CN110372352A - A kind of liquid phase synthesis multiple ion doping potassium fast-ionic conductor and preparation method thereof - Google Patents

A kind of liquid phase synthesis multiple ion doping potassium fast-ionic conductor and preparation method thereof Download PDF

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CN110372352A
CN110372352A CN201910617576.5A CN201910617576A CN110372352A CN 110372352 A CN110372352 A CN 110372352A CN 201910617576 A CN201910617576 A CN 201910617576A CN 110372352 A CN110372352 A CN 110372352A
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deionized water
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姘存芳
水淼
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Ningbo University
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Abstract

A kind of liquid phase synthesis multiple ion doping potassium fast-ionic conductor and preparation method thereof, it is characterized in that: stoichiometric equation K6.25Fe0.05Be0.2Ti0.05Si1.75O7；Using Be2+Part replaces Si4+Ion generates gap potassium ion in crystal and reduces potassium ion migration activation energy；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；Pass through Ti4+The lattice structure that part doping forms distortion increases lattice defect and is conducive to potassium ions conduct；Pass through Fe3+Part doping forms cation vacancy and increases potassium ion migration path；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 liquid phase synthesis multiple ion doping potassium fast-ionic conductor and preparation method thereof
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
The technical problem to be solved by the present invention is to for existing background technique and a kind of liquid phase synthesis for providing it is multiple from Son doping potassium fast-ionic conductor and preparation method thereof.Using Be2+Part replaces Si4+Ion generates high concentration gap in crystal Potassium ion helps to reduce potassium ion migration activation energy to generate more potassium ions collaboration migration of short distance；Pass through small ion The Be of radius2+Doping adjusts the size of the migrating channels of potassium ion to adapt to the fast transferring of potassium ion；Pass through Ti4+It mixes part The miscellaneous lattice structure for forming distortion increases lattice defect and is conducive to potassium ions conduct；Pass through Fe3+It is empty that part doping forms cation Position increases potassium ion migration path；And during the preparation process in K6Si2O7The surface of particle is modified, and easy-sintering characteristic is formed, Be conducive to improve the potassium fast-ionic conductor to reduce crystal boundary gap when preparing bulk devices, increase consistency to improve block potassium The potassium ion conductivity of fast-ionic conductor.These synergistic effects are so that the room temperature potassium ion conductivity of the potassium fast-ionic conductor is more than 5·10-4S/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 K6.25Fe0.05Be0.2Ti0.05Si1.75O7。
In the technical scheme, by solid KNO3∶Fe(NO3)3·9H2O is according to K6.25Fe0.05Be0.2Ti0.05Si1.75O7In The ratio uniform of the nonstoichiometric molar ratio of respective element mixes, intensively stirred while deionized water is added consolidates to all The dissolution of body substance, writes down the quality of deionized water be added, continuously adds recorded deionized water quality 1.0-1.5 thereafter The deionized water of times quality simultaneously stirs evenly, and continues to stir and be added 35wt% beryllium nitrate aqueous solution beryllium into solution system at this time The amount of substance meet K6.25Fe0.05Be0.2Ti0.05Si1.75O7Stoichiometric ratio, and be added substance amount be all metals from The tartaric acid of 1.5-2.5 times of sub- total amount is stirred to being completely dissolved；Remember that this solution is solution A；It will meet K6.25Fe0.05Be0.2Ti0.05Si1.75O7The tetraethyl orthosilicate and butyl titanate of stoichiometric ratio are dissolved in volume and are positive silicic acid In the dehydrated alcohol of 1.0-1.5 times of the sum of tetra-ethyl ester and butyl titanate volume, remember that this solution is solution B；Then under stiring Solution A is added dropwise in solution B to all adding, the temperature of solution system is then risen to 40-50 DEG C and keeps this temperature Deionized water is continuously added with 3-5 drop/minute speed under conditions of degree and stirring, until solution gradually becomes sticky and forms glue Freeze shape.Gelatin substance is ground 10-30 minutes in mortar after drying 20-48 hours in 130-200 DEG C of baking oven；Grinding Rate of the powder afterwards in air atmosphere with 5-30 DEG C/min is warming up to furnace cooling after 400-500 DEG C of heat preservation 3-10 hours； By powder after cooling agate grind alms bowl in regrind 10-30 minutes, the powder after grinding in air atmosphere with 5-15 DEG C/ The rate of minute is warming up to furnace cooling after 600-700 DEG C of heat preservation 10-20 hours；The hydroxide in 0.1-0.3M is ground after taking-up It filters, dry and in a press 1 × 10 after being impregnated 5-15 minutes in sodium solution7Pa-8×107The pressure of Pa depresses to thin Thin slice obtained is put into tube furnace and is warming up to 700- in the oxygen atmosphere of 10-60Pa with 5-10 DEG C/min of rate by piece 850 DEG C of furnace coolings after heat preservation 20-45 hours；The potassium ion fast-ionic conductor thin slice is made.As Fig. 1 is K6.25Fe0.05Be0.2Ti0.05Si1.75O7The XRD spectrum of potassium fast-ionic conductor, spectral line meet PDF card 72-1518 K6Si2O7 It is 6.210 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 Be2+Part replaces Si4+Ion generates in crystal High concentration gap potassium ion helps to reduce potassium ion migration activation energy to generate more potassium ions collaboration migration of short distance； 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；Pass through Ti4+The lattice structure that part doping forms distortion increases lattice defect and is conducive to potassium ions conduct；Pass through Fe3+Part doping shape Increase potassium ion migration path at cation vacancy；It will be particularly beneficial that during the preparation process in K6Si2O7The surface of particle carries out Modification forms easy-sintering characteristic, is conducive to improve the potassium fast-ionic conductor and reduces crystal boundary gap, increase when preparing bulk devices Consistency is to improve the potassium ion conductivity of block potassium fast-ionic conductor.These act synergistically so that the potassium fast-ionic conductor Room temperature potassium ion conductivity is more than 510-4S/cm is very beneficial for the building of full-solid potassium ion battery.
Detailed description of the invention
Fig. 1 is K6.25Fe0.05Be0.2Ti0.05Si1.75O7The XRD spectrum of potassium fast-ionic conductor.
Specific embodiment
Below in conjunction with embodiment, present invention is further described in detail.
Embodiment 1: by solid KNO3∶Fe(NO3)3·9H2O is according to K6.25Fe0.05Be0.2Ti0.05Si1.75O7Middle respective element Nonstoichiometric molar ratio ratio uniform mixing, intensively stirred while that deionized water is added is molten to all solid matters Solution, write down the quality of deionized water be added, continuously add thereafter 1.0 times of quality of recorded deionized water quality go from Sub- water simultaneously stirs evenly, and continues the amount symbol for stirring and being added 35wt% beryllium nitrate aqueous solution substance of beryllium into solution system at this time Close K6.25Fe0.05Be0.2Ti0.05Si1.75O7Stoichiometric ratio, and the amount that substance is added is 1.5 times of all metal ions total amount Tartaric acid is stirred to being completely dissolved；Remember that this solution is solution A；K will be met6.25Fe0.05Be0.2Ti0.05Si1.75O7Change The tetraethyl orthosilicate and butyl titanate for learning metering ratio be dissolved in volume be tetraethyl orthosilicate and butyl titanate volume it In 1.1 times of dehydrated alcohol, remember that this solution is solution B；Then solution A is added dropwise in solution B to whole under stiring It adds, with 3 drops/minute speed under conditions of the temperature of solution system is then risen to 40 DEG C and keeps this temperature and stirs Deionized water is continuously added, until solution gradually becomes sticky and formed gelatin.Gelatin substance is done in 130 DEG C of baking oven It is ground 10 minutes in mortar after dry 22 hours；Powder after grinding is warming up in air atmosphere with 6 DEG C/min of rate 410 DEG C heat preservation 3 hours after furnace cooling；Powder after cooling is ground in alms bowl in agate and is regrind 10 minutes, the powder after grinding Furnace cooling after body is warming up to 600 DEG C of heat preservations 10 hours in air atmosphere with 5 DEG C/min of rate；Grinding exists after taking-up It filters, dry and in a press 1.5 × 10 after being impregnated 6 minutes in the sodium hydroxide solution of 0.12M7The pressure of Pa depresses to Thin slice obtained is put into tube furnace in the oxygen atmosphere of 12Pa and is warming up to 700 DEG C of guarantors with 5 DEG C/min of rate by thin slice Furnace cooling after temperature 21 hours；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 2: by solid KNO3∶Fe(NO3)3·9H2O is according to K6.25Fe0.05Be0.2Ti0.05Si1.75O7Middle respective element Nonstoichiometric molar ratio ratio uniform mixing, intensively stirred while that deionized water is added is molten to all solid matters Solution, write down the quality of deionized water be added, continuously add thereafter 1.5 times of quality of recorded deionized water quality go from Sub- water simultaneously stirs evenly, and continues the amount symbol for stirring and being added 35wt% beryllium nitrate aqueous solution substance of beryllium into solution system at this time Close K6.25Fe0.05Be0.2Ti0.05Si1.75O7Stoichiometric ratio, and the amount that substance is added is 2.5 times of all metal ions total amount Tartaric acid is stirred to being completely dissolved；Remember that this solution is solution A；K will be met6.25Fe0.05Be0.2Ti0.05Si1.75O7Change The tetraethyl orthosilicate and butyl titanate for learning metering ratio be dissolved in volume be tetraethyl orthosilicate and butyl titanate volume it In 1.4 times of dehydrated alcohol, remember that this solution is solution B；Then solution A is added dropwise in solution B to whole under stiring It adds, with 5 drops/minute speed under conditions of the temperature of solution system is then risen to 48 DEG C and keeps this temperature and stirs Deionized water is continuously added, until solution gradually becomes sticky and formed gelatin.Gelatin substance is done in 190 DEG C of baking oven It is ground 30 minutes in mortar after dry 45 hours；Powder after grinding is warming up in air atmosphere with 30 DEG C/min of rate 500 DEG C heat preservation 9 hours after furnace cooling；Powder after cooling is ground in alms bowl in agate and is regrind 28 minutes, the powder after grinding Furnace cooling after body is warming up to 700 DEG C of heat preservations 20 hours in air atmosphere with 15 DEG C/min of rate；Grinding exists after taking-up It filters, dry and in a press 8 × 10 after being impregnated 15 minutes in the sodium hydroxide solution of 0.3M7The pressure of Pa depresses to thin Thin slice obtained is put into tube furnace in the oxygen atmosphere of 50Pa and is warming up to 820 DEG C of heat preservations with 10 DEG C/min of rate by piece Furnace cooling after 43 hours；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 3: by solid KNO3∶Fe(NO3)3·9H2O is according to K6.25Fe0.05Be0.2Ti0.05Si1.75O7Middle respective element Nonstoichiometric molar ratio ratio uniform mixing, intensively stirred while that deionized water is added is molten to all solid matters Solution, write down the quality of deionized water be added, continuously add thereafter 1.3 times of quality of recorded deionized water quality go from Sub- water simultaneously stirs evenly, and continues the amount symbol for stirring and being added 35wt% beryllium nitrate aqueous solution substance of beryllium into solution system at this time Close K6.25Fe0.05Be0.2Ti0.05Si1.75O7Stoichiometric ratio, and the amount that substance is added is 2.1 times of all metal ions total amount Tartaric acid is stirred to being completely dissolved；Remember that this solution is solution A；K will be met6.25Fe0.05Be0.2Ti0.05Si1.75O7Change The tetraethyl orthosilicate and butyl titanate for learning metering ratio be dissolved in volume be tetraethyl orthosilicate and butyl titanate volume it In 1.2 times of dehydrated alcohol, remember that this solution is solution B；Then solution A is added dropwise in solution B to whole under stiring It adds, with 4 drops/minute speed under conditions of the temperature of solution system is then risen to 46 DEG C and keeps this temperature and stirs Deionized water is continuously added, until solution gradually becomes sticky and formed gelatin.Gelatin substance is done in 180 DEG C of baking oven It is ground 25 minutes in mortar after dry 32 hours；Powder after grinding is warming up in air atmosphere with 20 DEG C/min of rate 450 DEG C heat preservation 7 hours after furnace cooling；Powder after cooling is ground in alms bowl in agate and is regrind 20 minutes, the powder after grinding Furnace cooling after body is warming up to 660 DEG C of heat preservations 15 hours in air atmosphere with 10 DEG C/min of rate；Grinding exists after taking-up It is impregnated in the sodium hydroxide solution of 0.2M and filters, dries and in a press 5 × 10 after ten minutes7The pressure of Pa depresses to thin Thin slice obtained is put into tube furnace in the oxygen atmosphere of 40Pa and is warming up to 760 DEG C of heat preservations with 7 DEG C/min of rate by piece Furnace cooling after 30 hours；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 4: by solid KNO3∶Fe(NO3)3·9H2O is according to K6.25Fe0.05Be0.2Ti0.05Si1.75O7Middle respective element Nonstoichiometric molar ratio ratio uniform mixing, intensively stirred while that deionized water is added is molten to all solid matters Solution, write down the quality of deionized water be added, continuously add thereafter 1.0 times of quality of recorded deionized water quality go from Sub- water simultaneously stirs evenly, and continues the amount symbol for stirring and being added 35wt% beryllium nitrate aqueous solution substance of beryllium into solution system at this time Close K6.25Fe0.05Be0.2Ti0.05Si1.75O7Stoichiometric ratio, and the amount that substance is added is 2.0 times of all metal ions total amount Tartaric acid is stirred to being completely dissolved；Remember that this solution is solution A；K will be met6.25Fe0.05Be0.2Ti0.05Si1.75O7Change The tetraethyl orthosilicate and butyl titanate for learning metering ratio be dissolved in volume be tetraethyl orthosilicate and butyl titanate volume it In 1.4 times of dehydrated alcohol, remember that this solution is solution B；Then solution A is added dropwise in solution B to whole under stiring It adds, with 5 drops/minute speed under conditions of the temperature of solution system is then risen to 40 DEG C and keeps this temperature and stirs Deionized water is continuously added, until solution gradually becomes sticky and formed gelatin.Gelatin substance is done in 190 DEG C of baking oven It is ground 20 minutes in mortar after dry 30 hours；Powder after grinding is warming up in air atmosphere with 20 DEG C/min of rate 450 DEG C heat preservation 7 hours after furnace cooling；Powder after cooling is ground in alms bowl in agate and is regrind 30 minutes, the powder after grinding Furnace cooling after body is warming up to 700 DEG C of heat preservations 20 hours in air atmosphere with 15 DEG C/min of rate；Grinding exists after taking-up It is impregnated in the sodium hydroxide solution of 0.3M and filters, dries and in a press 6 × 10 after ten minutes7The pressure of Pa depresses to thin Thin slice obtained is put into tube furnace in the oxygen atmosphere of 40Pa and is warming up to 830 DEG C of heat preservations with 10 DEG C/min of rate by piece Furnace cooling after 32 hours；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 5: by solid KNO3∶Fe(NO3)3·9H2O is according to K6.25Fe0.05Be0.2Ti0.05Si1.75O7Middle respective element Nonstoichiometric molar ratio ratio uniform mixing, intensively stirred while that deionized water is added is molten to all solid matters Solution, write down the quality of deionized water be added, continuously add thereafter 1.5 times of quality of recorded deionized water quality go from Sub- water simultaneously stirs evenly, and continues the amount symbol for stirring and being added 35wt% beryllium nitrate aqueous solution substance of beryllium into solution system at this time Close K6.25Fe0.05Be0.2Ti0.05Si1.75O7Stoichiometric ratio, and the amount that substance is added is 1.5 times of all metal ions total amount Tartaric acid is stirred to being completely dissolved；Remember that this solution is solution A；K will be met6.25Fe0.05Be0.2Ti0.05Si1.75O7Change The tetraethyl orthosilicate and butyl titanate for learning metering ratio be dissolved in volume be tetraethyl orthosilicate and butyl titanate volume it In 1.1 times of dehydrated alcohol, remember that this solution is solution B；Then solution A is added dropwise in solution B to whole under stiring It adds, with 4 drops/minute speed under conditions of the temperature of solution system is then risen to 45 DEG C and keeps this temperature and stirs Deionized water is continuously added, until solution gradually becomes sticky and formed gelatin.Gelatin substance is done in 170 DEG C of baking oven It is ground 10 minutes in mortar after dry 45 hours；Powder after grinding is warming up in air atmosphere with 30 DEG C/min of rate 460 DEG C heat preservation 5 hours after furnace cooling；Powder after cooling is ground in alms bowl in agate and is regrind 20 minutes, the powder after grinding Furnace cooling after body is warming up to 660 DEG C of heat preservations 10 hours in air atmosphere with 10 DEG C/min of rate；Grinding exists after taking-up It is impregnated in the sodium hydroxide solution of 0.3M and filters, dries and in a press 7 × 10 after ten minutes7The pressure of Pa depresses to thin Thin slice obtained is put into tube furnace in the oxygen atmosphere of 60Pa and is warming up to 850 DEG C of heat preservations with 10 DEG C/min of rate by piece Furnace cooling after 25 hours；The potassium ion fast-ionic conductor thin slice is made.

Claims (1)

1. a kind of liquid phase synthesis multiple ion adulterates potassium fast-ionic conductor, it is characterized in that: stoichiometric equation is K6.25Fe0.05Be0.2Ti0.05Si1.75O7；Room temperature potassium ion conductivity is more than 510-4S/cm；Its preparation process is by solid KNO3 ∶Fe(NO3)3·9H2O is according to K6.25Fe0.05Be0.2Ti0.05Si1.75O7The ratio uniform of the nonstoichiometric molar ratio of middle respective element Mixing writes down deionized water be added intensively stirred while deionized water to all solid matter is added dissolves Quality continuously adds thereafter the deionized water of recorded 1.0-1.5 times of quality of deionized water quality and stirs evenly, at this time after Continue to stir and 35wt% beryllium nitrate aqueous solution amount of the substance of beryllium into solution system is added and meet K6.25Fe0.05Be0.2Ti0.05Si1.75O7Stoichiometric ratio, and be added substance amount be 1.5-2.5 times of all metal ions total amount Tartaric acid stir to being completely dissolved；Remember that this solution is solution A；K will be met6.25Fe0.05Be0.2Ti0.05Si1.75O7 It is tetraethyl orthosilicate and butyl titanate volume that the tetraethyl orthosilicate and butyl titanate of stoichiometric ratio, which are dissolved in volume, The sum of in 1.0-1.5 times of dehydrated alcohol, remember that this solution is solution B；Then solution A is added dropwise in solution B under stiring To all adding, with 3-5 under conditions of the temperature of solution system is then risen to 40-50 DEG C and keeps this temperature and stirs Drop/minute speed continuously adds deionized water, until solution gradually becomes sticky and formed gelatin；Gelatin substance is existed Drying is ground 1030 minutes in mortar after 20-48 hours in 130-200 DEG C of baking oven；Powder after grinding is in air atmosphere Furnace cooling after being warming up to 400-500 DEG C of heat preservation 3-10 hours with 5-30 DEG C/min of rate；By powder after cooling in agate It grinds in alms bowl and regrinds 10-30 minutes, the powder after grinding is warming up to 600- in air atmosphere with 5-15 DEG C/min of rate 700 DEG C of furnace coolings after heat preservation 10-20 hours；Grinding is impregnated 5-15 minutes in the sodium hydroxide solution of 0.1-0.3M after taking-up It filters, dry and in a press 1 × 10 afterwards7Pa-8×107The pressure of Pa pushes flakiness, and thin slice obtained is put into pipe After rate in formula furnace in the oxygen atmosphere of 10-60Pa with 5-10 DEG C/min is warming up to 700-850 DEG C of heat preservation 20-45 hours The potassium fast-ionic conductor is made in furnace cooling.
CN201910617576.5A 2019-06-27 2019-06-27 A kind of liquid phase synthesis multiple ion doping potassium fast-ionic conductor and preparation method thereof Withdrawn CN110372352A (en)

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