CN110372348A - A kind of electric field induction crystallization K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7Potassium fast-ionic conductor and preparation method - Google Patents

A kind of electric field induction crystallization K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7Potassium fast-ionic conductor and preparation method Download PDF

Info

Publication number
CN110372348A
CN110372348A CN201910617186.8A CN201910617186A CN110372348A CN 110372348 A CN110372348 A CN 110372348A CN 201910617186 A CN201910617186 A CN 201910617186A CN 110372348 A CN110372348 A CN 110372348A
Authority
CN
China
Prior art keywords
solution
potassium
fast
ionic conductor
potassium 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Withdrawn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
CN201910617186.8A
Other languages
Chinese (zh)
Inventor
姘存芳
水淼
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 CN201910617186.8A priority Critical patent/CN110372348A/en
Publication of CN110372348A publication Critical patent/CN110372348A/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Withdrawn legal-status Critical Current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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • 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
    • C04B2235/443—Nitrates or nitrites
    • 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
    • C04B2235/02—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
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • 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
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
    • 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
    • C04B2235/70—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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Conductive Materials (AREA)

Abstract

A kind of electric field induction crystallization K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7Potassium fast-ionic conductor and preparation method, using Al3+、B3+Part replaces Si4+Ion generates high concentration gap potassium ion in crystal, helps to reduce potassium ion migration activation energy；Pass through P5+Doping further decreases the electron conduction of fast-ionic conductor；Pass through the B of small ionic radii3+Doping adjusts the size of the migrating channels of potassium ion to adapt to the fast transferring of potassium ion；Pass through Zr4+The lattice structure that part doping forms distortion increases lattice defect and is conducive to potassium ions conduct；Pass through Zn2+Doping generates cation vacancy to increase potassium ion flyway；And during the preparation process in K6Si2O7The surface of particle is modified, and easy-sintering characteristic is formed.The induction crystallization of strong dc electric field is introduced simultaneously to accelerate the speed of crystallization, reduce the temperature of crystallization and improve crystallization integrity degree.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 electric field induction crystallization K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7Potassium fastly from Sub- conductor and 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, et al., 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-xCrxP3012, 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 (Ramaawamy 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 a kind of electric field provided for existing background technique induction crystallizations K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7Potassium fast-ionic conductor and preparation method.Using Al3+、B3+Part replaces Si4+From Son generates high concentration gap potassium ion in crystal, to generate more potassium ions collaboration migration of short distance, helps to reduce potassium Ion transfer activation energy；Pass through P5+Doping further decreases the electron conduction of fast-ionic conductor；Pass through the B of small ionic radii3+ Doping adjusts the size of the migrating channels of potassium ion to adapt to the fast transferring of potassium ion；Pass through Zr4+Part doping forms distortion Lattice structure increase lattice defect be conducive to potassium ions conduct；Pass through Zn2+Doping generate cation vacancy to increase potassium from Sub- flyway；And during the preparation process in K6Si2O7The surface of particle is modified, and is formed easy-sintering characteristic, is conducive to improve The potassium fast-ionic conductor reduces crystal boundary gap when preparing bulk devices, increases consistency to improve block potassium fast-ionic conductor Potassium ion conductivity；Speed, the temperature for reducing crystallization and raising that crystallization is accelerated in the induction crystallization of strong dc electric field are introduced simultaneously Crystallize integrity degree.These synergistic effects are so that the room temperature potassium ion conductivity of the potassium fast-ionic conductor is more than 510-4S/cm, more The potassium ion conductivity of the nearly liquid electrolyte of adjunction.
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 K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7。
In the technical scheme, by solid KNO3∶Al(NO3)3·9H2O∶NH4H2PO4: boric acid: Zn (NO3)2·6H2O is pressed According to K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7The ratio uniform of the nonstoichiometric molar ratio of middle respective element mixes, strong Deionized water to all solid matters are added while strong stirring to dissolve, write down the quality of deionized water be added, thereafter It continuously adds the deionized water of recorded 1.0-1.5 times of quality of deionized water quality and stirs evenly, continue stirring at this time simultaneously The amount that substance is added is that the tartaric acid of 1.5-2.5 times of all metal ions total amount is stirred to being completely dissolved；Remember that this is molten Liquid is solution A；K will be met6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7The tetraethyl orthosilicate and zirconic acid four of stoichiometric ratio Butyl ester is dissolved in the dehydrated alcohol that volume is 1.0-1.5 times of the sum of tetraethyl orthosilicate and tetrabutyl zirconate volume, remembers that this is molten Liquid is solution B；Then solution A is added dropwise in solution B to all adding under stiring, it then will be in the temperature of solution system Deionized water is continuously added with 3-5 drop/minute speed under conditions of being raised to 40-50 DEG C and keeping this temperature and stir, until molten Liquid gradually becomes sticky and is formed gelatin；By gelatin substance, drying is being ground after 20-48 hours in 130-200 DEG C of baking oven It is ground 10-30 minutes in alms bowl；Powder after grinding is warming up to 400-500 DEG C in air atmosphere with 5-30 DEG C/min of rate Furnace cooling after heat preservation 3-10 hours；Powder after cooling is ground in alms bowl in agate and is regrind 10-30 minutes, the powder after grinding Rate of the body in air atmosphere with 5-15 DEG C/min is warming up to furnace cooling after 600-700 DEG C of heat preservation 10-20 hours；It takes out Filter, dry after being impregnated 5-15 minutes in the sodium hydroxide solution of 0.1-0.3M after grinding and in a press 1 × 107Pa-8×107The pressure of Pa pushes flakiness, and thin slice obtained is put into the tubular type of both ends setting 800-1100V DC voltage Rate in furnace in the oxygen atmosphere of 10-60Pa with 5-10 DEG C/min be warming up to 700-850 DEG C of heat preservation 10-20 hours after with Furnace is cooling；The potassium ion fast-ionic conductor thin slice is made.If Fig. 1 is K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7Potassium fastly from The XRD spectrum of sub- conductor, spectral line meet PDF card 72-1518 K6Si2O7Mutually without miscellaneous phase, surveyed through LCR821 impedance analyzer Determining conductivity is 8.510-4S/cm。
Compared with the prior art, the advantages of the present invention are as follows: use Al3+、B3+Part replaces Si4+Ion produces in crystal Raw high concentration gap potassium ion helps to reduce potassium ion migration activation to generate more potassium ions collaboration migration of short distance Energy；Pass through P5+Doping further decreases the electron conduction of fast-ionic conductor；Pass through the B of small ionic radii3+Doping adjust potassium from The size of the migrating channels of son is to adapt to the fast transferring of potassium ion；Pass through Zr4+The lattice structure that part doping forms distortion increases Lattice defect is added to be conducive to potassium ions conduct；Pass through Zn2+Doping generates cation vacancy to increase potassium ion flyway；It is special Not it is beneficial that during the preparation process in K6Si2O7The surface of particle is modified, and easy-sintering characteristic is formed, and is conducive to improve and is somebody's turn to do Potassium fast-ionic conductor reduces crystal boundary gap when preparing bulk devices, increases consistency to improve block potassium fast-ionic conductor Potassium ion conductivity；The induction crystallization of strong dc electric field is introduced simultaneously to accelerate the speed of crystallization, reduce the temperature of crystallization and improve knot Brilliant integrity degree.These synergistic effects are so that the room temperature potassium ion conductivity of the potassium fast-ionic conductor is more than 510-4S/cm, very Be conducive to the building of full-solid potassium ion battery.
Detailed description of the invention
Fig. 1 is K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7The 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∶Al(NO3)3·9H2O∶NH4H2PO4: boric acid: Zn (NO3)2·6H2O is according to K6.15 Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7The ratio uniform of the nonstoichiometric molar ratio of middle respective element mixes, and is stirring strongly While deionized water to all solid matter be added dissolve, write down the quality of deionized water be added, continue thereafter plus Enter the deionized water of recorded 1.1 times of quality of deionized water quality and stirs evenly, continue to stir at this time and substance is added Amount stirs for 1.6 times of all metal ions total amount of tartaric acid to being completely dissolved；Remember that this solution is solution A；It will symbol Close K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7The tetraethyl orthosilicate and tetrabutyl zirconate of stoichiometric ratio are dissolved in volume In 1.0 times of the sum of tetraethyl orthosilicate and tetrabutyl zirconate volume of dehydrated alcohols, to remember that this solution is solution B；Then stirring It mixes lower solution A is added dropwise in solution B to whole to add, the temperature of solution system is then risen to 40 DEG C and keeps this temperature Deionized water is continuously added with 3 drops/minute speed under conditions of degree and stirring, until solution gradually becomes sticky and forms jelly Shape.Gelatin substance is ground 10 minutes in mortar after drying 20 hours in 140 DEG C of baking oven；Powder after grinding is in sky Furnace cooling after being warming up to 410 DEG C of heat preservations 3 hours in gas atmosphere with 5 DEG C/min of rate；Powder after cooling is ground in agate It is regrind 10 minutes in alms bowl, the powder after grinding is warming up to 610 DEG C of heat preservations 10 in air atmosphere with 5 DEG C/min of rate Furnace cooling after hour；It takes out filtering after impregnating 6 minutes in the sodium hydroxide solution of 0.12M after grinding, dry and in pressure 1 × 10 in machine7The pressure of Pa pushes flakiness, thin slice obtained is put into the tube furnace of both ends setting 810V DC voltage Furnace cooling after being warming up to 700 DEG C of heat preservations 10 hours in the oxygen atmosphere of 15Pa with 5 DEG C/min of rate；Be made the potassium from Sub- fast-ionic conductor thin slice.
Embodiment 2: by solid KNO3∶Al(NO3)3·9H2O∶NH4H2PO4: boric acid: Zn (NO3)2·6H2O is according to K6.15 Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7The ratio uniform of the nonstoichiometric molar ratio of middle respective element mixes, and is stirring strongly While deionized water to all solid matter be added dissolve, write down the quality of deionized water be added, continue thereafter plus Enter the deionized water of recorded 1.5 times of quality of deionized water quality and stirs evenly, continue to stir at this time and substance is added Amount stirs for 2.4 times of all metal ions total amount of tartaric acid to being completely dissolved；Remember that this solution is solution A；It will symbol Close K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7The tetraethyl orthosilicate and tetrabutyl zirconate of stoichiometric ratio are dissolved in volume In 1.5 times of the sum of tetraethyl orthosilicate and tetrabutyl zirconate volume of dehydrated alcohols, to remember that this solution is solution B；Then stirring It mixes lower solution A is added dropwise in solution B to whole to add, the temperature of solution system is then risen to 48 DEG C and keeps this temperature Deionized water is continuously added with 5 drops/minute speed under conditions of degree and stirring, until solution gradually becomes sticky and forms jelly Shape.Gelatin substance is ground 30 minutes in mortar after drying 45 hours in 190 DEG C of baking oven；Powder after grinding is in sky Furnace cooling after being warming up to 490 DEG C of heat preservations 9 hours in gas atmosphere with 30 DEG C/min of rate；By powder after cooling in agate It grinds in alms bowl and regrinds 28 minutes, the powder after grinding is warming up to 690 DEG C of heat preservations in air atmosphere with 15 DEG C/min of rate Furnace cooling after 20 hours；Filtering after impregnating 13 minutes in the sodium hydroxide solution of 0.3M after grinding is taken out, dries and is pressing 8 × 10 in power machine7The pressure of Pa pushes flakiness, and thin slice obtained is put into the tubular type of both ends setting 1080V DC voltage Furnace cooling after being warming up to 850 DEG C of heat preservations 20 hours in the oxygen atmosphere of 50Pa with 10 DEG C/min of rate in furnace；This is made Potassium ion fast-ionic conductor thin slice.
Embodiment 3: by solid KNO3∶Al(NO3)3·9H2O∶NH4H2PO4: boric acid: Zn (NO3)2·6H2O is according to K6.15 Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7The ratio uniform of the nonstoichiometric molar ratio of middle respective element mixes, and is stirring strongly While deionized water to all solid matter be added dissolve, write down the quality of deionized water be added, continue thereafter plus Enter the deionized water of recorded 1.3 times of quality of deionized water quality and stirs evenly, continue to stir at this time and substance is added Amount stirs for 2.1 times of all metal ions total amount of tartaric acid to being completely dissolved；Remember that this solution is solution A；It will symbol Close K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7The tetraethyl orthosilicate and tetrabutyl zirconate of stoichiometric ratio are dissolved in volume In 1.2 times of the sum of tetraethyl orthosilicate and tetrabutyl zirconate volume of dehydrated alcohols, to remember that this solution is solution B；Then stirring It mixes lower solution A is added dropwise in solution B to whole to add, the temperature of solution system is then risen to 46 DEG C and keeps this temperature Deionized water is continuously added with 4 drops/minute speed under conditions of degree and stirring, until solution gradually becomes sticky and forms jelly Shape.Gelatin substance is ground 30 minutes in mortar after drying 32 hours in 180 DEG C of baking oven；Powder after grinding is in sky Furnace cooling after being warming up to 450 DEG C of heat preservations 7 hours in gas atmosphere with 20 DEG C/min of rate；By powder after cooling in agate It grinds in alms bowl and regrinds 20 minutes, the powder after grinding is warming up to 660 DEG C of heat preservations in air atmosphere with 10 DEG C/min of rate Furnace cooling after 15 hours；Filtering after ten minutes, drying are impregnated in the sodium hydroxide solution of 0.2M after taking out grinding and are being pressed 5 × 10 in power machine7The pressure of Pa pushes flakiness, and thin slice obtained is put into the tube furnace of both ends setting 980V DC voltage In in the oxygen atmosphere of 30Pa with 7 DEG C/min of rate be warming up to 780 DEG C heat preservation 15 hours after furnace cooling；The potassium is made Ion fast-ionic conductor thin slice.
Embodiment 4: by solid KNO3∶Al(NO3)3·9H2O∶NH4H2PO4: boric acid: Zn (NO3)2·6H2O is according to K6.15 Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7The ratio uniform of the nonstoichiometric molar ratio of middle respective element mixes, and is stirring strongly While deionized water to all solid matter be added dissolve, write down the quality of deionized water be added, continue thereafter plus Enter the deionized water of recorded 1.5 times of quality of deionized water quality and stirs evenly, continue to stir at this time and substance is added Amount stirs for 2.2 times of all metal ions total amount of tartaric acid to being completely dissolved；Remember that this solution is solution A；It will symbol Close K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7The tetraethyl orthosilicate and tetrabutyl zirconate of stoichiometric ratio are dissolved in volume In 1.2 times of the sum of tetraethyl orthosilicate and tetrabutyl zirconate volume of dehydrated alcohols, to remember that this solution is solution B；Then stirring It mixes lower solution A is added dropwise in solution B to whole to add, the temperature of solution system is then risen to 41 DEG C and keeps this temperature Deionized water is continuously added with 4 drops/minute speed under conditions of degree and stirring, until solution gradually becomes sticky and forms jelly Shape.Gelatin substance is ground 20 minutes in mortar after drying 30 hours in 150 DEG C of baking oven；Powder after grinding is in sky Furnace cooling after being warming up to 430 DEG C of heat preservations 7 hours in gas atmosphere with 20 DEG C/min of rate；By powder after cooling in agate It grinds in alms bowl and regrinds 20 minutes, the powder after grinding is warming up to 680 DEG C of heat preservations in air atmosphere with 15 DEG C/min of rate Furnace cooling after 20 hours；Filtering after ten minutes, drying are impregnated in the sodium hydroxide solution of 0.3M after taking out grinding and are being pressed 5 × 10 in power machine7The pressure of Pa pushes flakiness, and thin slice obtained is put into the tube furnace of both ends setting 900V DC voltage In in the oxygen atmosphere of 20Pa with 8 DEG C/min of rate be warming up to 760 DEG C heat preservation 20 hours after furnace cooling；The potassium is made Ion fast-ionic conductor thin slice.
Embodiment 5: by solid KNO3∶Al(NO3)3·9H2O∶NH4H2PO4: boric acid: Zn (NO3)2·6H2O is according to K6.15 Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7The ratio uniform of the nonstoichiometric molar ratio of middle respective element mixes, and is stirring strongly While deionized water to all solid matter be added dissolve, write down the quality of deionized water be added, continue thereafter plus Enter the deionized water of recorded 1.2 times of quality of deionized water quality and stirs evenly, continue to stir at this time and substance is added Amount stirs for 1.9 times of all metal ions total amount of tartaric acid to being completely dissolved；Remember that this solution is solution A；It will symbol Close K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7The tetraethyl orthosilicate and tetrabutyl zirconate of stoichiometric ratio are dissolved in volume In 1.1 times of the sum of tetraethyl orthosilicate and tetrabutyl zirconate volume of dehydrated alcohols, to remember that this solution is solution B；Then stirring It mixes lower solution A is added dropwise in solution B to whole to add, the temperature of solution system is then risen to 45 DEG C and keeps this temperature Deionized water is continuously added with 4 drops/minute speed under conditions of degree and stirring, until solution gradually becomes sticky and forms jelly Shape.Gelatin substance is ground 10 minutes in mortar after drying 45 hours in 150 DEG C of baking oven；Powder after grinding is in sky Furnace cooling after being warming up to 480 DEG C of heat preservations 5 hours in gas atmosphere with 30 DEG C/min of rate；By powder after cooling in agate It grinds in alms bowl and regrinds 20 minutes, the powder after grinding is warming up to 630 DEG C of heat preservations in air atmosphere with 10 DEG C/min of rate Furnace cooling after 10 hours；Filtering after ten minutes, drying are impregnated in the sodium hydroxide solution of 0.2M after taking out grinding and are being pressed 6 × 10 in power machine7The pressure of Pa pushes flakiness, and thin slice obtained is put into the tube furnace of both ends setting 920V DC voltage In in the oxygen atmosphere of 40Pa with 7 DEG C/min of rate be warming up to 840 DEG C heat preservation 15 hours after furnace cooling；The potassium is made Ion fast-ionic conductor thin slice.

Claims (1)

1. a kind of electric field induction crystallization K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7Potassium fast-ionic conductor, it is characterized in that: room temperature Potassium ion conductivity is more than 510-4S/cm；Its preparation process is by solid KNO3∶Al(NO3)3·9H2O∶NH4H2PO4: boric acid: Zn(NO3)2·6H2O is according to K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7The ratio of the nonstoichiometric molar ratio of middle respective element Example uniformly mixing, intensively stirred while deionized water to all solid matter is added dissolves, write down going of being added from The quality of sub- water continuously adds thereafter the deionized water of recorded 1.0-1.5 times of quality of deionized water quality and stirs evenly, The amount for continuing to stir and be added substance at this time stirs for the tartaric acid of 1.5-2.5 times of all metal ions total amount to complete Fully dissolved；Remember that this solution is solution A；K will be met6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7The positive silicic acid of stoichiometric ratio It is the anhydrous of 1.0-1.5 times of the sum of tetraethyl orthosilicate and tetrabutyl zirconate volume that tetra-ethyl ester and tetrabutyl zirconate, which are dissolved in volume, In ethyl alcohol, remember that this solution is solution B；Then solution A is added dropwise in solution B to all adding under stiring, it then will be molten The temperature of liquid system is risen to 40-50 DEG C and keeps being continuously added under conditions of this temperature and stirring with 3-5 drop/minute speed Deionized water, until solution gradually becomes sticky and formed gelatin；Gelatin substance is dry in 130-200 DEG C of baking oven It is ground 10-30 minutes in mortar after 20-48 hours；Powder after grinding is in air atmosphere with 5-30 DEG C/min of rate Furnace cooling after being warming up to 400-500 DEG C of heat preservation 3-10 hours；Powder after cooling is ground in alms bowl in agate and regrinds 10-30 Minute, rate of the powder in air atmosphere with 5-15 DEG C/min after grinding is warming up to 600-700 DEG C of heat preservation 10-20 hours Furnace cooling afterwards；Filtering after impregnating 5-15 minutes in the sodium hydroxide solution of 0.1-0.3M after grinding is taken out, dries and is pressing 1 × 10 in power machine7Pa-8×107The pressure of Pa pushes flakiness, and it is straight that thin slice obtained is put into both ends setting 800-1100V Rate in the tube furnace of galvanic electricity pressure in the oxygen atmosphere of 10-60Pa with 5-10 DEG C/min is warming up to 700-850 DEG C of heat preservation The potassium fast-ionic conductor is made in furnace cooling after 10-20 hours.
CN201910617186.8A 2019-06-27 2019-06-27 A kind of electric field induction crystallization K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7Potassium fast-ionic conductor and preparation method Withdrawn CN110372348A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910617186.8A CN110372348A (en) 2019-06-27 2019-06-27 A kind of electric field induction crystallization K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7Potassium fast-ionic conductor and preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910617186.8A CN110372348A (en) 2019-06-27 2019-06-27 A kind of electric field induction crystallization K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7Potassium fast-ionic conductor and preparation method

Publications (1)

Publication Number Publication Date
CN110372348A true CN110372348A (en) 2019-10-25

Family

ID=68250741

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910617186.8A Withdrawn CN110372348A (en) 2019-06-27 2019-06-27 A kind of electric field induction crystallization K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7Potassium fast-ionic conductor and preparation method

Country Status (1)

Country Link
CN (1) CN110372348A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112279233A (en) * 2020-10-21 2021-01-29 宁波大学 Cl-Doped epsilon-LiVOPO4Lithium fast ion conductor and liquid phase preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112279233A (en) * 2020-10-21 2021-01-29 宁波大学 Cl-Doped epsilon-LiVOPO4Lithium fast ion conductor and liquid phase preparation method thereof

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
CN108155413A (en) The Li of divalent alkaline-earth metal and tantalum codope7La3Zr2O12Solid electrolyte material and preparation method
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
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
CN102780029B (en) A kind of three component cation codope carbuncle type solid lithium-ion electrolytes
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
CN110372357A (en) A kind of P5+、Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof
CN110371981A (en) A kind of electric field induction crystallization K6.25Be0.1Al0.1P0.05Zr0.05Si1.7O7Potassium fast-ionic conductor and preparation method thereof
CN110350242A (en) A kind of liquid phase synthesis K2.41MgBa0.05Cu0.02Be0.2B0.15Ti0.05Si4.6O12Potassium fast-ionic conductor and preparation method thereof
CN110342920A (en) A kind of liquid phase synthesis K6.25Fe0.05Mg0.05Be0.2Al0.1Ti0.02Si1.68O7Potassium fast-ionic conductor and preparation method thereof
CN110330057A (en) A kind of liquid phase synthesis K6.4Fe0.05Be0.2Al0.15Ti0.05Si1.6O7Potassium fast-ionic conductor and preparation method thereof
CN110265710A (en) A kind of electric field induction crystallization K2.15MgCu0.05Be0.15P0.05Zr0.03Si4.77O12Potassium fast-ionic conductor and preparation method
CN102780030B (en) Four-component cation and anion co-doped garnet-type solid electrolyte
CN110372352A (en) A kind of liquid phase synthesis multiple ion doping potassium fast-ionic conductor and preparation method thereof
CN110364763A (en) A kind of liquid phase synthesis K6.4Fe0.05Cu0.05Be0.2Al0.1B0.15Ti0.02Si1.53O7Potassium fast-ionic conductor and preparation method
CN110372359A (en) A kind of electric field induction crystallization K2.26Ba0.05Cu0.02MgBe0.2Zr0.05Si4.75O12Potassium fast-ionic conductor and preparation method
CN110526699A (en) A kind of liquid phase synthesis K2.25MgBe0.1Al0.1P0.05Ti0.05Si4.7O12Potassium fast-ionic conductor and preparation method thereof
CN110336009A (en) A kind of liquid phase synthesis multiple ion doping K2MgSi5O12Potassium fast-ionic conductor and preparation method thereof
CN110372361A (en) A kind of liquid phase synthesis K2.4MgFe0.05Be0.2Al0.15Ti0.05Si4.6O12Potassium fast-ionic conductor and preparation method thereof
CN102867986B (en) One B3+, al3+, ti4+and Y3+cationic co-doped solid electrolyte Li7La3Zr2O12

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