CN110265706A - A kind of electric field induction crystallization P5+、Al3+、B3+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof - Google Patents

A kind of electric field induction crystallization P5+、Al3+、B3+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof Download PDF

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CN110265706A
CN110265706A CN201910617216.5A CN201910617216A CN110265706A CN 110265706 A CN110265706 A CN 110265706A CN 201910617216 A CN201910617216 A CN 201910617216A CN 110265706 A CN110265706 A CN 110265706A
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水淼
舒杰
任元龙
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Ningbo University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
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    • H01M2300/0068—Solid electrolytes inorganic
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Abstract

A kind of electric field induction crystallization P5+、Al3+、B3+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof, it is characterized in that: stoichiometric equation K6+x+y‑zBxAlyPzSi2‑x‑y‑zO7, in which: x=0.1-0.15；Y=0.1-0.15；Z=0.02-0.05；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；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 P5+、Al3+、B3+The K of ion collaboration doping6Si2O7Potassium fastly from Sub- 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 IiM2(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 (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 a kind of electric field provided for existing background technique induction crystallization P5+、 Al3+、B3+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof.Using Al3+、B3+Part replaces Si4+From Son generates gap potassium ion in crystal, to generate more potassium ions collaboration migration of short distance, helping, which reduces potassium ion, is moved Move activation energy；Pass through P5+Doping further decreases the electron conduction of fast-ionic conductor；Pass through the B of small ionic radii3+Doping is adjusted The size of the migrating channels of potassium ion is saved to adapt to the fast transferring of potassium ion；And during the preparation process in K6Si2O7The table of particle Face is modified, and easy-sintering characteristic is formed, and being conducive to improve the potassium fast-ionic conductor, to reduce crystal boundary when preparing bulk devices empty Gap increases consistency to improve the potassium ion conductivity of block potassium fast-ionic conductor；Strong dc electric field induction knot is introduced simultaneously Crystalline substance accelerates the speed of crystallization, reduces the temperature of crystallization and improve crystallization integrity degree.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+x+y-zBxAlyPzSi2-x-y-zO7, in which: x=0.1-0.15； Y=0.1-0.15；Z=0.02-0.05.
In the technical scheme, by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2∶B2O3According to K6+x+y- zBxAlyPzSi2-x-y-zO7Nonstoichiometric molar ratio ratio uniform mixing, be added quality be mixture quality 3%-9% nothing Water-ethanol 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 is drying 2-10 hours in 60 DEG C of -120 DEG C of vacuum drying ovens, grinds in alms bowl after taking-up in agate and re-grinds 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 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 the oxygen in the tube furnace of both ends setting 800-1100V DC voltage in 10-60Pa Rate in gas atmosphere with 5-10 DEG C/min is warming up to furnace cooling after 700-800 DEG C of heat preservation 10-30 hours；Be made the potassium from Sub- fast-ionic conductor thin slice.If Fig. 1 is that group becomes K6.18B0.1Al0.1P0.02Si1.78O7The XRD spectrum of potassium fast-ionic conductor, spectrum Line meets PDF card 72-1518 K6Si2O7It is 6.110 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+、B3+Part replaces Si4+Ion produces in crystal Raw gap potassium ion helps to reduce potassium ion migration activation energy to generate more potassium ions collaboration migration of short distance；Pass through P5+Doping further decreases the electron conduction of fast-ionic conductor；Pass through the B of small ionic radii3+Doping adjusts moving for potassium ion The size in Mobile Communication road is to adapt to the fast transferring of potassium ion；It will be particularly beneficial that 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；The induction crystallization of strong dc electric field is introduced simultaneously to add The temperature of the speed, reduction crystallization that crystallize fastly simultaneously improves crystallization integrity degree.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 that group becomes K6.18B0.1Al0.1P0.02Si1.78O7The 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 K2CO3∶NH4H2PO4∶Al2O3∶SiO2∶B2O3According to K6.18B0.1Al0.iP0.02Si1.78O7Change Learn stoichiometric mole ratio ratio uniform mixing, be added quality be mixture quality 4.5% dehydrated alcohol, in the ball mill with 120 revs/min of revolving speed ball milling 16 hours is done in 60 DEG C of vacuum drying ovens (gas pressure is in 5Pa in baking oven) after ball milling It dry 2 hours, 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 Rate is warming up to furnace cooling after 470 DEG C of heat preservations 3 hours；Powder after cooling is ground in alms bowl in agate and is regrind 10 minutes, Furnace cooling after powder after grinding is warming up to 750 DEG C of heat preservations 10 hours in air atmosphere with 5 DEG C/min of rate；It takes out It filters, dry and in a press 1 × 10 after being impregnated 6 minutes in the sodium hydroxide solution of 0.1M after grinding7The pressure of Pa Push flakiness, by thin slice obtained be put into both ends setting 800V DC voltage tube furnace in the oxygen atmosphere of 15Pa with 5 DEG C/min of rate is warming up to furnace cooling after 710 DEG C of heat preservations 10 hours；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 2: by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2∶B2O3According to K6.25B0.15Al0.15P0.05Si1.65O7's The ratio uniform of nonstoichiometric molar ratio mixes, and the dehydrated alcohol that quality is mixture quality 9% is added, in the ball mill with 480 revs/min of revolving speed ball milling 45 hours, after ball milling in 110 DEG C of vacuum drying ovens (gas pressure is in 20Pa in baking oven) It is 9 hours dry, it 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/minute The rate of clock is warming up to furnace cooling after 530 DEG C of heat preservations 10 hours；Powder after cooling is ground in alms bowl in agate and regrinds 30 Minute, the powder after grinding is cold with furnace after being warming up to 850 DEG C of heat preservations 19 hours with 15 DEG C/min of rate in air atmosphere But；Take out filtering after impregnating 12 minutes after grinding in the sodium hydroxide solution of 0.3M, dry and in a press 7 × 107The pressure of Pa pushes flakiness, and thin slice obtained is put into the tube furnace of both ends setting 1050V DC voltage 60Pa's Furnace cooling after being warming up to 800 DEG C of heat preservations 30 hours in oxygen atmosphere with 10 DEG C/min of rate；The fast ion of the potassium ion is made Conductor sheet.
Embodiment 3: by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2∶B2O3According to K6.22B0.12Al0.13P0.03Si1.72O7's The ratio uniform of nonstoichiometric molar ratio mixes, and the dehydrated alcohol that quality is mixture quality 5% is added, in the ball mill with 300 revs/min of revolving speed ball milling 30 hours is done in 80 DEG C of vacuum drying ovens (gas pressure is in 15Pa in baking oven) after ball milling It dry 7 hours, 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 Rate be warming up to 510 DEG C heat preservation 7 hours after furnace cooling；Powder after cooling is ground in agate and regrinds 20 points in alms bowl Clock, furnace cooling after the powder after grinding is warming up to 810 DEG C of heat preservations 15 hours in air atmosphere with 10 DEG C/min of rate； It takes out to impregnate in the sodium hydroxide solution of 0.2M after grinding and filters, dries and in a press 5 × 10 after ten minutes7Pa's Pressure pushes flakiness, and thin slice obtained is put into the oxygen atmosphere in the tube furnace of both ends setting 900V DC voltage in 30Pa In with 7 DEG C/min of rate be warming up to 750 DEG C heat preservation 20 hours after furnace cooling；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 4: by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2∶B2O3According to K6.18B0.1Al0.12P0.04Si1.74O7's The ratio uniform of nonstoichiometric molar ratio mixes, and the dehydrated alcohol that quality is mixture quality 8% is added, in the ball mill with 450 revs/min of revolving speed ball milling 40 hours, after ball milling in 110 DEG C of vacuum drying ovens (gas pressure is in 18Pa in baking oven) It is 8 hours dry, 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/minute The rate of clock is warming up to furnace cooling after 500 DEG C of heat preservations 5 hours；Powder after cooling is ground in agate and regrinds 12 points in alms bowl Clock, furnace cooling after the powder after grinding is warming up to 790 DEG C of heat preservations 10 hours in air atmosphere with 5 DEG C/min of rate；It takes It filters, dry and in a press 4 × 10 after being impregnated 7 minutes in the sodium hydroxide solution of 0.12M after grinding out7The pressure of Pa Power pushes flakiness, and thin slice obtained is put into the tube furnace of both ends setting 850V DC voltage in the oxygen atmosphere of 50Pa Furnace cooling after being warming up to 750 DEG C of heat preservations 20 hours with 8 DEG C/min of rate；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 5: by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2∶B2O3According to K6.23B0.1Al0.15P0.02Si1.73O7's The ratio uniform of nonstoichiometric molar ratio mixes, and the dehydrated alcohol that quality is mixture quality 7% is added, in the ball mill with 400 revs/min of revolving speed ball milling 20 hours, after ball milling in 100 DEG C of vacuum drying ovens (gas pressure is in 15Pa in baking oven) It is 8 hours dry, it grinds in alms bowl and re-grinds 20 minutes in agate after taking-up, the powder after grinding is in air atmosphere with 7 DEG C/min Rate be warming up to 520 DEG C heat preservation 7 hours after furnace cooling；Powder after cooling is ground in agate and regrinds 10 points in alms bowl Clock, furnace cooling after the powder after grinding is warming up to 780 DEG C of heat preservations 15 hours in air atmosphere with 7 DEG C/min of rate；It takes It is impregnated in the sodium hydroxide solution of 0.2M after grinding out and filters, dries and in a press 2 × 10 after ten minutes7The pressure of Pa Power pushes flakiness, and thin slice obtained is put into the oxygen atmosphere in the tube furnace of both ends setting 1000V DC voltage in 55Pa In with 9 DEG C/min of rate be warming up to 720 DEG C heat preservation 15 hours after furnace cooling；The potassium ion fast-ionic conductor thin slice is made.

Claims (1)

1. a kind of electric field induction crystallization P5+、Al3+、B3+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor, it is characterized in that: change Metering-type is K6+x+y-zBxAlyPzSi2-x-y-zO7, in which: x=0.1-0.15；Y=0.1-0.15；Z=0.02-0.05；Room temperature Potassium ion conductivity is more than 510-4S/cm；Its preparation process is by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2∶B2O3According to K6+x+y-zBxAlyPzSi2-x-y-zO7Nonstoichiometric molar ratio ratio uniform mixing, additions quality be mixture quality 3%- 9% dehydrated alcohol, in the ball mill with revolving speed ball milling 10-50 hours of 100-500 revs/min, in gas after ball milling Pressure is that 3Pa-20Pa temperature is drying 2-10 hours in 60 DEG C of -120 DEG C of vacuum drying ovens, grinds in alms bowl after taking-up in agate and grinds again Mill 10-30 minutes, rate of the powder in air atmosphere with 5-30 DEG C/min after grinding is warming up to 450-550 DEG C of heat preservation 3- Furnace cooling after 10 hours；Powder after cooling is ground in alms bowl in agate and is regrind 10-30 minutes, the powder after grinding is in sky Rate in gas atmosphere with 5-15 DEG C/min is warming up to furnace cooling after 750-850 DEG C of heat preservation 10-20 hours；After taking out grinding It filters, dry and in a press 1 × 10 after being impregnated 5-15 minutes in the sodium hydroxide solution of 0.1-0.3M7Pa-8× 107The pressure of Pa pushes flakiness, and thin slice obtained is put into the tube furnace of both ends setting 800-1100V DC voltage Rate in the oxygen atmosphere of 10-60Pa with 5-10 DEG C/min is warming up to furnace cooling after 700-800 DEG C of heat preservation 10-30 hours The potassium fast-ionic conductor is made.
CN201910617216.5A 2019-06-27 2019-06-27 A kind of electric field induction crystallization P5+、Al3+、B3+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof Withdrawn CN110265706A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111494979A (en) * 2020-04-08 2020-08-07 大连理工大学 Crystallization system and method for strengthening molecular crystallization process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111494979A (en) * 2020-04-08 2020-08-07 大连理工大学 Crystallization system and method for strengthening molecular crystallization process
CN111494979B (en) * 2020-04-08 2021-07-16 大连理工大学 Crystallization system and method for strengthening molecular crystallization process

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Application publication date: 20190920