CN110371996A - A kind of Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof - Google Patents

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

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CN110371996A
CN110371996A CN201910617220.1A CN201910617220A CN110371996A CN 110371996 A CN110371996 A CN 110371996A CN 201910617220 A CN201910617220 A CN 201910617220A CN 110371996 A CN110371996 A CN 110371996A
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水淼
舒杰
任元龙
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Ningbo University
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
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    • 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
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Abstract

A kind of Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof, it is characterized in that: stoichiometric equation K2+x+yMgBxAlySi5‑x‑yO12, in which: x=0.05-0.15；Y=0.05-0.15；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 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 Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and its system 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 Al that the technical problem to be solved by the present invention is to provide for existing background technique3+、B3+Ion collaboration The K of doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof.Using 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 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 is formed easy-sintering characteristic, is conducive to improve the fast ion of the potassium Conductor reduces crystal boundary gap when preparing bulk devices, increases consistency to improve the potassium ion electricity of block potassium fast-ionic conductor Conductance.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.
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+yMgBxAlySi5-x-yO12, in which: x=0.05-0.15； Y=0.05-0.15.
In the technical scheme, by solid K2CO3∶Al2O3∶SiO2∶B2O3: MgO is according to K2+x+yMgBxAlySi5-x-yO12's The ratio uniform of nonstoichiometric molar ratio mixes, and the dehydrated alcohol that quality is mixture quality 3%-9% is added, in the ball mill With revolving speed ball milling 10-50 hours of 100-500 revs/min, after ball milling gas pressure be 3Pa-20Pa temperature be 60 DEG C- It is 2-10 hours dry in 120 DEG C of vacuum drying ovens, it grinds in alms bowl and re-grinds 10-30 minutes in agate after taking-up, the powder after grinding Rate in air atmosphere with 5-30 DEG C/min is warming up to furnace cooling after 550-650 DEG C of heat preservation 3-10 hours；After cooling Powder agate grind alms bowl in regrind 10-30 minutes, the powder after grinding is in air atmosphere with 5-15 in platinum crucible DEG C/min rate be warming up to 1250-1350 DEG C of heat preservation 25-48 hours after take out burner hearth cool down rapidly；By material after cooling It filters, dry after being impregnated 5-15 minutes in the sodium hydroxide solution of 0.1-0.3M after crushing and grinding 30-50 minutes in grinding Dry doubling is in a press 1 × 107Pa-8×107The pressure of Pa pushes flakiness, by thin slice obtained embedment half full of porcelain boat In SiO 2 powder, which is put into tube furnace in the oxygen atmosphere of 10-60Pa with 5-10 DEG C/min of rate liter Temperature is to 750-850 DEG C of furnace cooling after heat preservation 80-150 hours；The potassium ion fast-ionic conductor thin slice is made.If Fig. 1 is composition For K2.1MgB0.05Al0.05Si4.9O12The XRD spectrum of potassium fast-ionic conductor, spectral line meet PDF card 82-0548K2MgSi5O12 It is 6.410 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 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 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；It is special Not it is beneficial that during the preparation process in K2MgSi5O12The 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.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 very beneficial for the building of full-solid potassium ion battery.
Detailed description of the invention
Fig. 1 is K2.1MgB0.05Al0.05Si4.9O12The 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∶Al2O3∶SiO2∶B2O3: MgO is according to K2.1MgB0.05Al0.05Si4.9O12Chemistry meter Measure molar ratio ratio uniform mixing, be added quality be mixture quality 3.2% dehydrated alcohol, in the ball mill with 120 turns/ Revolving speed ball milling 12 hours of minute, drying 2 is small in 60 DEG C of vacuum drying ovens (gas pressure is in 3Pa in baking oven) after ball milling When, 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 of rate Furnace cooling after being warming up to 560 DEG C of heat preservations 3 hours；Powder after cooling is ground in alms bowl in agate and is regrind 10 minutes, is ground Powder afterwards takes out furnace after being warming up to 1250 DEG C of heat preservations 30 hours with 5 DEG C/min of rate in platinum crucible in air atmosphere Thorax cools down rapidly；Material after cooling is crushed in grinding and is impregnated in the sodium hydroxide solution of 0.1M after grinding 30 minutes It filters, dry and in a press 1.2 × 10 after five minutes7The pressure of Pa pushes flakiness, and thin slice obtained embedment is partly filled In the SiO 2 powder of full porcelain boat, which is put into tube furnace in the oxygen atmosphere of 15Pa with 5 DEG C/min of rate Furnace cooling after being warming up to 760 DEG C of heat preservations 90 hours；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 2: by solid K2CO3∶Al2O3∶SiO2∶B2O3: MgO is according to K2.3MgB0.15Al0.15Si4.7O12Chemistry meter The ratio uniform mixing for measuring molar ratio, is added the dehydrated alcohol that quality is mixture quality 9%, in the ball mill with 480 revs/min The revolving speed ball milling of clock 43 hours, drying 10 is small in 115 DEG C of vacuum drying ovens (gas pressure is in 15Pa in baking oven) after ball milling When, 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/min of rate Furnace cooling after being warming up to 650 DEG C of heat preservations 10 hours；Powder after cooling is ground in alms bowl in agate and is regrind 30 minutes, is ground Powder afterwards takes out furnace after being warming up to 1350 DEG C of heat preservations 45 hours with 12 DEG C/min of rate in platinum crucible in air atmosphere Thorax cools down rapidly；Material after cooling is crushed in grinding and is impregnated in the sodium hydroxide solution of 0.3M after grinding 45 minutes It filters, dry and in a press 8 × 10 after 15 minutes7The pressure of Pa pushes flakiness, and thin slice obtained embedment is partly filled In the SiO 2 powder of full porcelain boat, which is put into tube furnace in the oxygen atmosphere of 60Pa with 10 DEG C/min of speed Rate is warming up to furnace cooling after 840 DEG C of heat preservations 150 hours；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 3: by solid K2CO3∶Al2O3∶SiO2∶B2O3: MgO is according to K2.15MgB0.07Al0.08Si4.85O12Chemistry The ratio uniform of stoichiometric mole ratio mixes, and the dehydrated alcohol that quality is mixture quality 6% is added, in the ball mill with 370 turns/ Revolving speed ball milling 25 hours of minute, drying 8 is small in 100 DEG C of vacuum drying ovens (gas pressure is in 15Pa in baking oven) after ball milling When, 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/min of rate Furnace cooling after being warming up to 610 DEG C of heat preservations 7 hours；Powder after cooling is ground in alms bowl in agate and is regrind 20 minutes, is ground Powder afterwards takes out furnace after being warming up to 1310 DEG C of heat preservations 38 hours with 10 DEG C/min of rate in platinum crucible in air atmosphere Thorax cools down rapidly；Material after cooling is crushed in grinding and is ground and is impregnated in the sodium hydroxide solution of 0.2M after forty minutes It filters, dry and in a press 3.6 × 10 after ten minutes7The pressure of Pa pushes flakiness, by thin slice obtained embedment half In SiO 2 powder full of porcelain boat, which is put into tube furnace in the oxygen atmosphere of 40Pa with 7 DEG C/min of speed Rate is warming up to furnace cooling after 810 DEG C of heat preservations 100 hours；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 4: by solid K2CO3∶Al2O3∶SiO2∶B2O3: MgO is according to K2.15MgB0.05Al0.1Si4.85O12Chemistry meter The ratio uniform mixing for measuring molar ratio, is added the dehydrated alcohol that quality is mixture quality 6%, in the ball mill with 370 revs/min The revolving speed ball milling of clock 10 hours, drying 10 is small in 90 DEG C of vacuum drying ovens (gas pressure is in 15Pa in baking oven) after ball milling When, it grinds in alms bowl and re-grinds 20 minutes in agate after taking-up, the powder after grinding is in air atmosphere with 25 DEG C/min of rate Furnace cooling after being warming up to 620 DEG C of heat preservations 10 hours；Powder after cooling is ground in alms bowl in agate and is regrind 30 minutes, is ground Powder afterwards takes out furnace after being warming up to 1300 DEG C of heat preservations 40 hours with 15 DEG C/min of rate in platinum crucible in air atmosphere Thorax cools down rapidly；Material after cooling is crushed in grinding and is ground and is impregnated in the sodium hydroxide solution of 0.1M after forty minutes It filters, dry and in a press 5.5 × 10 after ten minutes7The pressure of Pa pushes flakiness, by thin slice obtained embedment half In SiO 2 powder full of porcelain boat, which is put into tube furnace in the oxygen atmosphere of 50Pa with 10 DEG C/min Rate is warming up to furnace cooling after 850 DEG C of heat preservations 100 hours；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 5: by solid K2CO3∶Al2O3∶SiO2∶B2O3: MgO is according to K2.24MgB0.15Al0.09Si4.76O12Chemistry The ratio uniform of stoichiometric mole ratio mixes, and is added the dehydrated alcohol that quality is mixture quality 8%, and 420 revs/min in the ball mill The revolving speed ball milling of clock 10 hours, drying 10 is small in 100 DEG C of vacuum drying ovens (gas pressure is in 15Pa in baking oven) after ball milling When, 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/min of rate Furnace cooling after being warming up to 650 DEG C of heat preservations 10 hours；Powder after cooling is ground in alms bowl in agate and is regrind 30 minutes, is ground Powder afterwards takes out furnace after being warming up to 1300 DEG C of heat preservations 40 hours with 15 DEG C/min of rate in platinum crucible in air atmosphere Thorax cools down rapidly；Material after cooling is crushed in grinding and is impregnated in the sodium hydroxide solution of 0.2M after grinding 50 minutes It filters, dry and in a press 5 × 10 after ten minutes7The pressure of Pa pushes flakiness, and thin slice obtained embedment is partly filled In the SiO 2 powder of full porcelain boat, which is put into tube furnace in the oxygen atmosphere of 40Pa with 8 DEG C/min of rate Furnace cooling after being warming up to 800 DEG C of heat preservations 120 hours；The potassium ion fast-ionic conductor thin slice is made.

Claims (1)

1. a kind of Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor, it is characterized in that: stoichiometric equation K2+x+ yMgBxAlySi5-x-yO12, in which: x=0.05-0.15；Y=0.05-0.15；Room temperature potassium ion conductivity is more than 510-4S/ cm；Its preparation process is by solid K2CO3∶Al2O3∶SiO2∶B2O3: MgO is according to K2+x+yMgBxAlySi5-x-yO12Stoichiometry The ratio uniform of molar ratio mixes, and the dehydrated alcohol that quality is mixture quality 3%-9% is added, in the ball mill with 100- It is 60 DEG C -120 DEG C that 500 revs/min of revolving speed ball milling 10-50 hours, which is 3Pa-20Pa temperature in gas pressure after ball milling, It is 2-10 hours dry in vacuum drying oven, it grinds in alms bowl and re-grinds 10-30 minutes in agate after taking-up, the powder after grinding is in air Rate in atmosphere with 5-30 DEG C/min is warming up to furnace cooling after 550-650 DEG C of heat preservation 3-10 hours；By powder after cooling It grinds in alms bowl and regrinds 10-30 minutes in agate, the powder after grinding is in air atmosphere with 5-15 DEG C/min in platinum crucible Rate be warming up to 1250-1350 DEG C of heat preservation 25-48 hours after take out burner hearth cool down rapidly；By material after cooling in grinding It filtered after being impregnated 5-15 minutes in the sodium hydroxide solution of 0.1-0.3M after crushing and grinding 30-50 minutes, dry and pressing 1 × 10 in power machine7Pa-8×107The pressure of Pa pushes flakiness, and thin slice obtained embedment half is full of to the silica of porcelain boat In powder, which is put into tube furnace, 750- is warming up to 5-10 DEG C/min of rate in the oxygen atmosphere of 10-60Pa The potassium fast-ionic conductor is made in 850 DEG C of furnace coolings after heat preservation 80-150 hours.
CN201910617220.1A 2019-06-27 2019-06-27 A kind of Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof Withdrawn CN110371996A (en)

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