CN110357599A - A kind of P5+、Al3+、Be2+、Zn2+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof - Google Patents

A kind of P5+、Al3+、Be2+、Zn2+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof Download PDF

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CN110357599A
CN110357599A CN201910617470.5A CN201910617470A CN110357599A CN 110357599 A CN110357599 A CN 110357599A CN 201910617470 A CN201910617470 A CN 201910617470A CN 110357599 A CN110357599 A CN 110357599A
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potassium
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potassium ion
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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+、Be2+、Zn2+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof, it is characterized in that: stoichiometric equation K2+2x+y‑z‑ 2mMgBexAlyPzZnmSi5‑x‑y‑zO12, in which: x=0.05-0.15；Y=0.05-0.15；Z=0.01-0.03；M=0.01-0.03；Room temperature potassium ion conductivity is more than 510‑4S/cm.Using Al3+、Be2+Part replaces Si4+Ion generates gap potassium ion in crystal and reduces potassium ion migration activation energy；Pass through P5+Doping further decreases the electron conduction of fast-ionic conductor；Pass through the Be of small ionic radii2+Doping adjusts the size of the migrating channels of potassium ion to adapt to the fast transferring of potassium ion；Pass through Zn2+Part replaces potassium ion that cation vacancy is caused to increase potassium ion migrating channels；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+、Be2+、Zn2+The K of ion collaboration doping2MgSi5O12The fast ion of potassium is led Body 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, 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-xCrxP3O12, Li1+xGe2-xAlxP3O12, Li1+ xTi2-xInxP3O12Etc. systems or other such as Li1+2x+2yAlxMgyTi2-x-ySixP3-xO12, Li1+x+yAlxTi2-xSiyP3-yO12, Li1+ xAlxTi2-xP3O12Etc. systems all have higher lithium ion conductivity.But the room temperature lithium ion conductivity of these systems usually exists 10-4S/cm-10-6Between S/cm, requirement of the non-film lithium ion battery to electrolytic conductivity can't be met very well.In addition NASICON system is equally unstable to lithium anode.Ramaswamy Murugan is equal to 2007 in German application term A kind of novel lithium ion fast-ionic conductor Li has been reported on periodical7La3Zr2O12Its lithium ion conductivity at normal temperature is more than 1 × 10-4S·cm-1, decomposition voltage is more than 5.5V, and lithium metal can be used as cathode, be that one kind has very much to air and moisture stabilization The fast ion solid electrolyte of the lithium of application potential (Ramaswamy Murugan, Venkataraman Thangadurai, Werner Weppner, (2007) " Fast lithium ion conduction in garnet-type Li7La3Zr2O12" Angewandte Chemie-International Edition 46 (41): 7778-7781.).However 5.0 × 10 will often be reached to the higher occasion conductivity of current requirements-4S/cm or so just can satisfy normal battery operation It needs, in addition the solid electrolyte synthesis temperature is at 1350 DEG C or so, and temperature is high, and energy consumption is high.
It additionally needs and is pointed out that the consumption of lithium rises rapidly as secondary cell is quickly applied in power battery, Reserves of the elemental lithium in the earth's crust very it is low only PPM grade, rare lithium resource make future lithium ion battery cost it is continuous on It rises.The electrochemical energy storing device for seeking a kind of alternative low cost becomes urgent problem to be solved.Sodium and potassium element are in the earth The electrochemical properties very high and with lithium of abundance have certain similar, be following to be expected to replace most having for lithium ion all-solid-state battery uncommon The selection of prestige.However the building essential potassium ion conductor of potassium ion all-solid-state battery is also substantially at space state at present. Therefore screening has the potassium fast ion conducting material of high conductance to the inexpensive kalium ion battery of building and full-solid potassium ion Battery has great importance.
Summary of the invention
A kind of P that the technical problem to be solved by the present invention is to provide for existing background technique5+、Al3+、Be2+、Zn2+ The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof.Using Al3+、Be2+Part replaces Si4+Ion, In crystal generate high concentration gap potassium ion, thus generate short distance more potassium ions collaboration migration, facilitate reduce potassium from Son migration activation energy；Pass through P5+Doping further decreases the electron conduction of fast-ionic conductor；Pass through the Be of small ionic radii2+ Doping adjusts the size of the migrating channels of potassium ion to adapt to the fast transferring of potassium ion；Pass through Zn2+Part replaces potassium ion to make Increase potassium ion migrating channels at cation vacancy；And during the preparation process in K2MgSi5O12The surface of particle is modified, shape At easy-sintering characteristic, is conducive to improve the potassium fast-ionic conductor and reduces crystal boundary gap when preparing bulk devices, increase consistency 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 Ionic conductivity 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+2x+y-z-2mMgBexAlyPzZnmSi5-x-y-zO12, in which: x= 0.05-0.15；Y=0.05-0.15；Z=0.01-0.03；M=0.01-0.03.
In the technical scheme, by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2: BeO: ZnO: MgO according to K2+2x+y-z- 2mMgBexAlyPzZnmSi5-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, 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 550-650 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 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 It is cooling rapidly；In the sodium hydroxide solution 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 middle immersion 5-15 minutes7Pa-8×107The pressure of Pa pushes flakiness, will make In half SiO 2 powder full of porcelain boat of thin slice embedment obtained, which is put into the oxygen gas in tube furnace in 10-60Pa Rate in atmosphere with 5-10 DEG C/min is warming up to furnace cooling after 750-850 DEG C of heat preservation 80-150 hours；It is fast that the potassium ion is made Ion conductor thin slice.If Fig. 1 is that group becomes K2.09MgBe0.05Al0.05P0.02Zn0.02Si4.88O12The XRD diagram of potassium fast-ionic conductor Spectrum, spectral line meet PDF card 82-0548 K2MgSi5O12Mutually without miscellaneous phase, it is through LCR821 impedance analyzer measurement conductivity 7.4·10-4S/cm。
Compared with the prior art, the advantages of the present invention are as follows: use Al3+、Be2+Part replaces Si4+Ion, in crystal High concentration gap potassium ion is generated, to generate more potassium ions collaboration migration of short distance, helping, which reduces potassium ion migration, lives Change energy；Pass through P5+Doping further decreases the electron conduction of fast-ionic conductor；Pass through the Be of small ionic radii2+Doping is adjusted The size of the migrating channels of potassium ion is to adapt to the fast transferring of potassium ion；Pass through Zn2+Part replaces potassium ion to cause cation Vacancy increases potassium ion migrating channels；It will be particularly beneficial that during the preparation process in K2MgSi5O12The surface of particle is modified, Easy-sintering characteristic is formed, is conducive to improve the potassium fast-ionic conductor and reduces crystal boundary gap when preparing bulk devices, increases densification Degree 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 K2.09MgBe0.05Al0.05P0.02Zn0.02Si4.88O12The XRD spectrum of potassium fast-ionic conductor.
Specific embodiment
Below in conjunction with embodiment, present invention is further described in detail.
Embodiment 1: by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2: BeO: ZnO: MgO according to K2.09MgBe0.05Al0.0 5P0.02Zn0.02Si4.88O12Nonstoichiometric molar ratio ratio uniform mixing, be added quality be mixture quality 3% it is anhydrous Ethyl alcohol, in the ball mill with revolving speed ball milling 12 hours of 110 revs/min, in 60 DEG C of vacuum drying ovens (gas in baking oven after ball milling Body pressure is in 3Pa) in dry 2 hours, grind in alms bowl and re-grind 15 minutes in agate after taking-up, the powder after grinding is in air gas Furnace cooling after being warming up to 560 DEG C of heat preservations 3 hours in atmosphere with 8 DEG C/min of rate；Powder after cooling is ground in alms bowl in agate Regrinding 10 minutes, the powder after grinding is warming up to 1260 DEG C in platinum crucible in air atmosphere with 5 DEG C/min of rate Burner hearth is taken out after heat preservation 30 hours to cool down rapidly；0.1M's after material after cooling is crushed in grinding and is ground 30 minutes It is impregnated in sodium hydroxide solution and filters, dries and in a press 1.2 × 10 after five minutes7The pressure of Pa pushes flakiness, will In half SiO 2 powder full of porcelain boat of thin slice embedment obtained, which is put into the oxygen atmosphere in tube furnace in 15Pa In with 5 DEG C/min of rate be warming up to 750 DEG C heat preservation 90 hours after furnace cooling；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 2: by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2: BeO: ZnO: MgO according to K2.36MgBe0.15Al0.1 5P0.03Zn0.03Si4.67O12Nonstoichiometric molar ratio ratio uniform mixing, be added quality be mixture quality 9% it is anhydrous Ethyl alcohol, in the ball mill with revolving speed ball milling 43 hours of 500 revs/min, after ball milling in 110 DEG C of vacuum drying ovens (in baking oven Gas pressure is in 15Pa) in dry 10 hours, grind in alms bowl and re-grind 30 minutes in agate after taking-up, the powder after grinding is in sky Furnace cooling after being warming up to 650 DEG C of heat preservations 10 hours in gas atmosphere with 30 DEG C/min of rate；By powder after cooling in agate It grinds in alms bowl and regrinds 30 minutes, the powder after grinding is heated up in air atmosphere in platinum crucible with 12 DEG C/min of rate Burner hearth is taken out after keeping the temperature 45 hours to 1350 DEG C to cool down rapidly；After material after cooling is crushed in grinding and grinds 45 minutes 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 The porcelain boat is put into tube furnace 60Pa's by thin slice by half SiO 2 powder full of porcelain boat of thin slice obtained embedment Furnace cooling after being warming up to 830 DEG C of heat preservations 150 hours in oxygen atmosphere with 10 DEG C/min of rate；Be made the potassium ion fastly from Sub- conductor sheet.
Embodiment 3: by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2: BeO: ZnO: MgO according to K2.24MgBe0.1Al0. 1P0.02Zn0.02Si4.78O12Nonstoichiometric molar ratio ratio uniform mixing, be added quality be mixture quality 7% it is anhydrous Ethyl alcohol, in the ball mill with revolving speed ball milling 25 hours of 370 revs/min, in 90 DEG C of vacuum drying ovens (gas in baking oven after ball milling Body pressure is in 15Pa) in dry 8 hours, grind in alms bowl and re-grind 20 minutes in agate after taking-up, the powder after grinding is in air Furnace cooling after being warming up to 610 DEG C of heat preservations 7 hours in atmosphere with 20 DEG C/min of rate；Powder after cooling is ground in agate It is regrind 20 minutes in alms bowl, the powder after grinding is warming up in air atmosphere in platinum crucible with 10 DEG C/min of rate 1300 DEG C heat preservation 38 hours after take out burner hearth cool down rapidly；Material after cooling is crushed and ground in grinding and is existed after forty minutes It is impregnated in the sodium hydroxide solution of 0.2M and filters, dries and in a press 3.6 × 10 after ten minutes7The pressure of Pa depresses to The porcelain boat is put into tube furnace 40Pa's by thin slice by half SiO 2 powder full of porcelain boat of thin slice obtained embedment Furnace cooling after being warming up to 800 DEG C of heat preservations 110 hours in oxygen atmosphere with 7 DEG C/min of rate；The fast ion of the potassium ion is made Conductor sheet.
Embodiment 4: by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2: BeO: ZnO: MgO according to K2.37MgBe0.15Al0. 1P0.01Zn0.01Si4.74O12Nonstoichiometric molar ratio ratio uniform mixing, be added quality be mixture quality 6% it is anhydrous Ethyl alcohol, in the ball mill with revolving speed ball milling 10 hours of 350 revs/min, in 90 DEG C of vacuum drying ovens (gas in baking oven after ball milling Body pressure is in 15Pa) in dry 10 hours, grind in alms bowl and re-grind 20 minutes in agate after taking-up, the powder after grinding is in air Furnace cooling after being warming up to 620 DEG C of heat preservations 10 hours in atmosphere with 25 DEG C/min of rate；Powder after cooling is ground in agate It is regrind 30 minutes in alms bowl, the powder after grinding is warming up in air atmosphere in platinum crucible with 15 DEG C/min of rate 1310 DEG C heat preservation 40 hours after take out burner hearth cool down rapidly；Material after cooling is crushed and ground in grinding and is existed after forty minutes It is impregnated in the sodium hydroxide solution of 0.15M and filters, dries and in a press 5 × 10 after ten minutes7The pressure of Pa depresses to The porcelain boat is put into tube furnace 50Pa's by thin slice by half SiO 2 powder full of porcelain boat of thin slice obtained embedment Furnace cooling after being warming up to 850 DEG C of heat preservations 100 hours in oxygen atmosphere with 10 DEG C/min of rate；Be made the potassium ion fastly from Sub- conductor sheet.
Embodiment 5: by solid K2CO3∶NH4H2PO4∶Al2O3∶SiO2: BeO: ZnO: MgO according to K2.38MgBe0.15Al0.1 5P0.01Zn0.03Si4.69O12Nonstoichiometric molar ratio ratio uniform mixing, be added quality be mixture quality 8% it is anhydrous Ethyl alcohol, 400 revs/min of revolving speed ball milling 10 hours in the ball mill, in 100 DEG C of vacuum drying ovens (gas in baking oven after ball milling Body pressure is in 15Pa) in dry 10 hours, grind in alms bowl and re-grind 30 minutes in agate after taking-up, the powder after grinding is in air Furnace cooling after being warming up to 650 DEG C of heat preservations 10 hours in atmosphere with 30 DEG C/min of rate；Powder after cooling is ground in agate It is regrind 30 minutes in alms bowl, the powder after grinding is warming up in air atmosphere in platinum crucible with 15 DEG C/min of rate 1310 DEG C heat preservation 40 hours after take out burner hearth cool down rapidly；After material after cooling is crushed in grinding and is ground 50 minutes 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 The porcelain boat is put into the oxygen in tube furnace in 40Pa in half SiO 2 powder full of porcelain boat of thin slice obtained embedment by piece Furnace cooling after being warming up to 800 DEG C of heat preservations 120 hours in gas atmosphere with 8 DEG C/min of rate；The fast ion of the potassium ion is made to lead Body thin slice.

Claims (1)

1. a kind of P5+、Al3+、Be2+、Zn2+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor, it is characterized in that: chemistry meter Amount formula is K2+2x+y-z-2mMgBexAlyPzZnmSi5-x-y-zO12, in which: x=0.05-0.15；Y=0.05-0.15；Z=0.01- 0.03；M=0.01-0.03；Room temperature potassium ion conductivity is more than 510-4S/cm；Its preparation process is by solid K2CO3∶ NH4H2PO4∶Al2O3∶SiO2: BeO: ZnO: MgO according to K2+2x+y-z-2mMgBexAlyPzZnmSi5-x-y-zO12Stoichiometric molar The ratio uniform of ratio mixes, and the dehydrated alcohol that quality is mixture quality 3%-9% is added, turned in the ball mill with 100-500/ It is that 60 DEG C of -120 DEG C of vacuum are dried that revolving speed ball milling 10-50 hours of minute, which are 3Pa-20Pa temperature in gas pressure after ball milling, It is 2-10 hours dry in case, it grinds in alms bowl and re-grinds 10-30 minutes in agate after taking-up, the powder after grinding is in air atmosphere Furnace cooling after being warming up to 550-650 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 in air atmosphere with 5-15 DEG C/min of rate in platinum crucible Burner hearth is taken out after being warming up to 1250-1350 DEG C of heat preservation 25-48 hours to cool down rapidly；Material after cooling is crushed simultaneously in grinding Grinding 30-50 minute after is impregnated 5-15 minutes in the sodium hydroxide solution of 0.1-0.3M after filter, dry and in a press 1 × 107Pa-8×107The pressure of Pa pushes flakiness, and thin slice obtained embedment half is full of to the SiO 2 powder of porcelain boat In, which is put into tube furnace, 750-850 is warming up to 5-10 DEG C/min of rate in the oxygen atmosphere of 10-60Pa Furnace cooling is to be made the potassium fast-ionic conductor DEG C after heat preservation 80-150 hour.
CN201910617470.5A 2019-06-27 2019-06-27 A kind of P5+、Al3+、Be2+、Zn2+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof Withdrawn CN110357599A (en)

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