CN110357598A - A kind of P5+、Be2+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof - Google Patents

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

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CN110357598A
CN110357598A CN201910617190.4A CN201910617190A CN110357598A CN 110357598 A CN110357598 A CN 110357598A CN 201910617190 A CN201910617190 A CN 201910617190A CN 110357598 A CN110357598 A CN 110357598A
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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+、Be2+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof, it is characterized in that: stoichiometric equation K2+2x‑yMgBexPySi5‑x‑yO12, in which: x=0.1-0.15；Y=0.02-0.05；Room temperature potassium ion conductivity is more than 510‑ 4S/cm.Using Be2+Part replaces Si4+Ion generates gap potassium ion in crystal and reduces potassium ion migration activation energy；The electron conduction of fast-ionic conductor is further decreased by P5+ doping；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；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+、Be2+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(PO3)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+、Be2+Ion collaboration The K of doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof.Using Be2+Part replaces Si4+Ion generates high in crystal Concentration gap potassium ion helps to reduce potassium ion migration activation energy to generate more potassium ions collaboration migration of short distance；It is logical Cross P5+Doping further decreases the electron conduction of fast-ionic conductor；Pass through the Be of small ionic radii2+Doping adjusts potassium ion The size of migrating channels is to adapt to the fast transferring of potassium ion；And during the preparation process in K2MgSi5O12The surface of particle carries out Modification forms easy-sintering characteristic, is conducive to improve the potassium fast-ionic conductor and reduces crystal boundary gap, increase when preparing bulk devices Consistency 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 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-yMgBexPySi5-x-yO12, in which: x=0.1-0.15；y =0.02-0.05.
In the technical scheme, by solid K2CO3∶NH4H2PO4∶SiO2: BeO: MgO according to K2+2x-yMgBexPySi5-x-yO12 Nonstoichiometric molar ratio ratio uniform mixing, be added quality be mixture quality 3%-9% dehydrated alcohol, in ball mill In with revolving speed ball milling 10-50 hours of 100-500 revs/min, be 3Pa-20Pa temperature in gas pressure after ball milling be 60 It is 2-10 hour dry in DEG C -120 DEG C of vacuum drying ovens, it is re-grind 10-30 minutes in agate stone roller alms bowl after taking-up, the powder after grinding Rate of the body 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；It will cool down Powder afterwards is ground in alms bowl in agate to be regrind 10-30 minutes, and the powder after grinding is in air atmosphere with 5- in platinum crucible 15 DEG C/min of rate is taken out burner hearth after being warming up to 1250-1350 DEG C of heat preservation 25-48 hours and is cooled down rapidly；By material after cooling Material crush and grind 30-50 minute in grinding after impregnated 5-15 minutes in the sodium hydroxide solution of 0.1-0.3M after filter, It dries and in a press 1 × 107Pa-8×107The pressure of Pa pushes flakiness, and thin slice obtained embedment half is full of porcelain boat SiO 2 powder in, which is put into tube furnace in the oxygen atmosphere of 10-60Pa with 5-10 DEG C/min of rate Furnace cooling after being warming up to 750-850 DEG C of heat preservation 80-150 hours；The potassium ion fast-ionic conductor thin slice is made.If Fig. 1 is group As K2.18MgBe0.1P0.02Si4.88O12The XRD spectrum of potassium fast-ionic conductor, spectral line meet PDF card 82- 0548K2MgSi5O12It is 6.210 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 Be2+Part replaces Si4+Ion generates in crystal High concentration 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 Be of small ionic radii2+Doping adjusts potassium ion Migrating channels size to adapt to the fast transferring of potassium ion；It will be particularly beneficial that during the preparation process in K2MgSi5O12? The surface of grain is modified, and is formed easy-sintering characteristic, is conducive to improve potassium fast-ionic conductor reduction when preparing bulk devices Crystal boundary gap increases consistency to improve the potassium ion conductivity of block potassium fast-ionic conductor.These act synergistically so that should The room temperature potassium ion conductivity of 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 K2.18MgBe0.1P0.02Si4.88O12The XRD spectrum of potassium fast-ionic conductor.
Specific embodiment
Below in conjunction with embodiment, present invention is further described in detail.
Embodiment 1:K2CO3∶NH4H2PO4∶SiO2: BeO: MgO according to K2.18MgBe0.1P0.02Si4.88O12Stoichiometry rub The ratio uniform mixing of your ratio, is added the dehydrated alcohol that quality is mixture quality 3%, in the ball mill with 110 revs/min It is revolving speed ball milling 12 hours, 2 hours dry in 60 DEG C of vacuum drying ovens (gas pressure is in 3Pa in baking oven) after ball milling, it takes out It grinds in alms bowl and re-grinds 15 minutes in agate afterwards, the powder after grinding is warming up in air atmosphere with 8 DEG C/min of rate 550 DEG C heat preservation 3 hours after furnace cooling；Powder after cooling is ground in alms bowl in agate and is regrind 10 minutes, the powder after grinding It is rapid that body takes out burner hearth after being warming up to 1260 DEG C of heat preservations 30 hours with 5 DEG C/min of rate in platinum crucible in air atmosphere It is cooling；It is impregnated 5 minutes in the sodium hydroxide solution of 0.1M after material after cooling is crushed in grinding and is ground 30 minutes It filters, dry and in a press 1.2 × 10 afterwards7The pressure of Pa pushes flakiness, and thin slice obtained embedment half is full of porcelain In the SiO 2 powder of boat, which is put into tube furnace and is heated up in the oxygen atmosphere of 15Pa with 5 DEG C/min of rate Furnace cooling after keeping the temperature 90 hours to 750 DEG C；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 2:K2CO3∶NH4H2PO4∶SiO2: BeO: MgO according to K2.25MgBe0.15P0.05Si4.8O12Stoichiometry rub The ratio uniform mixing of your ratio, is added the dehydrated alcohol that quality is mixture quality 9%, in the ball mill with 450 revs/min It is revolving speed ball milling 43 hours, 10 hours dry in 110 DEG C of vacuum drying ovens (gas pressure is in 15Pa in baking oven) after ball milling, it takes It grinds in alms bowl and re-grinds 30 minutes in agate after out, the powder after grinding is heated up in air atmosphere with 30 DEG C/min of rate Furnace cooling after keeping the temperature 10 hours to 650 DEG C；Powder after cooling is ground in alms bowl in agate and is regrind 30 minutes, after grinding It is fast that powder takes out burner hearth after being warming up to 1340 DEG C of heat preservations 45 hours with 12 DEG C/min of rate in platinum crucible in air atmosphere Quickly cooling is but；15 points are impregnated after material after cooling is crushed in grinding and is ground 45 minutes in the sodium hydroxide solution of 0.3M It filters, dry and in a press 7.5 × 10 after clock7The pressure of Pa pushes flakiness, and thin slice obtained embedment is partly full of In the SiO 2 powder of porcelain boat, which is put into tube furnace in the oxygen atmosphere of 60Pa with 10 DEG C/min of rate Furnace cooling after being warming up to 830 DEG C of heat preservations 150 hours；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 3:K2CO3∶NH4H2PO4∶SiO2: BeO: MgO according to K2.21MgBe0.12P0.03Si4.85O12Stoichiometry The ratio uniform of molar ratio mixes, and the dehydrated alcohol that quality is mixture quality 7% is added, in the ball mill with 350 revs/min Revolving speed ball milling 25 hours, after ball milling dry 8 hours in 90 DEG C of vacuum drying ovens (gas pressure is in 15Pa in baking oven), take It grinds in alms bowl and re-grinds 20 minutes in agate after out, the powder after grinding is heated up in air atmosphere with 20 DEG C/min of rate Furnace cooling after keeping the temperature 7 hours to 600 DEG C；Powder after cooling is ground in alms bowl in agate and is regrind 20 minutes, after grinding It is fast that powder takes out burner hearth 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 Quickly cooling is but；Material after cooling is crushed in grinding and is ground and impregnates 10 points in the sodium hydroxide solution of 0.2M after forty minutes It filters, dry and in a press 3.9 × 10 after clock7The pressure of Pa pushes flakiness, and thin slice obtained embedment is partly full of In the SiO 2 powder of porcelain boat, which is put into tube furnace in the oxygen atmosphere of 40Pa with 7 DEG C/min of rate liter Furnace cooling after temperature keeps the temperature 110 hours to 810 DEG C；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 4:K2CO3∶NH4H2PO4∶SiO2: BeO: MgO according to K2.28MgBe0.15P0.02Si4.83O12Stoichiometry The ratio uniform of molar ratio mixes, and the dehydrated alcohol that quality is mixture quality 6% is added, in the ball mill with 300 revs/min Revolving speed ball milling 10 hours, after ball milling dry 10 hours in 80 DEG C of vacuum drying ovens (gas pressure is in 15Pa in baking oven), 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 liter Furnace cooling after temperature keeps the temperature 10 hours to 610 DEG C；Powder after cooling is ground in alms bowl in agate and is regrind 30 minutes, after grinding Powder in air atmosphere in platinum crucible with 15 DEG C/min of rate be warming up to 1300 DEG C heat preservation 40 hours after take out burner hearth It is cooling rapidly；Material after cooling is crushed in grinding and is ground and is impregnated in the sodium hydroxide solution of 0.15M after forty 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 50Pa with 10 DEG C/min of speed Rate is warming up to furnace cooling after 800 DEG C of heat preservations 100 hours；The potassium ion fast-ionic conductor thin slice is made.
Embodiment 5:K2CO3∶NH4H2PO4∶SiO2: BeO: MgO according to K2.23MgBe0.13P0.03Si4.84O12Stoichiometry The ratio uniform of molar ratio mixes, the dehydrated alcohol that quality is mixture quality 9% is added, and 420 revs/min in the ball mill It is revolving speed ball milling 10 hours, 10 hours dry in 100 DEG C of vacuum drying ovens (gas pressure is in 15Pa in baking oven) after ball milling, it takes It grinds in alms bowl and re-grinds 30 minutes in agate after out, the powder after grinding is heated up in air atmosphere with 30 DEG C/min of rate Furnace cooling after keeping the temperature 10 hours to 610 DEG C；Powder after cooling is ground in alms bowl in agate and is regrind 30 minutes, after grinding It is fast that powder takes out burner hearth after being warming up to 1340 DEG C of heat preservations 40 hours with 15 DEG C/min of rate in platinum crucible in air atmosphere Quickly cooling is but；10 points are impregnated after material after cooling is crushed in grinding and is ground 50 minutes in the sodium hydroxide solution of 0.2M It filters, dry and in a press 7 × 10 after clock7The pressure of Pa pushes flakiness, and thin slice obtained embedment half is full of porcelain In the SiO 2 powder of boat, which is put into tube furnace and is heated up in the oxygen atmosphere of 40Pa with 8 DEG C/min of rate Furnace cooling after keeping the temperature 120 hours to 820 DEG C；The potassium ion fast-ionic conductor thin slice is made.

Claims (1)

1. a kind of P5+、Be2+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor, it is characterized in that: stoichiometric equation is K2+2x-yMgBexPySi5-x-yO12, in which: x=0.1-0.15；Y=0.02-0.05；Room temperature potassium ion conductivity is more than 510- 4S/cm；Its preparation process is by solid K2CO3∶NH4H2PO4∶SiO2: BeO: MgO according to K2+2x-yMgBexPySi5-x-yO12Change Learn stoichiometric mole ratio ratio uniform mixing, be added quality be mixture quality 3%-9% dehydrated alcohol, in the ball mill with 100-500 revs/min of revolving speed ball milling 10-50 hours, 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 to 750-850 DEG C of furnace cooling after heat preservation 80-150 hours be that the potassium fast-ionic conductor is made.
CN201910617190.4A 2019-06-27 2019-06-27 A kind of P5+、Be2+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof Withdrawn CN110357598A (en)

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