CN110304912A - A kind of electric field induction crystallization P5+、Be2+Cooperate with the K of doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof - Google Patents
A kind of electric field induction crystallization P5+、Be2+Cooperate with the K of doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof Download PDFInfo
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- 239000010416 ion conductor Substances 0.000 title claims abstract description 28
- 238000002425 crystallisation Methods 0.000 title claims abstract description 17
- 230000008025 crystallization Effects 0.000 title claims abstract description 17
- 230000005684 electric field Effects 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 230000006698 induction Effects 0.000 title claims abstract description 7
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 33
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 31
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 19
- 239000011591 potassium Substances 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000000227 grinding Methods 0.000 claims description 21
- 238000004321 preservation Methods 0.000 claims description 21
- 238000010792 warming Methods 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910052573 porcelain Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000004020 conductor Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 abstract description 10
- 238000013508 migration Methods 0.000 abstract description 6
- 230000005012 migration Effects 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
- 230000007423 decrease Effects 0.000 abstract description 3
- 239000011244 liquid electrolyte Substances 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000010079 rubber tapping Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001504664 Crossocheilus latius Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910008026 Li1+x+yAlxTi2-xSiyP3-yO12 Inorganic materials 0.000 description 1
- 229910008043 Li1+x+yAlxTi2−xSiyP3-yO12 Inorganic materials 0.000 description 1
- 229910006188 Li1+x+yAlxTi2−xSiyP3−yO12 Inorganic materials 0.000 description 1
- 229910006209 Li1+xAlxTi2−x Inorganic materials 0.000 description 1
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 1
- 229910011122 LiM2(PO4)3 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 210000000038 chest Anatomy 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- -1 kalium ion Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
A kind of electric field induction crystallization P5+、Be2+Cooperate with the K of doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof, it is characterized in that: stoichiometric equation K2+2x‑zMgBexPzSi5‑x‑zO12, in which: x=0.1-0.2；Z=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；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；And during the preparation process in K2MgSi5O12The 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
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
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+、
Be2+Cooperate with the K of doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof.Using Be2+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 Be of small ionic radii2+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 K2MgSi5O12Particle
Surface modified, form easy-sintering characteristic, be conducive to improve the potassium fast-ionic conductor and reduce crystalline substance when preparing bulk devices
Boundary gap increases consistency to improve the potassium ion conductivity of block potassium fast-ionic conductor；Strong dc electric field is introduced simultaneously to lure
Crystallization is led to accelerate the speed of crystallization, reduce the temperature of crystallization and improve crystallization integrity degree.These act synergistically so that the potassium fastly from
The room temperature potassium ion conductivity of sub- 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+2x-zMgBexPzSi5-x-zO12, in which: x=0.1-0.2；z
=0.02-0.05.
In the technical scheme, by solid K2CO3∶NH4H2PO4∶MgO∶SiO2: BeO is according to K2+2x-zMgBexPzSi5-x-zO12
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, by the porcelain boat be put into both ends setting 800-1100V DC voltage tube furnace in 10-60Pa oxygen
Rate in gas atmosphere with 5-10 DEG C/min is warming up to furnace cooling after 700-800 DEG C of heat preservation 30-60 hours；Be made the potassium from
Sub- fast-ionic conductor thin slice.If Fig. 1 is that group becomes K2.18MgBe0.1P0.02Si4.88O12The XRD spectrum of potassium fast-ionic conductor, spectrum
Line meets PDF card 82-0548 K2MgSi5O12It is 7.110 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 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；Strong dc electric field is introduced simultaneously
Induction crystallization accelerates the speed of crystallization, reduces the temperature of crystallization and improve crystallization integrity degree.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 very beneficial for the building of full-solid potassium ion battery.
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: by solid K2CO3∶NH4H2PO4∶MgO∶SiO2: BeO is according to K2.18MgBe0.1P0.02Si4.88O12Chemistry
The ratio uniform of stoichiometric mole ratio mixes, and the dehydrated alcohol that quality is mixture quality 3% is added, in the ball mill with 120 turns/
Revolving speed ball milling 10 hours of minute, drying 3 is small in 60 DEG C of vacuum drying ovens (gas pressure is in 5Pa in baking oven) after ball milling
When, it grinds in alms bowl and re-grinds 12 minutes in agate after taking-up, the powder after grinding is in air atmosphere with 7 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 1260 DEG C of heat preservations 25 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 1.8 × 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 the oxygen in the tube furnace of both ends setting 810V DC voltage in 15Pa
Furnace cooling after being warming up to 700 DEG C of heat preservations 30 hours in atmosphere with 5 DEG C/min of rate；The potassium ion fast-ionic conductor is made
Thin slice.
Embodiment 2: by solid K2CO3∶NH4H2PO4∶MgO∶SiO2: BeO is according to K2.35MgBe0.2P0.05Si4.75O12Chemistry
The ratio uniform of stoichiometric mole ratio mixes, and the dehydrated alcohol that quality is mixture quality 9% is added, in the ball mill with 500 turns/
Revolving speed ball milling 50 hours of minute, after ball milling dry 10 in 110 DEG C of vacuum drying ovens (gas pressure is in 20Pa in baking oven)
Hour, 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 speed
Rate is warming up to furnace cooling after 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 after mill takes out after being warming up to 1350 DEG C of heat preservations 45 hours with 13 DEG C/min of rate in platinum crucible in air atmosphere
Burner hearth cools down rapidly；Material after cooling is crushed in grinding and is soaked in the sodium hydroxide solution of 0.3M after grinding 50 minutes
Bubble is filtered after 15 minutes, is dried and in a press 7.5 × 107The pressure of Pa pushes flakiness, and thin slice obtained is embedded to
In half SiO 2 powder full of porcelain boat, which is put into the tube furnace of both ends setting 1100V DC voltage in 60Pa
Oxygen atmosphere in 10 DEG C/min of rate be warming up to 790 DEG C heat preservation 60 hours after furnace cooling；Be made the potassium ion fastly from
Sub- conductor sheet.
Embodiment 3: by solid K2CO3∶NH4H2PO4∶MgO∶SiO2: BeO is according to K2.27MgBe0.15P0.03Si4.82O12Change
The ratio uniform mixing for learning stoichiometric mole ratio, is added the dehydrated alcohol that quality is mixture quality 6%, in the ball mill with 350
Rev/min revolving speed ball milling 30 hours, after ball milling dry 6 in 90 DEG C of vacuum drying ovens (gas pressure is in 15Pa in baking oven)
Hour, 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 speed
Rate is warming up to furnace cooling after 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 after mill takes out after being warming up to 1300 DEG C of heat preservations 35 hours with 10 DEG C/min of rate in platinum crucible in air atmosphere
Burner hearth cools down rapidly；Material after cooling is crushed in grinding and is ground and is soaked in the sodium hydroxide solution of 0.2M after forty minutes
Bubble is filtered after ten minutes, is dried and in a press 6 × 107The pressure of Pa pushes flakiness, by thin slice obtained embedment half
In SiO 2 powder full of porcelain boat, which is put into the oxygen in the tube furnace of both ends setting 900V DC voltage in 50Pa
Furnace cooling after being warming up to 760 DEG C of heat preservations 42 hours in gas atmosphere with 7 DEG C/min of rate；The fast ion of the potassium ion is made to lead
Body thin slice.
Embodiment 4: by solid K2CO3∶NH4H2PO4∶MgO∶SiO2: BeO is according to K2.19MgBe0.11P0.03Si4.86O12Change
The ratio uniform mixing for learning stoichiometric mole ratio, is added the dehydrated alcohol that quality is mixture quality 6%, in the ball mill with 450
Rev/min revolving speed ball milling 40 hours, it is dry in 110 DEG C of vacuum drying ovens (gas pressure is in 20Pa in baking oven) after ball milling
It 10 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 is warming up to furnace cooling after 610 DEG C of heat preservations 7 hours；Powder after cooling is ground in alms bowl in agate and is regrind 20 minutes,
Powder after grinding takes after being warming up to 1350 DEG C of heat preservations 45 hours with 10 DEG C/min of rate in platinum crucible in air atmosphere
Flake hearth-tapping cools down rapidly；After material after cooling is crushed in grinding and is ground 50 minutes in the sodium hydroxide solution of 0.2M
It impregnates and filters, dries and in a press 4.5 × 10 after ten minutes7The pressure of Pa pushes flakiness, and thin slice obtained is buried
Enter in half SiO 2 powder full of porcelain boat, which is put into the tube furnace of both ends setting 1000V DC voltage
Furnace cooling after being warming up to 760 DEG C of heat preservations 40 hours in the oxygen atmosphere of 50Pa with 10 DEG C/min of rate；The potassium ion is made
Fast-ionic conductor thin slice.
Embodiment 5: by solid K2CO3∶NH4H2PO4∶MgO∶SiO2: BeO is according to K2.29MgBe0.17P0.05Si4.78O12Change
The ratio uniform mixing for learning stoichiometric mole ratio, is added the dehydrated alcohol that quality is mixture quality 9%, in the ball mill with 100
Rev/min revolving speed ball milling 15 hours, it is dry in 60 DEG C of vacuum drying ovens (gas pressure is in 20Pa in baking oven) after ball milling
It 10 hours, grinds in alms bowl and re-grinds 20 minutes in agate after taking-up, the powder after grinding is in air atmosphere with 10 DEG C/min
Rate is warming up to furnace cooling after 550 DEG C of heat preservations 3 hours；Powder after cooling is ground in alms bowl in agate and is regrind 20 minutes,
Powder after grinding takes after being warming up to 1350 DEG C of heat preservations 40 hours with 10 DEG C/min of rate in platinum crucible in air atmosphere
Flake hearth-tapping cools down rapidly；Material after cooling is crushed in grinding and is ground after forty minutes in the sodium hydroxide solution of 0.1M
It impregnates and filters, dries and in a press 6 × 10 after ten minutes7The pressure of Pa pushes flakiness, and thin slice obtained is embedded to
In half SiO 2 powder full of porcelain boat, which is put into the tube furnace of both ends setting 850V DC voltage 10Pa's
Furnace cooling after being warming up to 780 DEG C of heat preservations 40 hours in oxygen atmosphere with 5 DEG C/min of rate；The fast ion of the potassium ion is made
Conductor sheet.
Claims (1)
1. a kind of electric field induction crystallization P5+、Be2+Cooperate with the K of doping2MgSi5O12Potassium fast-ionic conductor, it is characterized in that: stoichiometry
Formula is K2+2x-zMgBexPzSi5-x-zO12, in which: x=0.1-0.2；Z=0.02-0.05；Room temperature potassium ion conductivity is more than 5
10-4S/cm；Its preparation process is by solid K2CO3∶NH4H2PO4∶MgO∶SiO2: BeO is according to K2+2x-zMgBexPzSi5-x-zO12'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 the oxygen in the tube furnace of both ends setting 800-1100V DC voltage in 10-60Pa
After rate in atmosphere with 5-10 DEG C/min is warming up to 700-800 DEG C of heat preservation 30-60 hours furnace cooling be made the potassium fastly from
Sub- conductor.
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| CN201910617295.XA CN110304912A (en) | 2019-06-27 | 2019-06-27 | A kind of electric field induction crystallization P5+、Be2+Cooperate with the K of doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof |
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