CN110372357A - A kind of P5+、Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof - Google Patents

A kind of P5+、Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof Download PDF

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CN110372357A
CN110372357A CN201910617188.7A CN201910617188A CN110372357A CN 110372357 A CN110372357 A CN 110372357A CN 201910617188 A CN201910617188 A CN 201910617188A CN 110372357 A CN110372357 A CN 110372357A
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水淼
舒杰
任元龙
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Ningbo University
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Abstract

A kind of P5+、Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof, it is characterized in that: stoichiometric equation K2+x+y‑zMgBxAlyPzSi5‑x‑y‑zO12, in which: x=0.05-0.15；Y=0.05-0.15；Z=0.02-0.05；Room temperature potassium ion conductivity is more than 510‑4S/cm.Using Al3+、B3+Part replaces Si4+Ion generates gap potassium ion in crystal and reduces potassium ion migration activation energy；Pass through P5+Doping further decreases the electron conduction of fast-ionic conductor；Pass through the 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 K2MgSi5O12The surface of particle is modified, and easy-sintering characteristic is formed.These synergistic effects are so that the room temperature potassium ion conductivity of the potassium fast-ionic conductor is more than 510‑4S/cm is more nearly the potassium ion conductivity of liquid electrolyte.

Description

A kind of P5+、Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and its Preparation method
Technical field
The present invention relates to a kind of solid potassium fast-ionic conductor manufacturing fields.
Background technique
Lithium ion battery has volume, weight energy than high, voltage is high, self-discharge rate is low, memory-less effect, cycle life The absolute advantages such as length, power density height possess in global mobile power source market and exceed 30,000,000,000 dollar/year shares and far more than other The occupation rate of market of battery is electrochmical power source [Wu Yuping, Wan Chunrong, Jiang Changyin, the lithium ion two of most market development prospect Primary cell, Beijing: Chemical Industry Press, 2002.].Lithium ion secondary battery is most of using liquid both at home and abroad at present Electrolyte, liquid lithium ionic cell have some unfavorable factors, and such as: liquid organic electrolyte may be revealed, in excessively high temperature Lower generation explosion can not apply the occasion high in some pairs of security requirements to cause safety accident；Liquid electrolyte lithium from The sub- generally existing Capacity fading problem of battery, after a period of use due to electrode active material in the electrolyte molten Solution, reaction and degradation failure [Z.R.Zhang, Z.L.Gong, and Y.Yang, J.Phys.Chem.B, 108,2004, 17546.].And all-solid-state battery it is highly-safe, substantially without Capacity fading, wherein fast as the solid that electrolyte uses Ion conductor also acts the effect of diaphragm, simplifies the structure of battery；Further, since also simplifying life without completely cutting off air To the requirement of equipment during production, the configuration design of battery is also more convenient and flexible, and [Wen Zhaoyin, Zhu Xiujian know hero etc., entirely perhaps The research of solid secondary batteries, the 12nd Chinese solid-state ionics academic meeting paper collection, 2004.].
In all-solid lithium-ion battery, migration rate of the carrier in fast-ionic conductor is often far smaller than electrode surface Electric charge transfer and ion diffusion rates in positive electrode and become the rate determining step in entire electrode reaction dynamics, Therefore it is the core key for constructing high performance lithium ion battery that developing, which has the inorganic fast ionic conductor of higher li ionic conductivity, Place.From the point of view of current lithium fast-ionic conductor Development Status: LLTO (Li, La) TiO3Fast-ionic conductor has very high transgranular Conductivity is (10-3S/cm or so) and relatively high room temperature total conductivity (10-4S/cm-10-5S/cm), but LLTO decomposes electricity It forces down, the above all-solid-state battery of discharge voltage 3.7V and unstable to lithium anode can not be constituted；It is more with NASICON type Brilliant LiM2(PO4)3(M=Ti, Ge, Zr) is by tetrahedron PO4With octahedra MO6The grid structure collectively constituted, generation finish Hole and fillable coordination on structure, allow to regulate and control a large amount of Li ion, are a kind of up-and-coming high-lithium ion electricity Conductance fast-ionic conductor.By the substitution of aliovalent ion, introduce hole in the structure or calking lithium ion can further improve from Subconductivity [Xiaoxiong Xu, Zhaoyin Wen, ZhonghuaGu, 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
A kind of P that the technical problem to be solved by the present invention is to provide for existing background technique5+、Al3+、B3+Ion Cooperate with the K of doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof.Using Al3+、B3+Part replaces Si4+Ion, in crystal Middle generation high concentration gap potassium ion helps to reduce potassium ion migration to generate more potassium ions collaboration migration of short distance 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 to adapt to the fast transferring of potassium ion；And during the preparation process in K2MgSi5O12Particle Surface is modified, and easy-sintering characteristic is formed, and is conducive to improve the potassium fast-ionic conductor and is reduced crystal boundary when preparing bulk devices Gap increases consistency to improve the potassium ion conductivity of block potassium fast-ionic conductor.These synergistic effects are so that the potassium is fast The room temperature potassium ion conductivity of ion conductor 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 K2+x+y-zMgBxAlyPzSi5-x-y-zO12, in which: x=0.05- 0.15；Y=0.05-0.15；Z=0.02-0.05.
In the technical scheme, by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2∶B2O3: MgO is according to K2+x+y- zMgBxAlyPzSi5-x-y-zO12Nonstoichiometric 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, at 60 DEG C -120 after ball milling It is 2-10 hour dry in DEG C vacuum drying oven (gas pressure is in 3Pa-20Pa in baking oven), it is re-grind in agate stone roller alms bowl after taking-up 10-30 minutes, rate of the powder in air atmosphere with 5-30 DEG C/min after grinding was warming up to 550-650 DEG C of heat preservation 3-10 Furnace cooling after hour；Powder after cooling is ground in alms bowl in agate and is regrind 10-30 minutes, the powder after grinding is in air It is fast that rate in atmosphere in platinum crucible with 5-15 DEG C/min takes out burner hearth after being warming up to 1250-1350 DEG C of heat preservation 25-48 hours Quickly cooling is but；After material after cooling is crushed in grinding and is ground 30-50 minutes in the sodium hydroxide solution of 0.1-0.3M It filters, dry and in a press 1 × 10 after impregnating 5-15 minutes7Pa-8×107The pressure of Pa pushes flakiness, will be made Thin slice be put into the rate in tube furnace in the oxygen atmosphere of 10-60Pa with 5-10 DEG C/min and be warming up to 600-700 DEG C of heat preservation Furnace cooling after 80-150 hours；The potassium ion fast-ionic conductor thin slice is made.If Fig. 1 is that group becomes K2.08MgB0.05Al0.0 5P0.02Si4.88O12The XRD spectrum of potassium fast-ionic conductor, spectral line meet PDF card 82-0548 K2MgSi5O12Mutually without miscellaneous phase, It is 6.510 through LCR821 impedance analyzer measurement conductivity-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；It will be particularly beneficial that during the preparation process in K2MgSi5O12 The surface of particle is modified, and easy-sintering characteristic is formed, and is conducive to improve the potassium fast-ionic conductor and is subtracted when preparing bulk devices Few crystal boundary gap increases consistency to improve the potassium ion conductivity of block potassium fast-ionic conductor.These act synergistically so that The room temperature potassium ion conductivity of the potassium fast-ionic conductor is more than 510-4S/cm is very beneficial for the structure of full-solid potassium ion battery It builds.
Detailed description of the invention
Fig. 1 is that group becomes K2.08MgB0.05Al0.05P0.02Si4.88O12The XRD spectrum of potassium fast-ionic conductor.
Specific embodiment
Below in conjunction with embodiment, present invention is further described in detail.
Embodiment 1 is by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2∶B2O3: MgO is according to K2.08MgB0.05Al0.05P0.02 Si4.88O12Nonstoichiometric molar ratio ratio uniform mixing, be added quality be mixture quality 3% dehydrated alcohol, in ball With revolving speed ball milling 12 hours of 110 revs/min in grinding machine, in 60 DEG C of vacuum drying ovens, (gas pressure exists in baking oven after ball milling It is 2 hours dry in 3Pa), it grinds in alms bowl and re-grinds 15 minutes in agate after taking-up, the powder after grinding is in air atmosphere with 8 DEG C/min rate be warming up to 550 DEG C heat preservation 3 hours after furnace cooling；Powder after cooling is ground in alms bowl in agate and is ground again Mill 10 minutes, the powder after grinding are warming up to 1260 DEG C of heat preservations 30 in platinum crucible in air atmosphere with 5 DEG C/min of rate Burner hearth is taken out after hour to cool down rapidly；In the hydrogen-oxygen of 0.12M after material after cooling is crushed in grinding and is ground 30 minutes Change to impregnate in sodium solution and filters, dries and in a press 1.5 × 10 after five minutes7The pressure of Pa pushes flakiness, will be made Thin slice be put into tube furnace in the oxygen atmosphere of 15Pa with 5 DEG C/min of rate be warming up to 600 DEG C heat preservation 85 hours after with Furnace is cooling；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 2: by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2∶B2O3: MgO is according to K2.25MgB0.15Al0.15P0.05 Si4.65O12Nonstoichiometric molar ratio ratio uniform mixing, be added quality be mixture quality 9% dehydrated alcohol, in ball With revolving speed ball milling 43 hours of 450 revs/min in grinding machine, in 110 DEG C of vacuum drying ovens, (gas pressure exists in baking oven after ball milling Dry 10 hours in 15Pa), grind in alms bowl and re-grind 30 minutes in agate after taking-up, the powder after grinding in air atmosphere with 30 DEG C/min of rate is warming up to furnace cooling after 620 DEG C of heat preservations 10 hours；Powder after cooling is ground in alms bowl again in agate Grinding 30 minutes, the powder after grinding is warming up to 1350 DEG C of guarantors in platinum crucible in air atmosphere with 12 DEG C/min of rate Temperature is taken out burner hearth and is cooled down rapidly after 45 hours；In the hydrogen of 0.3M after material after cooling is crushed in grinding and is ground 45 minutes It filters, dry and in a press 7.5 × 10 after being impregnated 15 minutes in sodium hydroxide solution7The pressure of Pa pushes flakiness, will Thin slice obtained is put into tube furnace in the oxygen atmosphere of 60Pa that be warming up to 700 DEG C of heat preservations with 10 DEG C/min of rate 150 small When after furnace cooling；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 3: by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2∶B2O3: MgO according to K2.17MgB0.1Al0.1P0.03Si4.77O12Nonstoichiometric molar ratio ratio uniform mixing, additions quality be mixture quality 6% Dehydrated alcohol, in the ball mill with revolving speed ball milling 25 hours of 350 revs/min, after ball milling 90 DEG C of vacuum drying ovens (dry Gas pressure is in 15Pa in case) in dry 7 hours, grind in alms bowl and re-grind 20 minutes in agate after taking-up, the powder after grinding Furnace cooling after being warming up to 600 DEG C of heat preservations 7 hours in air atmosphere with 20 DEG C/min of rate；Powder after cooling is existed Agate, which is ground in alms bowl, to be regrind 20 minutes, and the powder after grinding is in air atmosphere with 10 DEG C/min of rate in platinum crucible Burner hearth is taken out after being warming up to 1310 DEG C of heat preservations 38 hours to cool down rapidly；Material after cooling is crushed in grinding and grinds 40 points It is impregnated in the sodium hydroxide solution of 0.2M after clock and filters, dries and in a press 3.6 × 10 after ten minutes7The pressure of Pa Flakiness is pushed, thin slice obtained is put into tube furnace and is warming up in the oxygen atmosphere of 40Pa with 7 DEG C/min of rate 650 DEG C heat preservation 110 hours after furnace cooling；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 4: by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2∶B2O3: MgO according to K2.13MgB0.1Al0.05P0.02Si4.83O12Nonstoichiometric molar ratio ratio uniform mixing, additions quality be mixture quality 5% dehydrated alcohol, in the ball mill with revolving speed ball milling 10 hours of 300 revs/min, in 90 DEG C of vacuum drying ovens after ball milling It is 10 hours dry in (gas pressure is in 15Pa in baking oven), it grinds in alms bowl and re-grinds 20 minutes, after grinding in agate after taking-up Furnace cooling after powder is warming up to 630 DEG C of heat preservations 10 hours in air atmosphere with 25 DEG C/min of rate；By powder after cooling Body is ground in alms bowl in agate to be regrind 30 minutes, and the powder after grinding is in air atmosphere with 15 DEG C/min in platinum crucible Rate is taken out burner hearth after being warming up to 1320 DEG C of heat preservations 40 hours and is cooled down rapidly；Material after cooling is crushed and ground in grinding It is impregnated in the sodium hydroxide solution of 0.15M after forty minutes and filters, dries and in a press 5 × 10 after ten minutes7Pa's Pressure pushes flakiness, and thin slice obtained is put into tube furnace in the oxygen atmosphere of 50Pa with 10 DEG C/min of rate liter Furnace cooling after temperature keeps the temperature 100 hours to 680 DEG C；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 5: by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2∶B2O3: MgO according to K2.2MgB0.15Al0.1P0.05Si4.7O12Nonstoichiometric molar ratio ratio uniform mixing, additions quality be mixture quality 7% Dehydrated alcohol, in the ball mill with revolving speed ball milling 10 hours of 320 revs/min, in 100 DEG C of vacuum drying ovens after ball milling It is 10 hours dry in (gas pressure is in 15Pa in baking oven), it grinds in alms bowl and re-grinds 30 minutes, after grinding in agate after taking-up Furnace cooling after powder is warming up to 620 DEG C of heat preservations 10 hours in air atmosphere with 30 DEG C/min of rate；By powder after cooling Body is ground in alms bowl in agate to be regrind 30 minutes, and the powder after grinding is in air atmosphere with 15 DEG C/min in platinum crucible Rate is taken out burner hearth after being warming up to 1300 DEG C of heat preservations 40 hours and is cooled down rapidly；Material after cooling is crushed and ground in grinding It is impregnated in the sodium hydroxide solution of 0.2M after 50 minutes and filters, dries and in a press 7 × 10 after ten minutes7The pressure of Pa Power pushes flakiness, and thin slice obtained is put into tube furnace and is warming up in the oxygen atmosphere of 50Pa with 8 DEG C/min of rate 690 DEG C heat preservation 120 hours after furnace cooling；The potassium ion fast-ionic conductor thin slice is made.

Claims (1)

1. a kind of P5+、Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor, it is characterized in that: stoichiometric equation is K2+x+y-zMgBxAlyPzSi5-x-y-zO12, in which: x=0.05-0.15；Y=0.05-0.15；Z=0.02-0.05；Room temperature potassium from Electron conductivity is more than 510-4S/cm；Its preparation process is by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2∶B2O3: MgO according to K2+x+y-zMgBxAlyPzSi5-x-y-zO12Nonstoichiometric molar ratio ratio uniform mixing, additions quality be mixture quality The dehydrated alcohol of 3%-9%, in the ball mill with revolving speed ball milling 10-50 hours of 100-500 revs/min, after ball milling For gas pressure in 3Pa-20Pa, temperature is drying 2-10 hours in 60 DEG C of -120 DEG C of vacuum drying ovens, is ground in alms bowl after taking-up in agate It re-grinds 10-30 minutes, the powder after grinding is warming up to 550-650 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 in platinum crucible with 5-15 DEG C/min takes after being warming up to 1250-1350 DEG C of heat preservation 25-48 hours Flake hearth-tapping cools down rapidly；In the hydroxide of 0.1-0.3M after material after cooling is crushed in grinding and is ground 30-50 minutes 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 600- in the oxygen atmosphere of 10-60Pa with 5-10 DEG C/min of rate by piece The potassium fast-ionic conductor is made in 700 DEG C of furnace coolings after heat preservation 80-150 hours.
CN201910617188.7A 2019-06-27 2019-06-27 A kind of P5+、Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof Withdrawn CN110372357A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112279257A (en) * 2020-10-20 2021-01-29 宁波大学 Partial oxygen vacancy B3+Doped glassy state potassium fast ion conductor K2O·4SiO2And method for preparing the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112279257A (en) * 2020-10-20 2021-01-29 宁波大学 Partial oxygen vacancy B3+Doped glassy state potassium fast ion conductor K2O·4SiO2And method for preparing the same

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