CN110372349A - A kind of P5+、Al3+、Be2+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof - Google Patents

A kind of P5+、Al3+、Be2+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof Download PDF

Info

Publication number
CN110372349A
CN110372349A CN201910617291.1A CN201910617291A CN110372349A CN 110372349 A CN110372349 A CN 110372349A CN 201910617291 A CN201910617291 A CN 201910617291A CN 110372349 A CN110372349 A CN 110372349A
Authority
CN
China
Prior art keywords
fast
potassium
hours
ionic conductor
ion
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.)
Withdrawn
Application number
CN201910617291.1A
Other languages
Chinese (zh)
Inventor
水淼
舒杰
任元龙
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 University
Original Assignee
Ningbo University
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 University filed Critical Ningbo University
Priority to CN201910617291.1A priority Critical patent/CN110372349A/en
Publication of CN110372349A publication Critical patent/CN110372349A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/447—Phosphates or phosphites, e.g. orthophosphate, hypophosphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • 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
    • 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

A kind of P5+、Al3+、Be2+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof, it is characterized in that: stoichiometric equation K6+2x+y‑zBexAlyPzSi2‑x‑y‑zO7, in which: x=0.05-0.10；Y=0.05-0.10；Z=0.02-0.05；Room temperature potassium ion conductivity is more than 510‑4S/cm.Using Al3+、Be2+Part replaces Si4+Ion generates gap potassium ion in crystal and reduces potassium ion migration activation energy；Pass through P5+Doping further decreases the electron conduction of fast-ionic conductor；Pass through the Be of small ionic radii2+Doping adjusts the size of the migrating channels of potassium ion to adapt to the fast transferring of potassium ion；And during the preparation process in K6Si2O7The surface of particle is modified, and easy-sintering characteristic is formed.These synergistic effects are so that the room temperature potassium ion conductivity of the potassium fast-ionic conductor is more than 510‑4S/cm is more nearly the potassium ion conductivity of liquid electrolyte.

Description

A kind of P5+、Al3+、Be2+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and its Preparation method
Technical field
The present invention relates to a kind of solid potassium fast-ionic conductor manufacturing fields.
Background technique
Lithium ion battery has volume, weight energy than high, voltage is high, self-discharge rate is low, memory-less effect, cycle life The absolute advantages such as length, power density height possess in global mobile power source market and exceed 30,000,000,000 dollar/year shares and far more than other The occupation rate of market of battery is electrochmical power source [Wu Yuping, Wan Chunrong, Jiang Changyin, the lithium ion two of most market development prospect Primary cell, Beijing: Chemical Industry Press, 2002.].Lithium ion secondary battery is most of using liquid both at home and abroad at present Electrolyte, liquid lithium ionic cell have some unfavorable factors, and such as: liquid organic electrolyte may be revealed, in excessively high temperature Lower generation explosion can not apply the occasion high in some pairs of security requirements to cause safety accident；Liquid electrolyte lithium from The sub- generally existing Capacity fading problem of battery, after a period of use due to electrode active material in the electrolyte molten Solution, reaction and degradation failure [Z.R.Zhang, Z.L.Gong, and Y.Yang, J.Phys.Chem.B, 108,2004, 17546.].And all-solid-state battery it is highly-safe, substantially without Capacity fading, wherein fast as the solid that electrolyte uses Ion conductor also acts the effect of diaphragm, simplifies the structure of battery；Further, since also simplifying life without completely cutting off air To the requirement of equipment during production, the configuration design of battery is also more convenient and flexible, and [Wen Zhaoyin, Zhu Xiujian know hero etc., entirely perhaps The research of solid secondary batteries, the 12nd Chinese solid-state ionics academic meeting paper collection, 2004.].
In all-solid lithium-ion battery, migration rate of the carrier in fast-ionic conductor is often far smaller than electrode surface Electric charge transfer and ion diffusion rates in positive electrode and become the rate determining step in entire electrode reaction dynamics, Therefore it is the core key for constructing high performance lithium ion battery that developing, which has the inorganic fast ionic conductor of higher li ionic conductivity, Place.From the point of view of current lithium fast-ionic conductor Development Status: LLTO (Li, La) TiO3Fast-ionic conductor has very high transgranular Conductivity is (10-3S/cm or so) and relatively high room temperature total conductivity (10-4S/cm-10-5S/cm), but LLTO decomposes electricity It forces down, the above all-solid-state battery of discharge voltage 3.7V and unstable to lithium anode can not be constituted；It is more with NASICON type Brilliant LiM2(PO4)3(M=Ti, Ge, Zr) is by tetrahedron PO4With octahedra MO6The grid structure collectively constituted, generation finish Hole and fillable coordination on structure, allow to regulate and control a large amount of Li ion, are a kind of up-and-coming high-lithium ion electricity Conductance fast-ionic conductor.By the substitution of aliovalent ion, introduce hole in the structure or calking lithium ion can further improve from Subconductivity [Xiaoxiong Xu, Zhaoyin Wen, ZhonghuaGu, etal., Solid State Ionics, 171, 2004,207-212.].Such as woods ancestral Zuxiang, Li Shichun [woods ancestral Zuxiang, Li Shichun, silicate journal, 9 (3), 1981,253-257.] It was found that Li1+xTi2-xGaxP3O12, Li1+2xTi2-xMgxP3O12, Li1+xGe2-xCrxP3O12, Li1+xGe2-xAlxP3O12, Li1+ xTi2-xInxP3O12Etc. systems or other such as Li1+2x+2yAlxMgyTi2-x-ySixP3-xO12, Li1+x+yAlxTi2-xSiyP3-yO12, Li1+ xAlxTi2-xP3O12Etc. systems all have higher lithium ion conductivity.But the room temperature lithium ion conductivity of these systems usually exists 10-4S/cm-10-6Between S/cm, requirement of the non-film lithium ion battery to electrolytic conductivity can't be met very well.In addition NASICON system is equally unstable to lithium anode.Ramaswamy Murugan is equal to 2007 in German application term A kind of novel lithium ion fast-ionic conductor Li has been reported on periodical7La3Zr2O12Its lithium ion conductivity at normal temperature is more than 1 × 10-4S·cm-1, decomposition voltage is more than 5.5V, and lithium metal can be used as cathode, be that one kind has very much to air and moisture stabilization The fast ion solid electrolyte of the lithium of application potential (Ramaswamy Murugan, Venkataraman Thangadurai, Werner Weppner, (2007) " Fast lithium ion conduction in garnet-type Li7La3Zr2O12" Angewandte Chemie-International Edition 46 (41): 7778-7781.).However 5.0 × 10 will often be reached to the higher occasion conductivity of current requirements-4S/cm or so just can satisfy normal battery operation It needs, in addition the solid electrolyte synthesis temperature is at 1350 DEG C or so, and temperature is high, and energy consumption is high.
It additionally needs and is pointed out that the consumption of lithium rises rapidly as secondary cell is quickly applied in power battery, Reserves of the elemental lithium in the earth's crust very it is low only PPM grade, rare lithium resource make future lithium ion battery cost it is continuous on It rises.The electrochemical energy storing device for seeking a kind of alternative low cost becomes urgent problem to be solved.Sodium and potassium element are in the earth The electrochemical properties very high and with lithium of abundance have certain similar, be following to be expected to replace most having for lithium ion all-solid-state battery uncommon The selection of prestige.However the building essential potassium ion conductor of potassium ion all-solid-state battery is also substantially at space state at present. Therefore screening has the potassium fast ion conducting material of high conductance to the inexpensive kalium ion battery of building and full-solid potassium ion Battery has great importance.
Summary of the invention
A kind of P that the technical problem to be solved by the present invention is to provide for existing background technique5+、Al3+、Be2+Ion Cooperate with the K of doping6Si2O7Potassium fast-ionic conductor and preparation method thereof.Using Al3+、Be2+Part replaces Si4+Ion, in crystal High concentration gap potassium ion is generated, to generate more potassium ions collaboration migration of short distance, helping, which reduces potassium ion migration, lives Change energy；Pass through P5+Doping further decreases the electron conduction of fast-ionic conductor；Pass through the Be of small ionic radii2+Doping is adjusted The size of the migrating channels of potassium ion is to adapt to the fast transferring of potassium ion；And during the preparation process in K6Si2O7The surface of particle Modified, form easy-sintering characteristic, be conducive to improve the potassium fast-ionic conductor reduced when preparing bulk devices crystal boundary gap, Increase consistency to improve the potassium ion conductivity of block potassium fast-ionic conductor.These synergistic effects are so that the fast ion of the potassium is led The room temperature potassium ion conductivity of body is more than 510-4S/cm is more nearly the potassium ion conductivity of liquid electrolyte.
The present invention reaches by the following technical solutions, which provides a kind of room temperature potassium ion conductivity and be more than 5·10-4The potassium fast-ionic conductor of S/cm, stoichiometric equation K6+2x+y-zBexAlyPzSi2-x-y-zO7, in which: x=0.05- 0.10；Y=0.05-0.10；Z=0.02-0.05.
In the technical scheme, by K2CO3∶NH4H2PO4∶Al2O3∶SiO2: BeO is according to K6+2x+y-zBexAlyPzSi2-x-y-zO7 Nonstoichiometric molar ratio ratio uniform mixing, be added quality be mixture quality 3%-9% dehydrated alcohol, in ball mill In with revolving speed ball milling 10-50 hours of 100-500 revs/min, in 60 DEG C of -120 DEG C of vacuum drying ovens (gas in baking oven after ball milling Body pressure is in 3Pa-20Pa) in dry 2-10 hour, re-grind 10-30 minutes, after grinding in agate stone roller alms bowl after taking-up Rate of the powder in air atmosphere with 5-30 DEG C/min is warming up to furnace cooling after 450-550 DEG C of heat preservation 3-10 hours；It will be cold But the powder after is ground in alms bowl in agate to be regrind 10-30 minutes, and the powder after grinding is in air atmosphere with 5-15 DEG C/min Rate be warming up to furnace cooling after 750-850 DEG C of heat preservation 10-20 hours；The sodium hydroxide taken out after grinding in 0.1-0.3M is molten It filters, dry and in a press 1 × 10 after being impregnated 5-15 minutes in liquid7Pa-8×107The pressure of Pa pushes flakiness, will Thin slice obtained is put into tube furnace and is warming up to 700-800 DEG C in the oxygen atmosphere of 10-60Pa with 5-10 DEG C/min of rate Furnace cooling after heat preservation 10-45 hours；The potassium ion fast-ionic conductor thin slice is made.If Fig. 1 is that group becomes K6.13Be0.05Al0.05P0.02Si1.88O7The XRD spectrum of potassium fast-ionic conductor, spectral line meet PDF card 72-1518 K6Si2O7 It is 5.910 through LCR821 impedance analyzer measurement conductivity mutually without miscellaneous phase-4S/cm。
Compared with the prior art, the advantages of the present invention are as follows: use Al3+、Be2+Part replaces Si4+Ion, in crystal High concentration gap potassium ion is generated, to generate more potassium ions collaboration migration of short distance, helping, which reduces potassium ion migration, lives Change energy；Pass through P5+Doping further decreases the electron conduction of fast-ionic conductor；Pass through the Be of small ionic radii2+Doping is adjusted The size of the migrating channels of potassium ion is to adapt to the fast transferring of potassium ion；It will be particularly beneficial that during the preparation process in K6Si2O7 The surface of particle is modified, and easy-sintering characteristic is formed, and is conducive to improve the potassium fast-ionic conductor and is subtracted when preparing bulk devices Few crystal boundary gap increases consistency to improve the potassium ion conductivity of block potassium fast-ionic conductor.These act synergistically so that The room temperature potassium ion conductivity of the potassium fast-ionic conductor is more than 510-4S/cm is very beneficial for the structure of full-solid potassium ion battery It builds.
Detailed description of the invention
Fig. 1 is that group becomes K6.13Be0.05Al0.05P0.02Si1.88O7The XRD spectrum of potassium fast-ionic conductor.
Specific embodiment
Below in conjunction with embodiment, present invention is further described in detail.
Embodiment 1: by K2CO3∶NH4H2PO4∶Al2O3∶SiO2: BeO is according to K6.13Be0.05Al0.05P0.02Si1.88O7Chemistry The ratio uniform of stoichiometric mole ratio mixes, and the dehydrated alcohol that quality is mixture quality 3% is added, in the ball mill with 110 turns/ Revolving speed ball milling 11 hours of minute, drying 2 is small in 65 DEG C of vacuum drying ovens (gas pressure is in 5Pa in baking oven) after ball milling When, it grinds in alms bowl and re-grinds 12 minutes in agate after taking-up, the powder after grinding is in air atmosphere with 6 DEG C/min of rate Furnace cooling after being warming up to 460 DEG C of heat preservations 3 hours；Powder after cooling is ground in alms bowl in agate and is regrind 10 minutes, is ground Furnace cooling after powder afterwards is warming up to 760 DEG C of heat preservations 10 hours in air atmosphere with 5 DEG C/min of rate；Take out grinding It filters, dry and in a press 1 × 10 after being impregnated 6 minutes in the sodium hydroxide solution of 0.1M afterwards7The pressure of Pa pushes Thin slice obtained is put into tube furnace and is warming up to 700 DEG C in the oxygen atmosphere of 12Pa with 5 DEG C/min of rate by flakiness Furnace cooling after heat preservation 20 hours；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 2: by K2CO3∶NH4H2PO4∶Al2O3∶SiO2: BeO is according to K6.19Be0.07Al0.07P0.02Si1.84O7Chemistry The ratio uniform of stoichiometric mole ratio mixes, and the dehydrated alcohol that quality is mixture quality 5% is added, in the ball mill with 350 turns/ Revolving speed ball milling 35 hours of minute, drying 7 is small in 80 DEG C of vacuum drying ovens (gas pressure is in 15Pa in baking oven) after ball milling When, it grinds in alms bowl and re-grinds 25 minutes in agate after taking-up, the powder after grinding is in air atmosphere with 20 DEG C/min of rate Furnace cooling after being warming up to 510 DEG C of heat preservations 7 hours；Powder after cooling is ground in alms bowl in agate and is regrind 21 minutes, is ground Furnace cooling after powder afterwards is warming up to 810 DEG C of heat preservations 15 hours in air atmosphere with 10 DEG C/min of rate；Take out grinding It is impregnated in the sodium hydroxide solution of 0.15M afterwards and filters, dries and in a press 3 × 10 after ten minutes7Under the pressure of Pa It is pressed into thin slice, thin slice obtained is put into tube furnace and is warming up to 800 in the oxygen atmosphere of 35Pa with 7 DEG C/min of rate DEG C heat preservation 40 hours after furnace cooling；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 3: by K2CO3∶NH4H2PO4∶Al2O3∶SiO2: BeO is according to K6.26Be0.1Al0.1P0.04Si1.76O7Chemistry The ratio uniform of stoichiometric mole ratio mixes, and the dehydrated alcohol that quality is mixture quality 8.5% is added, in the ball mill with 500 Rev/min revolving speed ball milling 45 hours, it is dry in 100 DEG C of vacuum drying ovens (gas pressure is in 18Pa in baking oven) after ball milling It 9 hours, grinds in alms bowl and re-grinds 30 minutes in agate after taking-up, the powder after grinding is in air atmosphere with 30 DEG C/min Rate is warming up to furnace cooling after 540 DEG C of heat preservations 9 hours；Powder after cooling is ground in alms bowl in agate and is regrind 25 minutes, Furnace cooling after powder after grinding is warming up to 820 DEG C of heat preservations 18 hours in air atmosphere with 15 DEG C/min of rate；It takes out It filters, dry and in a press 7 × 10 after being impregnated 13 minutes in the sodium hydroxide solution of 0.3M after grinding7The pressure of Pa Flakiness is pushed, thin slice obtained is put into tube furnace and is warming up in the oxygen atmosphere of 58Pa with 9 DEG C/min of rate 750 DEG C heat preservation 20 hours after furnace cooling；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 4: by K2CO3∶NH4H2PO4∶Al2O3∶SiO2: BeO is according to K6.18Be0.05Al0.1P0.02Si1.83O7Chemistry The ratio uniform of stoichiometric mole ratio mixes, and the dehydrated alcohol that quality is mixture quality 4% is added, in the ball mill with 400 turns/ Revolving speed ball milling 40 hours of minute, drying 8 is small in 100 DEG C of vacuum drying ovens (gas pressure is in 15Pa in baking oven) after ball milling When, it grinds in alms bowl and re-grinds 25 minutes in agate after taking-up, the powder after grinding is in air atmosphere with 20 DEG C/min of rate Furnace cooling after being warming up to 470 DEG C of heat preservations 8 hours；Powder after cooling is ground in alms bowl in agate and is regrind 15 minutes, is ground Furnace cooling after powder afterwards is warming up to 800 DEG C of heat preservations 15 hours in air atmosphere with 10 DEG C/min of rate；Take out grinding It is impregnated in the sodium hydroxide solution of 0.25M afterwards and filters, dries and in a press 6 × 10 after ten minutes7Under the pressure of Pa It is pressed into thin slice, thin slice obtained is put into tube furnace and is warming up to 770 in the oxygen atmosphere of 25Pa with 7 DEG C/min of rate DEG C heat preservation 25 hours after furnace cooling；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 5: by K2CO3∶NH4H2PO4∶Al2O3∶SiO2: BeO is according to K6.22Be0.08Al0.09P0.03Si1.8O7Chemistry Stoichiometric mole ratio ratio uniform mixing be added quality be mixture quality 5% dehydrated alcohol, in the ball mill with 400 turns/ Revolving speed ball milling 40 hours of minute, drying 8 is small in 100 DEG C of vacuum drying ovens (gas pressure is in 15Pa in baking oven) after ball milling When, it grinds in alms bowl and re-grinds 20 minutes in agate after taking-up, the powder after grinding is in air atmosphere with 20 DEG C/min of rate Furnace cooling after being warming up to 500 DEG C of heat preservations 7 hours；Powder after cooling is ground in alms bowl in agate and is regrind 20 minutes, is ground Furnace cooling after powder afterwards is warming up to 810 DEG C of heat preservations 15 hours in air atmosphere with 10 DEG C/min of rate；Take out grinding It filters, dry and in a press 5 × 10 after being impregnated 8 minutes in the sodium hydroxide solution of 0.1M afterwards7The pressure of Pa pushes Thin slice obtained is put into tube furnace and is warming up to 780 DEG C in the oxygen atmosphere of 55Pa with 7 DEG C/min of rate by flakiness Furnace cooling after heat preservation 32 hours；The potassium ion fast-ionic conductor thin slice is made.

Claims (1)

1. a kind of P5+、Al3+、Be2+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor, it is characterized in that: stoichiometric equation is K6+2x+y-zBexAlyPzSi2-x-y-zO7, in which: x=0.05-0.10；Y=0.05-0.10；Z=0.02-0.05；Room temperature potassium ion Conductivity is more than 510-4S/cm；Its preparation process is by K2CO3∶NH4H2PO4∶Al2O3∶SiO2: BeO is according to K6+2x+y- zBexAlyPzSi2-x-y-zO7Nonstoichiometric molar ratio ratio uniform mixing, it is mixture quality 3%-9% that quality, which is added, Dehydrated alcohol is in gas pressure after ball milling in the ball mill with revolving speed ball milling 10-50 hours of 100-500 revs/min 3Pa-20Pa, temperature are drying 2-10 hours in 60 DEG C of -120 DEG C of vacuum drying ovens, grind in alms bowl after taking-up in agate and re-grind 10- 30 minutes, rate of the powder in air atmosphere with 5-30 DEG C/min after grinding was warming up to 450-550 DEG C of heat preservation 3-10 hours Furnace cooling afterwards；Powder after cooling is ground in alms bowl in agate and is regrind 10-30 minutes, the powder after grinding is in air atmosphere In be warming up to 750-850 DEG C of heat preservation 10-20 hours with 5-15 DEG C/min of rate after furnace cooling；It takes out after grinding in 0.1- It filters, dry and in a press 1 × 10 after being impregnated 5-15 minutes in the sodium hydroxide solution of 0.3M7Pa-8×107The pressure of Pa Power pushes flakiness, and thin slice obtained is put into tube furnace in the oxygen atmosphere of 10-60Pa with 5-10 DEG C/min of rate The potassium fast-ionic conductor is made in furnace cooling after being warming up to 700-800 DEG C of heat preservation 10-45 hours.
CN201910617291.1A 2019-06-27 2019-06-27 A kind of P5+、Al3+、Be2+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof Withdrawn CN110372349A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910617291.1A CN110372349A (en) 2019-06-27 2019-06-27 A kind of P5+、Al3+、Be2+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910617291.1A CN110372349A (en) 2019-06-27 2019-06-27 A kind of P5+、Al3+、Be2+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof

Publications (1)

Publication Number Publication Date
CN110372349A true CN110372349A (en) 2019-10-25

Family

ID=68252463

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910617291.1A Withdrawn CN110372349A (en) 2019-06-27 2019-06-27 A kind of P5+、Al3+、Be2+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110372349A (en)

Similar Documents

Publication Publication Date Title
CN102780031B (en) A kind of Mg 2+, Al 3+, Zr 4+, F -ion co-doped garnet-type solid electrolyte
CN102867988B (en) B3+, Al3 +, Ti4 +, Y3+ F-codoped solid electrolyte Li7La3Zr2Ol2
CN102780028B (en) Four-component iron co-doped garnet type solid electrolyte
CN102867987B (en) A B3+, al3+, mg2+, Y3+, F- codoped solid electrolyte Li7La3Zr2O12
CN102769147B (en) Mg<2+>, Al<3+>, Zr<4+> and S<2-> ion co-doped garnet type solid electrolyte
CN110372350A (en) A kind of B3+、Al3+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method
CN102867985B (en) B<3+>, Al<3+>, Mg<2+>, Y<3+> and S<2-> co-doped solid electrolyte Li7La3Zr2O12
CN110372357A (en) A kind of P5+、Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof
CN110265706A (en) A kind of electric field induction crystallization P5+、Al3+、B3+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof
CN102780029B (en) A kind of three component cation codope carbuncle type solid lithium-ion electrolytes
CN110372348A (en) A kind of electric field induction crystallization K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7Potassium fast-ionic conductor and preparation method
CN110526697A (en) A kind of liquid phase synthesis K6.25Be0.1Al0.1P0.05Ti0.05Si1.7O7Potassium fast-ionic conductor and preparation method thereof
CN110372349A (en) A kind of P5+、Al3+、Be2+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof
CN110350250A (en) A kind of P5+、Al3+、B3+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof
CN102856584B (en) A B3+, al3+, ti4+, Y3+and S2- codoped solid electrolyte Li7La3Zr2O12
CN102867986B (en) One B3+, al3+, ti4+and Y3+cationic co-doped solid electrolyte Li7La3Zr2O12
CN110372351A (en) A kind of P5+、Al3+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof
CN110357599A (en) A kind of P5+、Al3+、Be2+、Zn2+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof
CN110357598A (en) A kind of P5+、Be2+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof
CN110371997A (en) A kind of P5+、Al3+、Be2+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof
CN110336008A (en) A kind of P5+、Al3+、Be2+、Zn2+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof
CN102780030B (en) Four-component cation and anion co-doped garnet-type solid electrolyte
CN110371996A (en) A kind of Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof
CN110371995A (en) A kind of electric field induction crystallization P5+、Al3+、Be2+Cooperate with the K of doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof
CN110372358A (en) A kind of electric field induction crystalline A l3+、Be2+The K of doping2MgSi5O12Potassium fast-ionic conductor and preparation method

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
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20191025