CN114050311A - Associated boron cage ionic compound fast ion conductor material and preparation method thereof - Google Patents
Associated boron cage ionic compound fast ion conductor material and preparation method thereof Download PDFInfo
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- CN114050311A CN114050311A CN202111217678.1A CN202111217678A CN114050311A CN 114050311 A CN114050311 A CN 114050311A CN 202111217678 A CN202111217678 A CN 202111217678A CN 114050311 A CN114050311 A CN 114050311A
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Abstract
The invention belongs to the technical field of fast ion conductors, and particularly relates to a combined boron cage ion compound fast ion conductor material and a preparation method thereof. The main component of the associated boron cage type fast ion conductor material of the invention is MB20H18And/or MB20H19(ii) a Wherein M is a metal cation and the anion is B20H18 2‑Or B20H19 3‑(ii) a The metal cation M is a single metal ion or a plurality of complex metal ions. The preparation method comprises the use of B20H18 2‑Or B20H19 3‑By reaction of the starting materials with the corresponding metals or metal compounds, to give MB20H18Or MB20H19A solution of the compound; and (3) evaporating to remove the solvent, and then carrying out vacuum high-temperature heat treatment to completely remove the solvent to obtain the solvent-free target compound. The fast ion conductor of the inventionHas the advantages of good thermal/chemical stability, high ionic conductivity, wide electrochemical window and the like, and can be used for liquid batteries, super capacitors, all-solid-state inorganic salt electrolytes and polymer electrolytes.
Description
Technical Field
The invention belongs to the technical field of fast ion conductors, and particularly relates to a combined boron cage fast ion conductor and a preparation method thereof.
Background
With the rapid development of energy and electronic industries, the demand of people for energy storage devices is gradually increasing. The research on secondary batteries such as lithium ion batteries, sodium ion batteries, potassium ion batteries, and the like is receiving more and more attention. This type of battery generally consists of four parts, a positive electrode, a negative electrode, a separator and an electrolyte, and mainly relies on the movement of metal ions between the positive and negative electrodes. The metal ions move back and forth between the positive electrode and the negative electrode through the electrolyte, so that the charge-discharge cycle of the battery is realized, and the diaphragm plays a role in preventing short circuit. Conventional electrolytes consist of metal salts and organic solvents. However, the organic solvent is very easy to damage the structure of the cathode material in the charging process, so that the electrode is passivated, and the safety problems of the battery, such as flammability, explosiveness, liquid leakage and the like, often occur. Therefore, it is required to develop a novel electrolyte to solve the above problems.
Fast ionic conductors, also known as solid electrolytes, exhibit high ionic conductivity over a specific temperature range. As a solid ion conductor, the high-temperature-resistant conductive material has the advantages of excellent safety, excellent high-temperature performance, large potential window and the like. Chinese patent CN113105239-a reports a garnet-type oxide lithium ion conductor. The method is characterized in that 1-10 wt.% of lithium sulfide is used as a dopant raw material and is prepared by a solid-phase sintering method. Lithium is supplemented into the lithium sulfide to replace sulfur element in the crystal structure, so that a cubic phase is formed, and the room-temperature conductivity of the lithium sulfide is improved. Chinese patent CN112151859-a describes a composite solid electrolyte, which is obtained by mixing a three-dimensional skeleton precursor of a ceramic filler layer with an anti-reduction polymer, an anti-oxidation polymer, a lithium salt and a plasticizer, adding a certain proportion of an initiator, and drying. In 2014, Orimo et al first proposedNa2B12H12Can be used as fast ion conductor, Na in the range of 270-300 DEG C2B12H12Has an ionic conductivity of approximately or more than 0.1S cm-1. Chinese patent 201711268024.5 reports a lithium borohydride based fast ion conductor. The conductor being LiBH4And NaCl or LiBH4 And NaI, and is obtained by mixing the two phases in a molar ratio of (1-10):1 under the condition of isolating air, and is characterized by excellent electric conductivity under low temperature. 2017, Yoshida et al prepared a series of Na mixed by ball milling in different proportions2B12H12/Na2B10H10Fast ion conductor, mixed at a 3:1 ratio, was found to have a maximum ionic conductivity of 10 at room temperature- 3.5S cm−1. First para-carborane CB of Udovic et al in 20159H10 -、CB11H12 -Application exploration is carried out in the field of fast ion conductors. MCB11H12Compared with M2B12H12(M = Li, Na) has a lower phase transition temperature and a similarly high conductivity.
Researches find that the boron cage compound has excellent thermal/chemical stability, higher ionic conductivity and wide electrochemical window, and is suitable for being used as a fast ion conductor for development and application. The invention develops a novel associated boron cage fast ion conductor MB20H18And MB20H19M cation is a metal ion and anion is B20H18 2-Or B20H19 3-. The material is used as a fast ion conductor material of cations such as hydrogen, sodium, lithium, potassium, magnesium, calcium, aluminum, zinc, silver and the like, and has the advantages of higher ionic conductivity, excellent electrochemical stability, good thermal stability and the like; meanwhile, the material is simple and safe to prepare, is suitable for all-solid-state inorganic salt electrolytes, polymer electrolytes and liquid electrolytes, and is expected to be applied to energy storage devices such as batteries and super capacitors.
Disclosure of Invention
The invention aims to provide a coupled boron cage ionic compound fast ion conductor material with high ionic conductivity, excellent electrochemical stability and good thermal stability and a preparation method thereof.
The invention provides a coupled boron cage ionic compound fast ion conductor material, which mainly comprises MB20H18And MB20H19Wherein M is a metal cation and the anion is B20H18 2-Or B20H19 3-(ii) a The metal ion M is a single metal ion or a plurality of composite metal ions.
Further, M is selected from Na, Li, K, Mg, Zn, Al, Ag, Ca and H;
the fast ion conductor has good ionic conductivity, thermal/chemical stability and electrochemical stability, and has application prospects in the aspects of solid electrolytes, liquid electrolytes, electrolytes used in combination with other salts of metal ion batteries, polymer electrolytes formed by polymer matrixes and the like.
The invention provides a preparation method of the associated boron cage ionic compound fast ion conductor material, which comprises the following specific steps:
first, use B20H18 2-Or B20H19 3-By reaction of the starting materials with the corresponding metals or metal compounds, to give MB20H18Or MB20H19A solution of the compound;
then, the solvent was distilled off to obtain MB20H18Or MB20H19A solvent compound of the compound; and continuing vacuum high-temperature heat treatment, and completely removing the solvent to obtain the solvent-free target compound.
In the present invention, said B20H18 2-The starting material is H2B20H18A hydrate, or a salt of the material in combination with an amine; b is20H19 3-The starting material is H3B20H19Hydrates, or salts of the material in combination with amines.
In the present invention, the metal or metal compound is selected from sodium, lithium, potassium, magnesium, calcium, aluminum, zinc; the metal compound is selected from the group consisting of hydroxides, hydrides, carbonates.
In the invention, the vacuum high-temperature heat treatment is carried out at the temperature of 60-200 ℃ for 0.5-3 hours.
The associated boron cage ionic compound fast ion conductor material provided by the invention can be used independently or can be used after being compounded with other materials; the mode of use includes direct application to a solid electrolyte, or use as a salt in a liquid electrolyte or polymer electrolyte.
Compared with the organic electrolyte which is widely used in the metal ion battery and is formed by combining metal salt and organic liquid, the fast ion conductor not only has the advantages of good thermal/chemical stability, high ionic conductivity, wide electrochemical window and the like, but also can be independently used as a battery electrolyte, can also have excellent room-temperature ionic conductivity when being independently used as a solid electrolyte, and can be used in a liquid battery, a super capacitor, an all-solid inorganic salt electrolyte and a polymer electrolyte.
Drawings
FIG. 1 shows Na2B20H18Ion conductivity of fast ion conductors at different temperatures.
FIG. 2 shows Na2B20H18Na/Na in 0-5V vs+Scanning voltammogram of (a).
FIG. 3 is Na2B20H18Wherein the inset is the impedance plot before and after polarization.
FIG. 4 is Li2B20H18Ion conductivity of fast ion conductors at different temperatures.
FIG. 5 shows Na2B20H18/Na2B12H12The ionic conductivity of the composite fast ionic conductor at different temperatures.
FIG. 6 shows Na3B20H19Ion conductivity of fast ion conductors at different temperatures.
FIG. 7 is Li3B20H19Different temperatures of fast ion conductorDegree of ionic conductivity.
Detailed Description
The invention is further described below by means of specific examples.
Example 1, Na2B20H18Fast ion conductor preparation
Taking dry (Et)4N)2B20H18Dissolving in acetonitrile/water solvent, passing through strong acid cation resin to obtain (H)3O)2B20H18The solution is reacted with sodium hydroxide aqueous solution to obtain Na2B20H18The solution was rotary evaporated to dryness and the product was heated at 150 ℃ under vacuum for 3.0 hours to give Na2B20H18. Conductivity test of fast ion conductor with electrochemical workstation (CHI 760E, Shanghai) as detection device, and three-electrode system, solid fast ion conductor Na2B20H18Tabletting to obtain a test sheet with a certain thickness and area; assembling the stainless steel substrate, the fast ion conductor test piece and the stainless steel substrate from bottom to top, testing alternating current impedance (AC impedance) at different temperatures, and according to the formula: σ =d / (R × A) Wherein d is the sample thickness, R is the impedance value, and A is the sample area. The ionic conductivities of the materials at different temperatures were calculated as shown in fig. 1. The results show that the material has an ionic conductivity of 2.5X 10 at room temperature-6S/cm. Assembly of Na | Na2B20H18SUS half-cell and Na2B20H18| Na symmetrical cell, test Na2B20H18The electrochemical window and ion transport number of (2) are shown in FIGS. 2 and 3. The results show that Na2B20H18Has a wide electrochemical window (5V vs. Na/Na)+Above) and higher ion transport number (. tau.Na)+=0.87）。
Example 2, Li2B20H18Fast ion conductor preparation
Drying (Et)4N)2B20H18Dissolving in acetonitrile/water, etc., and passing through strong acid cationAfter resinating, obtaining (H)3O)2B20H18Then reacting with lithium hydroxide solution to obtain Li2B20H18After the solution is evaporated and dried, the product is heated for 3.0 hours at the high temperature of 150 ℃ to obtain the fast ion conductor Li2B20H18. At different temperatures, ac impedance tests were performed and the ionic conductivities of the materials at different temperatures were calculated according to the formula, with the results shown in fig. 4. The measurement results show that Li at room temperature2B20H18Ionic conductivity of 1.1X 10-6S/cm。
Example 3, Na2B20H18/Na2B12H12Composite fast ion conductor
Drying Na2B20H18And Na2B12H12Mixing the materials in a molar ratio of 1:1, 1:2, 1:3, 1:4, 1:5 and 1:6 respectively, adding the mixture into a ball milling tank respectively, and ball milling the mixture for 3.0 hours in the absence of air at a rotating speed of 400 revolutions per minute to obtain Na2B20H18/Na2B12H12And compounding the fast ion conductor. At different temperatures, the ac impedance test was performed separately and the ionic conductivities of the materials at different temperatures were calculated according to the formula, the results are shown in fig. 5. The measurement and calculation results show that Na is contained at room temperature2B20H18-4Na2B12H12The conductivity is 2.8 x 10 at most-4S/cm。
Example 4, Na3B20H19Fast ion conductor preparation
Taking dry (Et)4N)3B20H19Dissolving in acetonitrile/water solvent, passing through strong acid cation resin to obtain (H)3O)3B20H19The solution is reacted with sodium hydroxide aqueous solution to obtain Na3B20H19The solution was rotary evaporated to dryness and the product was heated at 150 ℃ under vacuum for 3.0 hours to give Na3B20H19. Mixing solid fast ion conductor Na3B20H19Tabletting to obtain a tablet of a certain thicknessTest sheet of area and at different temperatures, an alternating current impedance (AC impedance) test was carried out and according to the formula: σ =d / (R × A) The ionic conductivities of the materials at different temperatures were calculated as shown in fig. 6. The results show that the material has an ionic conductivity of 1.2X 10 at room temperature-5S/cm。
Example 5, Li3B20H19Fast ion conductor preparation
Taking dry (Et)4N)3B20H19Dissolving in acetonitrile/water solvent, passing through strong acid cation resin to obtain (H)3O)3B20H19The solution is reacted with lithium hydroxide aqueous solution to obtain Li3B20H19The solution is rotary evaporated and dried, and the product is obtained at 150 deg.CoHeating the mixture in vacuum for 3.0 hours to obtain Li3B20H19. At different temperatures, alternating current impedance (AC impedance) tests were performed and according to the formula: σ =d / (R × A). The ionic conductivities of the materials at different temperatures were calculated as shown in fig. 7. The results show that the material has an ionic conductivity of 10 at room temperature-6S/cm。
Claims (7)
1. A coupled boron cage ionic compound fast ion conductor material is characterized in that the main component is MB20H18And/or MB20H19(ii) a Wherein M is a metal cation and the anion is B20H18 2-And/or B20H19 3-(ii) a The metal cation M is a single metal ion or a plurality of complex metal ions.
2. The associated boron caged ion compound fast ion conductor material of claim 1, wherein the metal cation M is selected from lithium, potassium, sodium, calcium, magnesium, aluminum, zinc, silver, hydrogen.
3. The preparation method of the associated boron caged ionic compound fast ion conductor material of claim 1 or 2, which is characterized by comprising the following specific steps:
(1) using B20H18 2-Or B20H19 3-By reaction of the starting materials with the corresponding metals or metal compounds, to give MB20H18Or MB20H19A solution of the compound;
(2) distilling off the solvent to obtain MB20H18Or MB20H19A solvent compound of the compound; and continuing vacuum high-temperature heat treatment, and completely removing the solvent to obtain the solvent-free target compound.
4. The method for preparing the associated boron caged ionic compound fast ion conductor material of claim 3, wherein B is20H18 2-The starting material is H2B20H18A hydrate, or a salt of the material in combination with an amine; b is20H19 3-The starting material is H3B20H19Hydrates, or salts of the material in combination with amines.
5. The method for preparing the associated boron cage ionic compound fast ion conductor material according to claim 3, wherein the metal or the metal in the metal compound is selected from sodium, lithium, potassium, magnesium, calcium, aluminum, zinc; the metal compound is selected from the group consisting of hydroxides, hydrides, carbonates.
6. The method for preparing the associated boron caged-ion compound fast-ion conductor material according to claim 3, wherein the vacuum high-temperature heat treatment is carried out at a temperature of 60-200 ℃ for 0.5-3 hours.
7. The use method of the associated boron caged ionic compound fast ion conductor material according to claim 1 or 2, characterized in that the associated boron caged ionic compound fast ion conductor material is used alone or after being compounded with other materials; the mode of use includes direct application to a solid electrolyte, or use as a salt in a liquid electrolyte or polymer electrolyte.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070068071A1 (en) * | 2005-09-21 | 2007-03-29 | Kelly Michael T | Compositions and methods for hydrogen generation |
| CN108155411A (en) * | 2017-12-05 | 2018-06-12 | 东南大学 | A kind of lithium borohydride compound fast-ionic conductor and preparation method thereof |
| CN112467197A (en) * | 2020-11-24 | 2021-03-09 | 安徽工业大学 | Lithium borohydride/decaborane solid electrolyte and preparation method thereof |
| US20210234192A1 (en) * | 2019-04-24 | 2021-07-29 | University Of Shanghai For Science And Technology | All-Solid-State Lithium Battery and Preparation Method Thereof |
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- 2021-10-19 CN CN202111217678.1A patent/CN114050311A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070068071A1 (en) * | 2005-09-21 | 2007-03-29 | Kelly Michael T | Compositions and methods for hydrogen generation |
| CN108155411A (en) * | 2017-12-05 | 2018-06-12 | 东南大学 | A kind of lithium borohydride compound fast-ionic conductor and preparation method thereof |
| US20210234192A1 (en) * | 2019-04-24 | 2021-07-29 | University Of Shanghai For Science And Technology | All-Solid-State Lithium Battery and Preparation Method Thereof |
| CN112467197A (en) * | 2020-11-24 | 2021-03-09 | 安徽工业大学 | Lithium borohydride/decaborane solid electrolyte and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| TERRENCE J. UDOVIC等: "Sodium superionic conduction in Na2B12H12", 《CHEMICAL COMMUNICATIONS》 * |
| 程勇强等: "硼氢化锂及其衍生物固态电解质研究进展", 《广州化工》 * |
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