3、Sb2Se3、Sb2S5、Sb2Se5、P2S5、P2S3、As2S3、As2S5、S、Se、SnS2、SiS2、SnS、GeS2And GeS;
and drying and grinding the precursor solution, and carrying out heat treatment under a protective atmosphere to obtain the all-solid-state sodium secondary battery electrolyte, wherein the granularity of the all-solid-state sodium secondary battery electrolyte is 10 nm-10 mu m.
4. The method of claim 3, wherein the first component, the second component, the solvent are further mixed with a dopant;
the dopant is selected from one or more of a third component, an oxide and a halide;
the third component is selected from SiS2、GeS2、SnS2、SiS、GeS、SnS、TiS2、FeS、Sb2S3、Sb2Se3、Sb2S5、Sb2Se5、P2S5、P2S3、As2S3、As2S5、S、Se、FeS2、MoS2、B2S3、Al2S3、MnS、ZnS、NiS、Ni2S3、NiS2And MnS2One or more of; the third component and the second component are different in composition.
5. The method according to claim 3, wherein the solvent is one or more selected from the group consisting of water, acetonitrile, tetrahydrofuran, N-methylformamide, ethylene glycol dimethyl ether, dimethyl carbonate, ethyl acetate, chlorobenzene, N-hexane, ethanol, methanol, and dimethylformamide.
6. The preparation method of claim 3, wherein the temperature of the heat treatment is 150 ℃ to 1000 ℃, and the time of the heat treatment is 0.5h to 36 h.
7. An all-solid-state sodium secondary battery comprises a positive electrode, a negative electrode and an all-solid-state sodium secondary battery electrolyte arranged between the positive electrode and the negative electrode;
the all-solid-state sodium secondary battery electrolyte is the all-solid-state sodium secondary battery electrolyte as defined in any one of claims 1 to 2 or the all-solid-state sodium secondary battery electrolyte prepared by the preparation method as defined in any one of claims 3 to 6.
CN201810757815.2A 2018-07-11 2018-07-11 All-solid-state sodium secondary battery electrolyte, preparation method and application thereof Active CN108695553B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810757815.2A CN108695553B (en) 2018-07-11 2018-07-11 All-solid-state sodium secondary battery electrolyte, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810757815.2A CN108695553B (en) 2018-07-11 2018-07-11 All-solid-state sodium secondary battery electrolyte, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN108695553A CN108695553A (en) 2018-10-23
CN108695553B true CN108695553B (en) 2020-10-09

Family

ID=63850524

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810757815.2A Active CN108695553B (en) 2018-07-11 2018-07-11 All-solid-state sodium secondary battery electrolyte, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN108695553B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110534801A (en) * 2019-09-05 2019-12-03 中国科学院宁波材料技术与工程研究所 All solid state electrolyte material and preparation method thereof and solid state secondary battery
CN111040061B (en) * 2019-12-26 2021-04-23 中国科学技术大学 Solid sodium ion electrolyte, preparation method thereof and all-solid-state sodium battery
BR112022012247A2 (en) * 2020-01-17 2022-08-30 Mitsubishi Gas Chemical Co METHOD FOR PRODUCING A SOLID SULFIDE-BASED ELECTROLYTE

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3134595B2 (en) * 1993-05-28 2001-02-13 松下電器産業株式会社 Sulfide-based lithium ion conductive solid electrolyte and its synthesis method
US9640835B2 (en) * 2012-03-06 2017-05-02 Japan Science And Technology Agency Ion conducting glass-ceramics, method for manufacturing same and all-solid-state secondary battery including same
US10439198B2 (en) * 2013-10-03 2019-10-08 Japan Science And Technology Agency Solution for forming layer that contains solid electrolyte for all-solid-state alkali metal secondary batteries, coated active material particles, electrode, all-solid-state alkali metal secondary battery and method for manufacturing same
US10840507B2 (en) * 2016-08-22 2020-11-17 Osaka Prefecture University Public Corporation Composite positive electrode active material for all-solid-state secondary battery, method for manufacturing same, positive electrode, and all-solid-state secondary battery
CN106505247A (en) * 2016-12-26 2017-03-15 中国科学院宁波材料技术与工程研究所 All solid state sode cell electrolyte, its preparation method and all solid state sodium rechargeable battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
progress in the development of sodium-ion solid electrolytes;Jung-Joon Kim等;《Small Methods》;20171016;第1卷(第10期);第1-9页 *
钠离子固体电解质材料研究进展;刘丽露等;《储能科学与技术》;20170930;第961-975页 *

Also Published As

Publication number Publication date
CN108695553A (en) 2018-10-23

Similar Documents

Publication Publication Date Title
EP3944390A1 (en) Composite material and preparation method therefor, and lithium ion battery
EP3021386B1 (en) Layered oxide material containing copper, and preparation method and use thereof
CN108832172B (en) All-solid-state electrolyte material, preparation method thereof and all-solid-state lithium secondary battery
WO2016009768A1 (en) Sulfide-based solid electrolyte for lithium ion batteries
CN110233298A (en) A kind of preparation method of novel all-solid lithium-ion battery
WO2020098427A1 (en) Lithium ion battery negative electrode material and non-aqueous electrolyte battery
CN108695553B (en) All-solid-state sodium secondary battery electrolyte, preparation method and application thereof
CN101719545A (en) Anode composite material of lithium sulfur battery and preparation method thereof
CN107093739B (en) Potassium manganese oxide for potassium ion battery anode material and preparation method thereof
CN108091923B (en) Solid electrolyte, method for preparing same, and all-solid-state lithium secondary battery
CN103500826A (en) Preparation method of positive composite material of graphene-lithium battery
CN103187556B (en) Lithium ion battery and its negative material, preparation method
KR20180072469A (en) Organic-inorganic composite solid electrolyte, lithium secondary cell comprising the same, and manufacturing method for the lithium secondary cell
KR20180071438A (en) Positive electrode active material, methods for manufacture thereof and all solid-state battery using the same
CN110137568A (en) A kind of composite solid electrolyte, preparation method and all-solid-state battery system
CN108461712A (en) A kind of potassium/potassium ferrite/Prussian blue solid state battery and preparation method thereof
KR101768452B1 (en) Anode, all solid lithium secondary batteries including the same and manufacturing method for the same
CN107293747B (en) Magnesium-site-doped magnesium ion battery positive electrode material and preparation method thereof
CN104485443A (en) Preparation method for graphene polymer cladding niobium-doping cobalt and lithium aluminate composite anode material
CN107256963A (en) Negative material and preparation method, negative pole and the full battery of lithium ion and preparation method
CN111224166A (en) Ether electrolyte, preparation method and application thereof
Huang et al. Synthesis and electrochemical properties of nanostructured LiAl x Mn 2− x O 4− y Br y particles
CN113206292B (en) Polymer-based composite solid electrolyte and preparation method and application thereof
CN109994720A (en) A kind of S-CNTs@MnO2The preparation method of lithium sulfur battery anode material
CN114843592A (en) Mixed conductor sulfide solid electrolyte, preparation method and all-solid-state battery

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
GR01 Patent grant
GR01 Patent grant