CN111313088A - Nd3+ and/or Eu3+ doped electrolyte, preparation method thereof and room-temperature solid-state fluorine ion battery - Google Patents

Nd3+ and/or Eu3+ doped electrolyte, preparation method thereof and room-temperature solid-state fluorine ion battery Download PDF

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CN111313088A
CN111313088A CN202010139056.0A CN202010139056A CN111313088A CN 111313088 A CN111313088 A CN 111313088A CN 202010139056 A CN202010139056 A CN 202010139056A CN 111313088 A CN111313088 A CN 111313088A
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electrolyte
snf
solid
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王先友
刘磊
谢鑫
曹爽
刘敏
陈曼芳
阳立
邵鼎盛
罗凯丽
邹长飞
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Xiangtan University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • 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
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • 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

Abstract

The invention provides a method based on Nd3+And/or Eu3+Doped electrolyte, a preparation method thereof and a room-temperature solid-state fluoride ion battery, belonging to the technical field of new energy materials and devices. The invention provides a material based on Nd3+And/or Eu3+The chemical composition of the doped electrolyte is Ba1‑xMxSnF4+XM is Nd and/or Eu, x is more than 0 and less than or equal to 0.5, and the room-temperature ionic conductivity can reach 1-9 x 10‑4S·cm‑1. The invention provides a preparation method of the electrolyte, which is simple and easy to operate and can realize industrialized mass production. The invention provides a room-temperature solid-state fluorine ion battery which uses Nd3+And/or Eu3+The doped electrolyte is used as an electrolyte and has good charge and discharge performance at room temperature.

Description

Nd3+ and/or Eu3+ doped electrolyte, preparation method thereof and room-temperature solid-state fluorine ion battery
Technical Field
The invention relates to the technical field of new energy materials and devices, in particular to a material based on Nd3+And/or Eu3+Doped electrolyte, a preparation method thereof and a room-temperature solid-state fluoride ion battery.
Background
The high-speed development of the new energy industry puts higher requirements on the energy density and the safety of new energy materials and devices, the existing lithium ion battery energy storage system cannot meet the requirements, and some novel energy storage battery systems such as sodium ion batteries, potassium ion batteries, magnesium ion batteries, chloride ion batteries, fluoride ion batteries and the like have attracted extensive attention in the scientific and industrial fields. Among these novel battery systems, Fluorine Ion Batteries (FIBs) have been favored by researchers because of their high theoretical energy density and high safety, and the theoretical volumetric energy density of fluorine ion batteries has been as high as 5000 wh.l-1。
Unlike traditional battery systems such as lithium ion batteries and sodium ion batteries, fluorine ion batteries are prepared by anion F-Shuttling in a fluorine ion conductor to achieve energy transfer between positive and negative electrodes, in short F in a fluorine ion battery-Is a carrier in the charge and discharge process. The AnjiReddy and Fichtner topic groups LaF3And BaF2Mixing, and ball milling to obtain La with bastnaesite structure for selective passage of fluorine ions0.9Ba0.1F2.9(LBF10) and was successfully applied to solid-state fluorine ion batteries, which was also the first time confirmed. The bastnaesite-structured LBF10 electrolyte has an ionic conductivity of 2.8 at 160 deg.C×10-4S·cm-1Its room temperature ionic conductivity is extremely low, which limits the further development of solid-state fluorine ion batteries.
Disclosure of Invention
In view of the above, the present invention is to provide a Nd-based optical film3+And/or Eu3+Doped electrolyte, preparation method thereof and room-temperature solid-state fluorine ion battery, and Nd-based electrolyte provided by the invention3+And/or Eu3+The doped electrolyte has high room-temperature ionic conductivity and can be successfully applied to the preparation of room-temperature solid fluorine ion batteries.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a method based on Nd3+And/or Eu3+Doped electrolyte with chemical composition of Ba1-xMxSnF4+XM is Nd and/or Eu, and x is more than 0 and less than or equal to 0.5.
Preferably, when M is Nd and Eu, the molar ratio of Nd and Eu is 1: 0 to 0.5.
The invention provides a method based on Nd3+And/or Eu3+A method of preparing a doped electrolyte comprising the steps of:
(1) providing precursor powder;
the preparation method of the precursor powder comprises the following steps: mixing BaF2、SnF2And MF3Mixing, and sequentially performing high-energy ball milling and drying to obtain precursor powder; the MF3Is NdF3And/or EuF3；
Or comprises the following steps:
carrying out precipitation reaction on soluble salt of Ba, soluble salt of Sn and soluble salt of M with water and soluble fluorine salt under the condition of stirring, and sequentially carrying out solid-liquid separation, washing and drying on the product of the precipitation reaction to obtain precursor powder; m is Nd and/or Eu;
(2) sintering the precursor powder to obtain the Nd-based powder3+And/or Eu3+A doped electrolyte.
Preferably, the BaF2、SnF2And MF3The molar ratio of (a) to (b) is [0.5 to 1): (0 to 0.5)]：(4～4.5]；
The molar ratio of the soluble salt of Ba to the soluble salt of Sn to the soluble salt of M is (0.5-1): (0 to 0.5) and (4 to 4.5).
Preferably, the rotation speed of the high-energy ball mill is 500-5000 rpm, and the time is 0.5-30 h; the drying temperature is independently 40-100 ℃, and the drying time is independently 2-10 h.
Preferably, the soluble fluoride salt is NH4F. One or more of NaF and KF, wherein the addition coefficient of the soluble fluorine salt is 1-2.0.
Preferably, the precipitation reaction time is 0.5-20 h, and the stirring speed is 100-1000 rpm.
Preferably, the sintering temperature is 200-600 ℃, and the time is 2-20 h.
The invention provides a room-temperature solid-state fluoride ion battery which comprises a positive electrode, a solid-state electrolyte and a negative electrode, wherein the solid-state electrolyte is based on Nd3+And/or Eu3+A doped electrolyte; the material of the positive electrode includes a metal fluoride, and the material of the negative electrode includes an active metal.
Preferably, the metal fluoride is CaF2、LaF3、CeF3、BiF3、MgF2、MnF3、 FeF3、CuF2、PbF2And one or more of their dopants; the active metal is one or more of Cu, Ag, Ni, Co, Pb, Ce, Mn, Au, Pt, Rh, V, Os, Ru, Fe, Cr, Bi, Nb, Sb, Ti, Sn, Zn and Li.
The invention provides a method based on Nd3+And/or Eu3+Doped electrolyte with chemical composition of Ba1-xMxSnF4+XM is Nd and/or Eu, and x is more than 0 and less than or equal to 0.5. The invention adopts rare earth metal ions Nd with high valence and small atomic radius3+And/or Eu3+Doped substituted layered fluoride ion electrolyte BaSnF4Of Ba2+Can be in BaSnF4Introduction of defects or gaps into the structure can be further improvedFluorine ion conductivity of the high room temperature solid electrolyte. The results of the examples show that Nd-based materials according to the invention3+And/or Eu3 +The room-temperature ionic conductivity of the doped electrolyte can reach 1-9 multiplied by 10-4S·cm-1。
The invention provides a method based on Nd3+And/or Eu3+The preparation method of the doped electrolyte is simple and easy to operate, and can realize industrial mass production.
The invention provides a room-temperature solid-state fluorine ion battery which uses the Nd-based fluorine ion battery3+And/or Eu3+The doped electrolyte is used as an electrolyte and can show better charge and discharge performance at room temperature.
Drawings
FIG. 1 shows Ba prepared by coprecipitation in example 10.98Nd0.02SnF4.02XRD patterns of the precursor powder before and after sintering;
FIG. 2 shows Ba in example 10.98Nd0.02SnF4.02A physical drawing of the electrolyte sheet, wherein (a) is a diameter measurement drawing of the electrolyte sheet and (b) is a cross-sectional SEM drawing of the electrolyte sheet;
FIG. 3 shows Ba in example 10.98Nd0.02SnF4.02Impedance plots of the electrolyte at different temperatures;
FIG. 4 shows BiF in example 13/Ba0.98Nd0.02SnF4.02the/Sn room temperature solid state fluorine ion battery is 12.7 mu A cm-2A charge-discharge curve at current density;
FIG. 5 shows Ba in example 20.94Eu0.06SnF4.06Impedance plot of electrolyte at 30 ℃;
FIG. 6 shows Ba in example 30.95Eu0.05SnF4.05Impedance plot of electrolyte at 30 ℃;
FIG. 7 shows Ba in example 40.9Nd0.1SnF4.1Impedance plot of electrolyte at 30 ℃.
Detailed Description
The invention provides a method based on Nd3+And/or Eu3+Doped electrolyte with chemical composition of Ba1-xMxSnF4+XM is Nd and/or Eu, and x is more than 0 and less than or equal to 0.5.
In the present invention, the preferable range of x is 0.05. ltoreq. x.ltoreq.0.1. In the present invention, when M is Nd and Eu, the molar ratio of Nd and Eu is 1: 0 to 0.5, preferably 1: 0.2 to 0.4. In a specific embodiment of the invention, said Nd-based3+And/or Eu3+The chemical composition of the doped electrolyte is preferably Ba0.98Nd0.02SnF4.02、Ba0.94Eu0.06SnF4.06、Ba0.95Eu0.05SnF4.05And Ba0.9Nd0.1SnF4.1One or more of them.
The invention adopts rare earth metal ions Nd with high valence and small atomic radius3+And/or Eu3+Doped substituted layered fluoride ion electrolyte BaSnF4Of Ba2+Can be in BaSnF4Defects or gaps are introduced into the structure, so that the room-temperature fluorine ion conductivity of the solid electrolyte can be further improved, and is 1-9 multiplied by 10-4S·cm-1。
The invention provides a method based on Nd3+And/or Eu3+A doped electrolyte comprising the steps of:
(1) providing precursor powder;
the method of precursor powder comprises the steps of: mixing BaF2、SnF2And MF3Mixing, and sequentially performing high-energy ball milling and drying to obtain precursor powder; the MF3Is NdF3And/or EuF3；
Or comprises the following steps:
carrying out precipitation reaction on soluble salt of Ba, soluble salt of Sn and soluble salt of M with water and soluble fluorine salt under the condition of stirring, and sequentially carrying out solid-liquid separation, washing and drying on the product of the precipitation reaction to obtain precursor powder; m is Nd and/or Eu;
(2) sintering the precursor powder to obtain the Nd-based powder3+And/or Eu3+A doped electrolyte.
Unless otherwise specified, the starting materials used in the present invention are commercially available.
The invention provides a precursor powder. In the present invention, the method of providing the precursor powder includes two methods, the first method including the steps of: mixing BaF2、SnF2And MF3Mixing, and performing high-energy ball milling and drying in sequence to obtain precursor powder. In the present invention, the BaF2、SnF2And MF3The molar ratio of (a) to (b) is preferably [0.5 to 1): (0 to 0.5)]：(4～4.5]More preferably [0.6 to 0.95 ]]：[0.05～0.1]： [4.05～4.1]In the present invention, the "[", "") "]"is intended to mean that the value of the end point is included, and" (",") is intended to mean that the value of the end point is not included. In the present invention, when the MF is used3Is NdF3And EuF3In the case of a mixture of (1), NdF3And EuF3Is preferably 1: 0 to 0.5, more preferably 1: 0.2 to 0.4. The present invention does not require any particular mixing means, and mixing means known to those skilled in the art may be used. In the invention, the rotation speed of the high-energy ball mill is preferably 500-5000 rpm, more preferably 1000-4000 rpm; the time is preferably 0.5 to 30 hours, and more preferably 5 to 20 hours. The invention has no special requirement on the ball milling medium of the high-energy ball milling, and the ball milling medium which is well known to the technical personnel in the field can be used. In the invention, the ball-to-material ratio of the high-energy ball mill is preferably 2-40: 1, more preferably 10 to 30: 1. in the invention, the particle size of the solid obtained after ball milling is preferably 0-800 μm, and more preferably 200-600 μm.
In the invention, the drying temperature is preferably 40-100 ℃, more preferably 60-80 ℃, and the time is preferably 2-10 hours, more preferably 4-8 hours. In the present invention, the drying is preferably performed by air-blast drying.
Alternatively, the present invention provides a second method of precursor powder comprising the steps of: carrying out precipitation reaction on soluble salt of Ba, soluble salt of Sn and soluble salt of M with water and soluble fluorine salt under the condition of stirring, and sequentially carrying out solid-liquid separation on products of the precipitation reactionSeparating, washing and drying to obtain precursor powder; and M is Nd and/or Eu. In the present invention, the soluble salt of Ba is preferably BaCl2And/or Ba (NO)3)2In the present invention, the BaCl2Preferably a hydrate thereof, particularly preferably BaCl2·2H2O; the soluble salt of Sn is preferably SnCl2And/or Sn (NO)3)2In the present invention, the SnCl2Preferably a hydrate thereof, particularly preferably SnCl2·2H2O; the soluble salt of M is preferably the chloride of M and/or the nitrate of M. In the invention, the mole ratio of the soluble salt of Ba, the soluble salt of Sn and the soluble salt of M is preferably [ 0.5-1): (0 to 0.5)]： (4～4.5]More preferably [0.6 to 0.95 ]]：[0.05～0.1]：[4.05～4.1]. In the present invention, when M is a mixture of Nd and Eu, the molar ratio of Nd and Eu is preferably 1: 0 to 0.5, more preferably 1: 0.2 to 0.4. In the invention, the water is preferably deionized water, and the invention has no special requirement on the dosage of the water, and can completely dissolve soluble salt of Ba, soluble salt of Sn and soluble salt of M.
In the present invention, the soluble fluorine salt is preferably NH4F. One or more of NaF and KF; in the present invention, the addition coefficient of the soluble fluorine salt is preferably 1 to 2.0, and more preferably 0.5 to 1.5. In the present invention, the soluble fluoride salt functions as a precipitant.
In the invention, preferably, the soluble salt of Ba, the soluble salt of Sn and the soluble salt of M are mixed with water, and then the soluble villiaumite is added. In the invention, the mixing mode is preferably stirring mixing, and the mixing time is preferably 100-1000 rpm, more preferably 300-600 rpm; the mixing time is preferably 0.5-12 h, and more preferably 5-8 h. In the present invention, the soluble fluorine salt is preferably added in the form of an aqueous solution, and in the present invention, the molar concentration of the aqueous solution of the soluble fluorine salt is preferably 0.01 to 0.9mol · L-1More preferably 0.2 to 0.7 mol.L-1。
In the present invention, the time of the precipitation reactionPreferably 0.5 to 20 hours, more preferably 5 to 10 hours; the rotation speed of the stirring is preferably 100-1000 rpm, and more preferably 300-600 rpm. The invention makes the soluble salt of Ba, the soluble salt of Sn, the soluble salt of M and the soluble fluorine salt react through the precipitation reaction to generate Ba1-xMxSnF4+XAnd (4) precipitating.
In the invention, the time for solid-liquid separation is preferably 3-10 min. In the invention, the solid-liquid separation mode is preferably centrifugation, and the rotation speed of the centrifugation is preferably 3000-10000 rpm, and more preferably 5000-8000 rpm. In the present invention, the washing detergent is preferably water; the number of washing is preferably 3 to 10. In the present invention, the drying is preferably air-blast drying; the drying temperature is preferably 40-100 ℃, and more preferably 60-80 ℃; the drying time is preferably 2-10 h, and more preferably 4-8 h.
After the precursor powder is obtained, sintering the precursor powder to obtain the Nd-based powder3+And/or Eu3+A doped electrolyte. In the invention, the sintering temperature is preferably 200-600 ℃, and more preferably 300-500 ℃; the sintering time is preferably 2-20 h, and more preferably 5-15 h; according to the invention, the sintering time is calculated from the temperature rise to the sintering temperature, and the temperature rise rate of the temperature rise to the sintering temperature is preferably 1-10 ℃/min, and more preferably 4-6 ℃/min. The sintering is preferably carried out under the protection of an inert gas, preferably argon. The present invention preferably uses a high temperature tube furnace apparatus for the sintering. The present invention can further reduce the grain resistance of the electrolyte by the sintering, thereby improving the ionic conductivity.
The invention provides a room-temperature solid-state fluoride ion battery which comprises a positive electrode, a solid-state electrolyte and a negative electrode, wherein the solid-state electrolyte is based on Nd3+And/or Eu3+A doped electrolyte; the material of the positive electrode includes a metal fluoride, and the material of the negative electrode includes an active metal.
When the base is Nd3+And/or Eu3+Doped electrolytes as room temperature solid state fluoride ion electrodesIn the case of cell electrolytes, the invention preferably bases the Nd3+And/or Eu3+The doped electrolyte is processed into an electrolyte sheet or an electrolyte film for use. In the present invention, the method for processing the electrolyte sheet is preferably cold pressing or hot pressing, and the present invention has no special requirement on the specific operation mode of the cold pressing or hot pressing, and the above mode known to those skilled in the art can be used; in the specific embodiment of the invention, the cold pressing temperature is preferably normal temperature, and the pressure is preferably 30-50 MPa, and more preferably 40 MPa; the pressure maintaining time is preferably 30-50 s, and more preferably 40 s; the hot pressing temperature is preferably 130-220 ℃, and more preferably 150-200 ℃; the pressure is preferably 10-30 MPa, and more preferably 20 MPa; the dwell time is preferably 10 to 30s, and more preferably 20 s. The invention has no special requirements on the diameter and the thickness of the electrolyte sheet, and the diameter and the thickness are determined according to the requirements of the room-temperature solid-state fluorine ion battery. In a particular embodiment of the invention, the electrolyte sheet preferably has a diameter of 14mm and a thickness of 1500 μm.
In the present invention, the electrolyte film is preferably formed by magnetron sputtering or electrodeposition. The present invention has no special requirement on the specific operation mode of the magnetron sputtering or the electrodeposition, and the operation mode can be realized by using the operation mode which is well known to the technical personnel in the field. In the present invention, the thickness of the electrolyte thin film is preferably 20 to 800 μm, and more preferably 200 to 600 μm.
In the present invention, the metal fluoride is preferably CaF2、LaF3、CeF3、BiF3、MgF2、 MnF3、FeF3、CuF2、PbF2And one or more of their dopants, more preferably BiF3、 FeF3、MgF2、CuF2One or more of the above; the active metal is preferably one or more of Cu, Ag, Ni, Co, Pb, Ce, Mn, Au, Pt, Rh, V, Os, Ru, Fe, Cr, Bi, Nb, Sb, Ti, Sn, Zn and Li. In the present invention, the negative electrode is preferably a sheet-like active metal or a film-like active metal. In the present invention, the thickness of the sheet metal is preferably 400 to 1000 μm, more preferably 600 to 800 μm; the thickness of the film-like metal is preferably 20 to 800 μm, and more preferably 200 to 500 μm. In the present invention, the preparation method of the thin film-like active metal is preferably one of magnetron sputtering, electrodeposition and hot melting. The present invention has no particular requirement on the specific operation modes of magnetron sputtering, electrodeposition and hot melting, and the modes can be realized by using the modes which are well known to the technical personnel in the field.
In the present invention, the material of the positive electrode and the negative electrode preferably further includes an auxiliary material. The invention has no special requirement on the types of the auxiliary materials, and the auxiliary materials used for preparing the anode and the cathode, which are well known to the technical personnel in the field, can be used.
The invention uses the Nd-based3+And/or Eu3+The doped electrolyte is used as the electrolyte of the room-temperature solid-state fluorine ion battery, and can show better charge and discharge performance at room temperature.
The Nd-based material provided by the invention is combined with the embodiment3+And/or Eu3+The doped electrolyte, the method of preparing the same, and the room temperature solid-state fluoride ion battery are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Weighing 3.5486gBaCl2·2H2O、3.4671gSnCl2·2H2O and 0.2667g Nd (NO)3)3·6H2Adding O into 250mL beaker, adding 100mL distilled water after weighing, stirring at 300rpm for 6h, and weighing 3.4858gNH4F (1.5 times addition factor) was dissolved in 50mL of distilled water until BaCl was present2·2H2O、SnCl2·2H2O and Nd (NO)3)3·6H2After O is completely dissolved, NH is added4Slowly dripping the solution F into the mixed solution, stirring for 16h after dripping, wherein the stirring speed is 200rpm, centrifuging for 6min at 5000rpm after complete reaction, washing the solid product for 4 times, and drying for 2.5h at 90 ℃ to obtain Ba0.98Nd0.02SnF4.02And (3) precursor powder.
Ba to be prepared0.98Nd0.02SnF4.02Precursor powderHeating to 300 ℃ at a heating rate of 6 ℃/min under the protection of argon gas, and sintering for 16h to obtain Ba0.98Nd0.02SnF4.02A solid electrolyte powder.
Ba0.98Nd0.02SnF4.02XRD patterns of the precursor powder before and after sintering are shown in figure 1, and XRD results show Ba before and after sintering0.98Nd0.02SnF4.02No structural change occurred. The invention can reduce the gaps among the particles by sintering, thereby improving the performance of the electrolyte without changing the chemical structure of the electrolyte.
Mix Ba with0.98Nd0.02SnF4.02The solid electrolyte powder was prepared into an electrolyte sheet with a diameter of 14mm and a thickness of 1500 μm by cold pressing (25 ℃, 40MPa, 45s holding pressure), and the physical diagram is shown in fig. 2, wherein (a) is a diameter measurement diagram of the electrolyte sheet, and (b) is a cross-sectional SEM diagram of the electrolyte sheet. Spraying gold on both sides of the ceramic, and assembling SS/Ba0.98Nd0.02SnF4.02The solid electrolyte impedance of the/SS symmetrical battery is measured under different temperature conditions. FIG. 3 shows Ba in this embodiment0.98Nd0.02SnF4.02The impedance diagram of the electrolyte at different temperatures is that the impedance of the electrolyte is continuously reduced as the temperature is increased. Calculated Ba0.98Nd0.02SnF4.02The solid electrolyte has a fluorine ion conductivity of 5.8 × 10 at 30 deg.C-4S·cm-1And the requirements of room-temperature solid-state fluorine ion batteries can be met.
Using BiF3/Ba0.98Nd0.02SnF4.02The/carbon nano tube composite material is a positive electrode of a fluorine ion battery, Ba0.98Nd0.02SnF4.02Electrolyte sheet, Sn/Ba0.98Nd0.02SnF4.02The/carbon nano tube composite material is a negative electrode of the fluorine ion battery, a 2025 button battery is assembled, and the battery is subjected to charge and discharge tests at 25 ℃. FIG. 4 shows BiF of this example3/Ba0.98Nd0.02SnF4.02the/Sn room temperature solid state fluorine ion battery is 12.7 mu A cm-2Charge and discharge curves at current density. Fig. 4 shows that the solid-state fluoride ion battery can exhibit good charge and discharge characteristics at room temperatureCan be used.
Example 2
Weighing 3.2529gBaCl2·2H2O、3.4671gSnCl2·2H2O and 0.6621gEuCl3·6H2Adding O into 250mL beaker, adding 100mL distilled water after weighing, stirring at 700rpm for 6h, weighing 2.9048gNH4F (1.25 times addition factor) was dissolved in 50mL of distilled water until BaCl was present2·2H2O、SnCl2·2H2O and EuCl3·6H2After O is completely dissolved, NH is added4Slowly dripping the solution F into the mixed solution, stirring for 12h after dripping, wherein the stirring rotation speed is 300rpm, centrifuging for 4min at 6000rpm after complete reaction, washing the solid product for 5 times, and drying for 8h at 60 ℃ to obtain Ba0.94Eu0.06SnF4.06And (3) precursor powder.
Ba to be prepared0.94Eu0.06SnF4.06Heating the precursor powder to 500 ℃ at a heating rate of 3 ℃/min under the protection of argon gas, and sintering for 15h to obtain Ba0.94Eu0.06SnF4.06A solid electrolyte powder.
Mix Ba with0.94Eu0.06SnF4.06The solid electrolyte powder is prepared into an electrolyte sheet with the diameter of 14mm and the thickness of 1500 mu m by a cold pressing (25 ℃, 30MPa, and 50s of pressure maintaining) mode. Spraying gold on both sides of the ceramic, and assembling SS/Ba0.94Eu0.06SnF4.06The impedance of the solid electrolyte measured at 30 ℃ in a/SS symmetrical cell is shown in FIG. 5. Calculated, Ba0.94Eu0.06SnF4.06The solid electrolyte has a fluorine ion conductivity of 1.01X 10 at 30 deg.C-4S·cm-1And the requirements of room-temperature solid-state fluorine ion batteries can be met.
Example 3
Separately weighing 4.7518gBaF2、4.7195gSnF2And 0.6304gEuF3Under the protection of argon, the ball milling rotation speed is 1200rpm, the ball milling time is 14h, the obtained ball milling product is dried for 7h at 70 ℃, and Ba is prepared0.95Eu0.05SnF4.05And (3) precursor powder.
Prepared Ba0.95Eu0.05SnF4.05And heating the precursor powder to 500 ℃ at the heating rate of 8 ℃/min under the protection of argon, and sintering for 13h to obtain electrolyte powder.
Mix Ba with0.95Eu0.05SnF4.05Preparing solid electrolyte powder into electrolyte sheets with the diameter of 14mm and the thickness of 1500 mu m by cold pressing (25 ℃, 30MPa, pressure maintaining for 45s), spraying gold on two sides, and assembling SS/Ba0.95Eu0.05SnF4.05The impedance of the solid electrolyte measured at 30 ℃ in a/SS symmetrical cell is shown in FIG. 6. Calculated, Ba0.95Eu0.05SnF4.05The solid electrolyte has a fluorine ion conductivity of 1.1X 10 at 30 deg.C-4S·cm-1And the requirements of room-temperature solid-state fluorine ion batteries can be met.
Example 4
Separately weighing 4.2238gBaF2、4.7195gSnF2And 1.2128gNdF3Under the protection of argon, ball milling rotating speed is 3000rpm, ball milling time is 11h, and the obtained ball milling product is dried for 9h at 60 ℃ to prepare Ba0.9Nd0.1SnF4.1And (3) precursor powder.
Ba to be prepared0.9Nd0.1SnF4.1Heating the precursor powder to 450 ℃ at a heating rate of 2 ℃/min under the protection of argon gas, and sintering for 11h to obtain Ba0.9Nd0.1SnF4.1An electrolyte powder.
Mix Ba with0.9Nd0.1SnF4.1Preparing solid electrolyte powder into electrolyte sheet with diameter of 14mm and thickness of 1500 μm by cold pressing (25 deg.C, 50MPa, and holding pressure for 30s), spraying gold on both sides, and assembling SS/Ba0.9Nd0.1SnF4.1The impedance of the solid electrolyte measured at 30 ℃ in a/SS symmetrical cell is shown in FIG. 7. Calculated, Ba0.9Nd0.1SnF4.1The solid electrolyte has a fluorine ion conductivity of 1.8X 10 at 30 deg.C-4S·cm-1And the requirements of room-temperature solid-state fluorine ion batteries can be met.
Example 5
Separately weighing 3.6958gBaF2、4.7195gSnF2、1.2128gNdF3And 0.6304g EuF3Under the protection of argon, the ball milling rotation speed is 1600rpm, the ball milling time is 12 hours, the obtained ball milling product is dried for 9 hours at the temperature of 60 ℃, and Ba is prepared0.85Nd0.1Eu0.05SnF4.15And (3) precursor powder.
Ba to be prepared0.85Nd0.1Eu0.05SnF4.15Heating the precursor powder to 400 ℃ at a heating rate of 3 ℃/min under the protection of argon gas, and sintering for 12h to obtain Ba0.85Nd0.1Eu0.05SnF4.15An electrolyte powder.
Mix Ba with0.85Nd0.1Eu0.05SnF4.15Preparing solid electrolyte powder into electrolyte sheet with diameter of 14mm and thickness of 1500 μm by cold pressing (25 deg.C, 40MPa, and holding pressure for 40s), spraying gold on both sides, and assembling SS/Ba0.85Nd0.1Eu0.05SnF4.15The solid electrolyte impedance of the/SS symmetrical battery is measured at the temperature of 30 ℃. Calculated, Ba0.85Nd0.1Eu0.05SnF4.15The solid electrolyte has a fluorine ion conductivity of 1.3X 10 at 30 deg.C-4S·cm-1And the requirements of room-temperature solid-state fluorine ion batteries can be met.
From the above results, it can be seen that the Nd-based material provided by the present invention3+And/or Eu3+The doped electrolyte has high room-temperature ionic conductivity, and the battery has good charge and discharge performance when being used as the room-temperature solid fluoride ion battery electrolyte.
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 (10)

1. Based on Nd3+And/or Eu3+Doped electrolyte with chemical composition of Ba1-xMxSnF4+XM is Nd and/or Eu, and x is more than 0 and less than or equal to 0.5.
2. The Nd-based according to claim 13+And/or Eu3+Doped electrolyte, characterized in that, when M is Nd and Eu, the molar ratio of Nd and Eu is 1: 0 to 0.5.
3. Nd-based according to claim 1 or 23+And/or Eu3+A method of preparing a doped electrolyte comprising the steps of:
(1) providing precursor powder;
the preparation method of the precursor powder comprises the following steps: mixing BaF2、SnF2And MF3Mixing, and sequentially performing high-energy ball milling and drying to obtain precursor powder; the MF3Is NdF3And/or EuF3；
Or comprises the following steps:
carrying out precipitation reaction on soluble salt of Ba, soluble salt of Sn and soluble salt of M with water and soluble fluorine salt under the condition of stirring, and sequentially carrying out solid-liquid separation, washing and drying on the product of the precipitation reaction to obtain precursor powder; m is Nd and/or Eu;
(2) sintering the precursor powder to obtain the Nd-based powder3+And/or Eu3+A doped electrolyte.
4. The method according to claim 3, wherein the BaF is used as a binder2、SnF2And MF3The molar ratio of (a) to (b) is [0.5 to 1): (0 to 0.5)]：(4～4.5]；
The molar ratio of the soluble salt of Ba to the soluble salt of Sn to the soluble salt of M is (0.5-1): (0 to 0.5) and (4 to 4.5).
5. The preparation method of claim 3, wherein the rotation speed of the high-energy ball mill is 500-5000 rpm, and the time is 0.5-30 h; the drying temperature is independently 40-100 ℃, and the drying time is independently 2-10 h.
6. The method of claim 3Characterized in that the soluble fluorine salt is NH4F. One or more of NaF and KF, wherein the addition coefficient of the soluble fluorine salt is 1-2.0.
7. The preparation method according to claim 3, wherein the precipitation reaction time is 0.5 to 20 hours, and the rotation speed of the stirring is 100 to 1000 rpm.
8. The preparation method according to claim 3, wherein the sintering temperature is 200-600 ℃ and the sintering time is 2-20 h.
9. A room-temperature solid-state fluorine ion battery comprising a positive electrode, a solid-state electrolyte and a negative electrode, wherein the solid-state electrolyte is the Nd-based electrolyte according to claim 1 or 23+And/or Eu3+Doped electrolyte or Nd-based electrolyte prepared by the preparation method of any one of claims 3 to 83+And/or Eu3+A doped electrolyte; the material of the positive electrode includes a metal fluoride, and the material of the negative electrode includes an active metal.
10. The room temperature solid state fluoride ion battery of claim 9, wherein the metal fluoride is CaF2、LaF3、CeF3、BiF3、MgF2、MnF3、FeF3、CuF2、PbF2And one or more of their dopants; the active metal is one or more of Cu, Ag, Ni, Co, Pb, Ce, Mn, Au, Pt, Rh, V, Os, Ru, Fe, Cr, Bi, Nb, Sb, Ti, Sn, Zn and Li.
CN202010139056.0A 2020-03-03 2020-03-03 Nd3+ and/or Eu3+ doped electrolyte, preparation method thereof and room-temperature solid-state fluorine ion battery Pending CN111313088A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112374525A (en) * 2020-11-12 2021-02-19 西南大学 Solid electrolyte material, solid electrolyte layer and preparation method thereof
CN112768761A (en) * 2021-02-25 2021-05-07 江汉大学 Sulfide solid electrolyte and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109309242A (en) * 2018-10-26 2019-02-05 湘潭大学 A kind of preparation method of all solid state fluoride ion battery to be shuttled based on fluorine ion
CN110021739A (en) * 2019-02-28 2019-07-16 湘潭大学 One kind being based on tinbase fluoride MSnF4The preparation method of the room temperature solid fluoride ion battery of stratiform fluorine ion electrolyte
US20190372111A1 (en) * 2016-12-15 2019-12-05 Honda Motor Co., Ltd. Nanostructural designs for electrode materials of fluoride ion batteries

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190372111A1 (en) * 2016-12-15 2019-12-05 Honda Motor Co., Ltd. Nanostructural designs for electrode materials of fluoride ion batteries
CN109309242A (en) * 2018-10-26 2019-02-05 湘潭大学 A kind of preparation method of all solid state fluoride ion battery to be shuttled based on fluorine ion
CN110021739A (en) * 2019-02-28 2019-07-16 湘潭大学 One kind being based on tinbase fluoride MSnF4The preparation method of the room temperature solid fluoride ion battery of stratiform fluorine ion electrolyte

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
L. N. PATRO & K. HARIHARAN: "Rare earth ions (Eu3+ and Nd3+) doped BaSnF4: transport and photoluminescence characteristics", 《IONICS》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112374525A (en) * 2020-11-12 2021-02-19 西南大学 Solid electrolyte material, solid electrolyte layer and preparation method thereof
CN112768761A (en) * 2021-02-25 2021-05-07 江汉大学 Sulfide solid electrolyte and preparation method and application thereof
CN112768761B (en) * 2021-02-25 2022-06-07 江汉大学 Sulfide solid electrolyte and preparation method and application thereof

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Application publication date: 20200619