CN105655630A - NASICON type magnesium ion solid electrolyte and preparation method thereof - Google Patents
NASICON type magnesium ion solid electrolyte and preparation method thereof Download PDFInfo
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- CN105655630A CN105655630A CN201610083033.6A CN201610083033A CN105655630A CN 105655630 A CN105655630 A CN 105655630A CN 201610083033 A CN201610083033 A CN 201610083033A CN 105655630 A CN105655630 A CN 105655630A
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic electrolyte
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
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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
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- 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 discloses an NASICON type magnesium ion solid electrolyte and a preparation method thereof. A stoichiometric equation of the NASICON type magnesium ion solid electrolyte is Mg(0.5+0.5x)AlxZr(2-x)(PO4)3, wherein x ranges from 0.1 to 0.3. According to the Al<3+> doped NASICON type magnesium ion solid electrolyte, energy required by magnesium ions in a transition process is reduced, so that the room-temperature ion conductivity of the solid electrolyte exceeds 10<-5>S/cm, the conductivity of the NASICON type magnesium ion solid electrolyte is improved to a greater extent, and building of an all-solid magnesium ion battery is greatly facilitated.
Description
Technical field
The invention belongs to magnesium ion solid electrolyte and manufacture field, be specifically related to a kind of NASICON type magnesium ion solid electrolyte and preparation method thereof.
Background technology
Along with the rapid expansion of China's generation of electricity by new energy scale, wind-power electricity generation, water generating, photovoltaic generation, regulate electric power in short-term, peak load shifting, pure electric automobile access the industrial energy storage market that will form over 200,000,000,000 yuan. Now, electrical network is just more and more prominent with the contradiction of new forms of energy development, and the demand of energy storage is also more urgent. The own important component part through becoming following intelligent grid of large-scale energy-storage system, exploitation high-efficiency energy-storage technology has great social and economic effects for improving the utilization ratio of electricity generation system, power quality and promotion regenerative resource extensive use. In current energy storage technology, one of technology of most industrialization promotion prospect is electrochemical energy storage technology, and lithium ion battery is with regard to currently used maximum electrochemical energy storing device, but lithium ion battery also exists the shortcomings such as inflammable, explosive, perishable, overcharge, overheated, short circuit all may cause fire and blast. Therefore, find a kind of high safety, the novel battery of low cost meets the market demand day by day expanded and just seems particularly urgent.
Magnesium cell is exactly a kind of potential replacer of existing lithium ion battery. In the periodic table of elements, lithium and magnesium are diagonal elements, have similar physicochemical properties, and magnesium is a kind of cheap, and storage is abundant, the element of light weight, environmental protection and relatively easily processing; In chemical property, magnesium has higher theoretical charging capacity (2205Ah kg-1) and theoretical energy density (3.8Ah cm-3), therefore so that magnesium becomes a kind of possibility in battery applications. but the technical difficult points that currently exploitation magnesium cell exists is exactly do not find suitable electrolyte, and the compound of NASICON type is a kind of potential ideal chose being applied to following all solid state Magnesium ion battery, this is because NASICON structure just has sufficiently large gap to fill other ions, and the high structural stability based on its 3D network skeleton, and it is a kind of structure being beneficial to magnesium ion transmission, the Magnesium ion battery solid electrolyte therefore with NASICON structure has the possibility being applied to all solid state Magnesium ion battery, therefore develop a kind of suitable magnesium ion electrolyte be applied to all solid state Magnesium ion battery will be very meaningful.
Summary of the invention
The technical problem to be solved is a kind of Al provided for existing background technology3+The NASICON type magnesium ion solid electrolyte Mg of doping0.5+0.5xAlxZr2-x(PO4)3, there is A in NASICON framing structureIAnd AIITwo kinds of magnesium ion interstitial sites, for Mg0.5+0.5xAlxZr2-x(PO4)3, pass through Al3+Doping, magnesium ion concentration increases, and the increase of carrier concentration improves magnesium ion and occupies A simultaneouslyIAnd AIIThe probability of position, reduces the energy that magnesium ion needs in transition process so that the room temperature ionic conductivity of this solid electrolyte is more than 10-5S/cm so that it is all-solid-state battery can be applied to.
The present invention reaches by the following technical solutions, and this technical scheme provides a kind of magnesium ion electrical conductivity more than 10-5The magnesium ion solid electrolyte of S/cm, its stoichiometric equation is Mg0.5+0.5xAlxZr2-x(PO4)3, wherein: x=0.1-0.3. In this technical scheme, by C4H6O4Mg��4H2O:Zr (NO3)4��5H2O:(NH4)2HPO4: Al (NO3)3��9H2O is the weighing accurate in scale of 0.55-0.65:1.7-1.9:3:0.1-0.3 (mol ratio), inserts beaker and adds appropriate amount of deionized water mix homogeneously, and at 60-100 DEG C of temperature, continuous constant temperature stirring 1h-10h is so as to generate co-precipitation thing. The precipitate being obtained by reacting is 60-90 DEG C of drying in air dry oven, 4h is calcined subsequently in the air atmosphere of 400 DEG C, obtain presoma, presoma is put in ball grinder, with isopropanol be solvent, zirconia ball mill for ball-milling medium, under 300-500r/min speed, forward and reverse ball milling 6h that hockets, interval is 1h, dries the powder obtaining even particle size. It is 10mm that powder is pressed into diameter under 50-100MPa pressure, and thickness is the thin slice of 2mm. Adopt pressureless sintering method to calcine 5h-10h at 650-850 DEG C and obtain electrolyte sheet.
Compared with prior art, it is an advantage of the current invention that:
Al3+Introducing can make Pedicellus et Pericarpium Trapae side's mutually at room temperature stable existence and Al3+Part substitutes Zr4+, make magnesium ion concentration increase, the increase of carrier concentration improves magnesium ion and occupies A simultaneouslyIAnd AIIThe probability of position, reduces the energy that magnesium ion needs in transition process so that the room temperature ionic conductivity of this solid electrolyte is more than 10-5S/cm, improves the electrical conductivity of NASICON type magnesium ion solid electrolyte significantly. It is very beneficial for the structure of all solid state Magnesium ion battery.
Accompanying drawing explanation
Fig. 1 is the magnesium ion solid electrolyte flake of the embodiment of the present invention 1 preparation AC impedance figure under electrochemical workstation;
Fig. 2 is the magnesium ion solid electrolyte flake of the embodiment of the present invention 2 preparation AC impedance figure under electrochemical workstation;
Fig. 3 is the magnesium ion solid electrolyte flake of the embodiment of the present invention 3 preparation AC impedance figure under electrochemical workstation;
Fig. 4 is the X ray diffracting spectrum of the magnesium ion solid electrolyte flake of the embodiment of the present invention 3 preparation;
Fig. 5 is the electron scanning micrograph of the magnesium ion solid electrolyte flake cross section of the embodiment of the present invention 3 preparation.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: in this embodiment,
By C4H6O4Mg��4H2O:Zr (NO3)4��5H2O:(NH4)2HPO4: Al (NO3)3��9H2O is the weighing accurate in scale of 0.55:1.9:3:0.1 (mol ratio), inserts beaker and adds appropriate amount of deionized water mix homogeneously, and at 60 DEG C of temperature, continuous constant temperature stirring 5h is so as to generate co-precipitation thing. The precipitate being obtained by reacting is 70 DEG C of drying in air dry oven, 4h is calcined subsequently in the air atmosphere of 400 DEG C, obtain presoma, presoma is put in ball grinder, with isopropanol be solvent, zirconia ball mill for ball-milling medium, under 350r/min speed, forward and reverse ball milling 6h that hockets, interval is 1h, dries the powder obtaining even particle size. It is 10mm that powder is pressed into diameter under 50MPa pressure, and thickness is the thin slice of 2mm. Adopting pressureless sintering method to calcine 10h at 750 DEG C and obtain electrolyte sheet, its stoichiometric equation is Mg0.55Al0.1Zr1.9(PO4)3. Being illustrated in figure 1 magnesium ion solid electrolyte flake AC impedance figure under electrochemical workstation, the all-in resistance of electrolyte sheet is 12000 ��, by the computing formula of electrical conductivityCan calculate the lithium ion conductivity obtaining electrolyte sheet is 2.12 �� 10- 5S/cm��
Embodiment 2: in this embodiment,
By C4H6O4Mg��4H2O:Zr (NO3)4��5H2O:(NH4)2HPO4: Al (NO3)3��9H2O is the weighing accurate in scale of 0.60:1.8:3:0.2 (mol ratio), inserts beaker and adds appropriate amount of deionized water mix homogeneously, and at 70 DEG C of temperature, continuous constant temperature stirring 5h is so as to generate co-precipitation thing.The precipitate being obtained by reacting is 70 DEG C of drying in air dry oven, 4h is calcined subsequently in the air atmosphere of 400 DEG C, obtain presoma, presoma is put in ball grinder, with isopropanol be solvent, zirconia ball mill for ball-milling medium, under 300r/min speed, forward and reverse ball milling 6h that hockets, interval is 1h, dries the powder obtaining even particle size. It is 10mm that powder is pressed into diameter under 60MPa pressure, and thickness is the thin slice of 2mm. Adopting pressureless sintering method to calcine 10h at 700 DEG C and obtain electrolyte sheet, its stoichiometric equation is Mg0.6Al0.2Zr1.8(PO4)3. Being illustrated in figure 2 magnesium ion solid electrolyte flake AC impedance figure under electrochemical workstation, the all-in resistance of electrolyte sheet is 16000 ��, by the computing formula of electrical conductivityCan calculate the lithium ion conductivity obtaining electrolyte sheet is 1.59 �� 10- 5S/cm��
Embodiment 3: in this embodiment,
By C4H6O4Mg��4H2O:Zr (NO3)4��5H2O:(NH4)2HPO4: Al (NO3)3��9H2O is the weighing accurate in scale of 0.65:1.9:3:0.3 (mol ratio), inserts beaker and adds appropriate amount of deionized water mix homogeneously, and at 80 DEG C of temperature, continuous constant temperature stirring 5h is so as to generate co-precipitation thing. The precipitate being obtained by reacting is 70 DEG C of drying in air dry oven, 4h is calcined subsequently in the air atmosphere of 400 DEG C, obtain presoma, presoma is put in ball grinder, with isopropanol be solvent, zirconia ball mill for ball-milling medium, under 300r/min speed, forward and reverse ball milling 6h that hockets, interval is 1h, dries the powder obtaining even particle size. It is 10mm that powder is pressed into diameter under 100MPa pressure, and thickness is the thin slice of 2mm. Adopting pressureless sintering method to calcine 5h at 750 DEG C and obtain electrolyte sheet, its stoichiometric equation is Mg0.65Al0.3Zr1.7(PO4)3, Fig. 3 is the magnesium ion solid electrolyte flake prepared of this embodiment AC impedance figure under electrochemical workstation, sees that the all-in resistance of electrolyte sheet is 30000 �� from figure, and the all-in resistance of electrolyte sheet is 13000 ��, by the computing formula of electrical conductivityCan calculate the lithium ion conductivity obtaining electrolyte sheet is 1.95 �� 10-5S/cm. , Fig. 4 is the X ray diffracting spectrum of magnesium ion solid electrolyte flake prepared by this embodiment, can determine the crystal structure of electrolyte powder body from figure. Fig. 5 is the electron scanning micrograph of magnesium ion solid electrolyte flake cross section prepared by this embodiment.
Embodiment 4: in this embodiment,
By C4H6O4Mg��4H2O:Zr (NO3)4��5H2O:(NH4)2HPO4: Al (NO3)3��9H2O is the weighing accurate in scale of 0.65:1.9:3:0.3 (mol ratio), inserts beaker and adds appropriate amount of deionized water mix homogeneously, and at 80 DEG C of temperature, continuous constant temperature stirring 5h is so as to generate co-precipitation thing. The precipitate being obtained by reacting is 70 DEG C of drying in air dry oven, 4h is calcined subsequently in the air atmosphere of 400 DEG C, obtain presoma, presoma is put in ball grinder, with isopropanol be solvent, zirconia ball mill for ball-milling medium, under 400r/min speed, forward and reverse ball milling 6h that hockets, interval is 1h, dries the powder obtaining even particle size. It is 10mm that powder is pressed into diameter under 50MPa pressure, and thickness is the thin slice of 2mm. Adopting pressureless sintering method to calcine 10h at 800 DEG C and obtain electrolyte sheet, its stoichiometric equation is Mg0.65Al0.3Zr1.7(PO4)3��
Claims (5)
1. a NASICON type magnesium ion solid electrolyte, it is characterised in that: its stoichiometric equation is Mg0.5+0.5xAlxZr2-x(PO4)3, wherein: x=0.1-0.3.
2. NASICON type magnesium ion solid electrolyte according to claim 1, it is characterised in that: x=0.1.
3. a NASICON type magnesium ion method for preparing solid electrolyte, comprises the following steps:
1) by C4H6O4Mg��4H2O:Zr (NO3)4��5H2O:(NH4)2HPO4: Al (NO3)3��9H2O is (0.55-0.65) according to mol ratio: (1.7-1.9): 3:(0.1-0.3) add in reaction vessel, rear addition deionized water mix homogeneously;
2) at 60-100 DEG C of temperature, continuous constant temperature stirring 1h-10h generates co-precipitation thing;
3) by step 2) in the co-precipitation thing that obtains put in air dry oven, dry at 60-90 DEG C of temperature, after in the air atmosphere of 400 DEG C, calcine 4h, obtain presoma;
4) presoma is put in ball grinder, grind post-drying and obtain powder;
5) powder is pressed into thin slice under 50-100MPa pressure, adopts pressureless sintering method to calcine 5h-10h at 650-850 DEG C and obtain NASICON type magnesium ion solid electrolyte sheet.
4. NASICON type magnesium ion method for preparing solid electrolyte according to claim 3, it is characterized in that: step 4) particularly as follows: presoma is put in ball grinder, with isopropanol be solvent, zirconia ball mill is for ball-milling medium, under 300-500r/min speed, forward and reverse ball milling 6h that hockets, interval is 1h, dries the powder obtaining even particle size.
5. the NASICON type magnesium ion method for preparing solid electrolyte according to claim 3 or 4, it is characterised in that: the diameter of described thin slice is 10mm, and thickness is 2mm.
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| CN201610083033.6A CN105655630A (en) | 2016-02-05 | 2016-02-05 | NASICON type magnesium ion solid electrolyte and preparation method thereof |
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| CN201610083033.6A CN105655630A (en) | 2016-02-05 | 2016-02-05 | NASICON type magnesium ion solid electrolyte and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526697A (en) * | 2019-06-27 | 2019-12-03 | 宁波大学 | A kind of liquid phase synthesis K6.25Be0.1Al0.1P0.05Ti0.05Si1.7O7Potassium fast-ionic conductor and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811828A (en) * | 2009-02-23 | 2010-08-25 | 中国科学院上海硅酸盐研究所 | NASICON structure glass ceramic sodion solid electrolytes and preparation method thereof |
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2016
- 2016-02-05 CN CN201610083033.6A patent/CN105655630A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811828A (en) * | 2009-02-23 | 2010-08-25 | 中国科学院上海硅酸盐研究所 | NASICON structure glass ceramic sodion solid electrolytes and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| LEZHI HUANG等: ""Electrochemical properties of Li1.4Al0.4Ti1.6(PO4)3 synthesized by a co-precipitation method"", 《JOURNAL OF POWER SOURCES》 * |
| N.K.ANUAR等: ""Characterization of Mg0.5Zr2(PO4)3 for potential use as electrolyte in solid state magnesium batteries"", 《CERAMICS INTERNATIONAL》 * |
| XIAOJUAN LU等: ""Study of NASICON Structured Lithium Ion Conductor Li1+xAlxZr2-x(PO4)3"", 《INTERNATIONAL CONFERENCE ON ADVANCES IN ENERGY, ENVIRONMENT AND CHEMICAL ENGINEERING (AEECE) 》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526697A (en) * | 2019-06-27 | 2019-12-03 | 宁波大学 | A kind of liquid phase synthesis K6.25Be0.1Al0.1P0.05Ti0.05Si1.7O7Potassium fast-ionic conductor and preparation method thereof |
| CN110526697B (en) * | 2019-06-27 | 2021-12-03 | 宁波大学 | Liquid phase synthesis K6.25Be0.1Al0.1P0.05Ti0.05Si1.7O7Potassium fast ion conductor and preparation method thereof |
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