CN104900912A - Na fast-ion conductor Na3PSe4 and preparation method thereof - Google Patents

Na fast-ion conductor Na3PSe4 and preparation method thereof Download PDF

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Publication number
CN104900912A
CN104900912A CN201510282131.8A CN201510282131A CN104900912A CN 104900912 A CN104900912 A CN 104900912A CN 201510282131 A CN201510282131 A CN 201510282131A CN 104900912 A CN104900912 A CN 104900912A
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pse
ion conductor
preparation
ball
quartz ampoule
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张隆
杨坤
董建英
芦磊
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Yanshan University
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Yanshan University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • 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
    • H01M10/0562—Solid materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a Na fast-ion conductor Na3PSe4 which is a conductor with a cubic phase structure and has a high ion conducting characteristic, and the preparation method of Na3PSe4 is as follows: weighing the original material, such as Na, P, and Se in a glove box, then putting to a crucible, then putting into a quartz tube to vacuum seal, fusing in a muffle furnace, at last cooling to room temperature, forming into blocks, making into powder. The preparation technology of the invention is simple, the Na ionic conductivity of the prepared Na3PSe4 solid electrolyte is more than 1ms/cm at most, and the performance of the Na3PSe4 is the highest in the sulfur compound at present.

Description

A kind of Fast ion conductor Na 3pSe 4and preparation method thereof
Technical field
The invention belongs to new energy materials field, particularly a kind of Fast ion conductor Na that can be used for solid electrolyte 3pSe 4and preparation method thereof.
Background technology
Along with the large-scale promotion of green energy resource uses, energy storage technology has been regarded as the important component part (electric power network technique, 32 (2008) 1) in operation of power networks process.In addition, the development of pure electric automobile also needs high performance large-scale energy-storage battery.Lithium ion battery possess lightweight, specific energy is high, unique advantage such as without memory, be widely used in recent years in energy storage device.But along with the sharply expansion to the lithium battery market demand, limited lithium resource will face shortage problem, the manufacturing cost of battery will be caused to rise.Compared to lithium, sodium has low, the resourceful advantage of price, and working mechanism in the secondary battery and lithium similar.Although little more next than lithium ion battery of the theoretical specific capacity of sodium-ion battery, it is highly suitable for energy storage and electric automobile (Energy Environ.Sci., 5 (2012) 5884 of large scale electric network system; Chemical industry is in progress, and 32 (2013) 1789).
As everyone knows, commercial at present organic electrolyte is volatile, inflammable, service life is not long, is the principal element (Nature, 414 (2001) 359) causing lithium battery safety problem.Solid electrolyte is adopted to replace electrolyte development all-solid-state battery to be solve the most effective approach of cell safety problem.Solid electrolyte has significant advantage in large-scale energy-storage battery and hull cell, particularly under extreme service condition or when safety issue appears in local unit, adopt the inorganic solid electrolyte do not fired completely, fundamentally can ensure fail safe (energy storage science and technology, 2 (2013) 331 that battery uses; Energy storage science and technology, 3 (2014) 376; Chemistry journal, 71 (2014) 869).
Although solid electrolyte has above-mentioned many advantages, be limited by its lower conductivity at room temperature and (be usually less than 1 × 10 -4s/cm), current solid electrolyte is mostly used in film all-solid-state battery.Such as, typical LiPON solid electrolyte, its ionic conductivity is lower than 1 × 10 -5s/cm.In recent years, inorganic solid electrolyte particularly sulfide gets the attention, comprising Toyota and the three large factories of magnitude battery (energy storage science and technology, 2 (2013) 331).The sulfide sodium solid electrolyte that under current room temperature, performance is the highest is Na 3pS 4– Na 4siS 4composite material, although its ionic conductivity reaches 7.4 × 10 -4s/cm (RSC Adv., 4 (2014) 17120), but still lower than think can be practical 1 × 10 -3s/cm.Therefore, how improving ionic conductivity is the subject matter that solid electrolyte application needs to solve.
Summary of the invention
The object of the invention is to propose a kind of with low cost, technique is simple, repeatable high, the Fast ion conductor Na with high ionic conductivity 3pSe 4and preparation method thereof.
Fast ion conductor Na of the present invention 3pSe 4it is a kind of conductor with the Emission in Cubic structure of macroion conductive characteristic.
Preparation method of the present invention is as follows:
(1) raw material is selected: preferred highly purified initiation material, the simple substance Na, the purity that adopt business-like purity to be greater than 99% be 99.999% red phosphorus, purity be the selenium of 99.999%.
(2) ratio of Na:P:Se=3:0.9 ~ 1.1:3.9 ~ 4.1 in molar ratio, in glove box, raw material sodium, red phosphorus and selenium are weighed, then above-mentioned raw materials is put into crucible (crucible material is aluminium oxide, zirconia, vitreous carbon), crucible is put into the quartz ampoule that one end is closed, be evacuated to 0.1Pa, burn envelope quartz ampoule; Put into Muffle furnace by burning the closed quartz tube of being honored as a queen again, with 0.2 DEG C/min more slowly heating rate be heated to 750 ~ 900 DEG C, be incubated 24 hours, is finally cooled to room temperature, cooler environment be cool in cooling, stove outer air in stove, water-cooled or oil cooling.
(3) cooled block is taken out from quartz ampoule; clayed into power; in glove box, manually its pulverize or employing ball mill are carried out ball milling with mortar; ball milling adopts the slow-speed of revolution; that is: 100 ~ 200 revs/min; Ball-milling Time 4 ~ 15 hours, ball grinder and the preferred stainless steel of abrading-ball, ball milling under high-purity argon gas (99.999%) protection.
The present invention compared with prior art tool has the following advantages:
1, (the PSe containing Se is utilized 4) 3-the wide ionic transport passages size that anionic group skeleton has, increases ionic conductivity, so the Na of preparation 3pSe 4fast ion conductor has high ionic conductivity, and sodium ion conductivity is more than 1 × 10 -3s/cm is that in current chalcogenide, performance is the highest.
2, raw material used is cheap to be easy to get, and preparation technology is simple, repeatable high, is applicable to large-scale industrial production, and the compound prepared is in the interval stable performance of the service temperature of material.
Accompanying drawing explanation
Fig. 1 is the Na that the embodiment of the present invention 1 obtains 3pSe 4the X-ray diffractogram of Fast ion conductor.
Fig. 2 is the Na that the embodiment of the present invention 1 and 2 obtains 3pSe 4the AC impedance contrast figure of Fast ion conductor.Wherein, curve (a) is the AC impedance figure of embodiment 1; Curve (b) is the AC impedance figure of embodiment 2.Illustration is the enlarged drawing of curve (b) impedance spectrum high frequency region.
Fig. 3 is the Na that the embodiment of the present invention 1 obtains 3pSe 4the temperature variant graph of a relation of ionic conductivity of Fast ion conductor.Figure mid point is experiment value, and oblique line is the linear fit to experimental point.
Fig. 4 is the Na that the embodiment of the present invention 2 obtains 3pSe 4the X-ray diffractogram of Fast ion conductor.
Fig. 5 is the Na that the embodiment of the present invention 2 obtains 3pSe 4the temperature variant graph of a relation of ionic conductivity of Fast ion conductor.Figure mid point is experiment value, and oblique line is the linear fit to experimental point.Illustration is embodiment 2 impedance variation with temperature graph of a relation, can be calculated the ionic conductivity of relevant temperature by the impedance spectrum of temperature spot each in illustration.
Embodiment
Embodiment 1:
By simple substance Na (>99%), P (red phosphorus, 99.999%), in glove box, Na:P:Se=3:1:4's Se (99.999%) weighs in molar ratio, and puts into alumina crucible; Afterwards crucible is put into the quartz ampoule that one end is closed, be evacuated to 0.1Pa, burn envelope quartz ampoule.Putting into Muffle furnace by burning the closed quartz tube of being honored as a queen again, being heated to 850 DEG C with the heating rate of 0.2 DEG C/min, being incubated 24 hours, in last stove, being cooled to room temperature.Cooled block is taken out from quartz ampoule, puts into glove box mortar manually by its pulverize.
X-ray diffraction (XRD) test is carried out after the sealing of sample powder polyimide film, test employing SmartLab (40kV, 40mA, Cu Ka, ), test specification 5 ~ 75 °, speed 3 °/minute.As shown in Figure 1, curve is Na 3pSe 4the X-ray diffractogram of sodium solid electrolyte, shows that prepared sample is the Na of pure Emission in Cubic 3pSe 4.
Sample powder taken a certain amount of with indium electrode slice common cold moudling (150MPa) in carbide alloy grinding tool in glove box, grinding tool diameter is 9 millimeters.Print after colding pressing loads in test grinding tool, carries out AC impedance (AC) test, test frequency scope 100mHz ~ 1MHz with electric impedance analyzer (Princeton P4000) to sample.As shown in Figure 2, curve (a) medium and low frequency segment table reveals linear oblique line, is the impedance operator of electrolyte interface when typically adopting blocking electrode, illustrates that compound is ion conductor; The grain boundary resistance of the half-circle area representative sample of high band.The room-temperature conductivity that can calculate sample in the intercept of transverse axis from curve (a) bend part is about 2.7 × 10 -4s/cm.
As shown in Figure 3, by formula σ=A exp (-E a/ k bt) (σ is ionic conductivity, and A is pre-exponential factor, E afor activation energy, k bfor Boltzmann constant, T is thermodynamic temperature), known conductivity logarithm and thermodynamic temperature inverse linear.Carry out linear fit by the experiment value of Fig. 3, linear relationship good between experiment value can be found out, meet arrhenius law well, show the phase stability at solid electrolyte high temperature simultaneously, embody the extremely wide application of temperature of material interval.The activation energy of sample can be calculated by the slope of Fig. 3 oblique line aabout 0.24eV.
Embodiment 2:
By simple substance Na (>99%), P (red phosphorus, 99.999%), in glove box, Na:P:Se=3:1:4's Se (99.999%) weighs in molar ratio, and put into alumina crucible, crucible is put into the quartz ampoule that one end is closed, be evacuated to 0.1Pa, burn envelope quartz ampoule.Putting into Muffle furnace by burning the closed quartz tube of being honored as a queen again, being heated to 850 DEG C with the heating rate of 0.2 DEG C/min, being incubated 24 hours, finally take out oil cooling to room temperature.Cooled block is taken out from quartz ampoule, puts into ball mill ball milling.Drum's speed of rotation is 160 revs/min, Ball-milling Time 6 hours, ball grinder and the preferred stainless steel of abrading-ball, under high-purity argon gas (99.999%) protection, carry out ball milling.Adopt the X-ray diffraction method of testing test described in embodiment 1, as shown in Figure 4, curve shows that prepared sample is the Na of pure Emission in Cubic 3pSe 4(bulge between 15 ~ 25 ° comes from the film by sample and air exclusion), but after ball milling refinement its peak shape broadening.
Sample powder taken a certain amount of with the common cold moudling in carbide alloy grinding tool of indium electrode slice (240Mpa, the sample after ball milling refinement can corresponding increase cold pressing strength, makes intercrystalline contact good) in glove box, grinding tool diameter is 9 millimeters.Print after colding pressing loads in test grinding tool, carries out AC impedance (AC) test, test frequency scope 100mHz ~ 1MHz with electric impedance analyzer (Princeton P4000) to sample.As shown in Figure 2, in figure, curve (b) medium and low frequency segment table reveals linear oblique line, is the impedance operator of electrolyte interface when typically adopting blocking electrode, illustrates that compound is ion conductor; The grain boundary resistance of the half-circle area representative sample of high band, compared with curve (a), the half-circle area of curve (b) in illustration obviously reduces, and all-in resistance also significantly reduces relative to non-milled sample.The room-temperature conductivity that can calculate sample in the intercept of transverse axis from curve (b) magnification region oblique line portion is about 1.16 × 10 -3s/cm.
As shown in Figure 5, embody the rising along with temperature, the characteristic that impedance reduces, relevant temperature ionic conductivity can be calculated by the impedance spectrum of temperature spot each in illustration.By formula σ=A exp (-E a/ k bt) (σ is ionic conductivity, and A is pre-exponential factor, E afor activation energy, k bfor Boltzmann constant, T is thermodynamic temperature), known conductivity logarithm and thermodynamic temperature inverse linear.Carry out linear fit by the experiment value of Fig. 5, linear relationship good between experiment value can be found out, meet arrhenius law well, show the phase stability at solid electrolyte high temperature simultaneously, embody the extremely wide application of temperature of material interval.The activation energy of sample can be calculated by the slope of Fig. 5 oblique line aabout 0.21eV.
Embodiment 3:
By simple substance Na (>99%), P (red phosphorus, 99.999%), in glove box, Na:P:Se=3:1.1:4.1's Se (99.999%) weighs in molar ratio, and puts into zirconia crucible; Crucible is put into the quartz ampoule that one end is closed, be evacuated to 0.1Pa, burn envelope quartz ampoule.Putting into Muffle furnace by burning the closed quartz tube of being honored as a queen again, being heated to 900 DEG C with the heating rate of 0.2 DEG C/min, being incubated 24 hours, finally taking out and be cooled to room temperature in stove outer air.Cooled block is taken out from quartz ampoule, puts into ball mill ball milling.Drum's speed of rotation is 200 revs/min, Ball-milling Time 4 hours, ball grinder and the preferred stainless steel of abrading-ball, under high-purity argon gas (99.999%) protection, carry out ball milling.The sample prepared is the Na of pure Emission in Cubic through X-ray diffraction test 3pSe 4.Adopt the ac impedance measurement method described in embodiment 2, show that its room-temperature conductivity is 1.02 × 10 -3s/cm.
Embodiment 4:
By simple substance Na (>99%), P (red phosphorus, 99.999%), in glove box, Na:P:Se=3:0.9:3.9's Se (99.999%) weighs in molar ratio, and puts into vitreous carbon crucible; Afterwards crucible is put into the quartz ampoule that one end is closed, be evacuated to 0.1Pa, burn envelope quartz ampoule.Putting into Muffle furnace by burning the closed quartz tube of being honored as a queen again, being heated to 750 DEG C with the heating rate of 0.2 DEG C/min, being incubated 24 hours, finally take out water-cooled to room temperature.Cooled block is taken out from quartz ampoule, puts into ball mill ball milling.Drum's speed of rotation is 100 revs/min, Ball-milling Time 15 hours, ball grinder and the preferred stainless steel of abrading-ball, under high-purity argon gas (99.999%) protection, carry out ball milling.The sample prepared is the Na of pure Emission in Cubic through X-ray diffraction test 3pSe 4.Adopt the ac impedance measurement method described in embodiment 1, show that its room-temperature conductivity is 9.4 × 10 -4s/cm.
Embodiment 5:
By simple substance Na (>99%), P (red phosphorus, 99.999%), in glove box, Na:P:Se=3:0.9:4.1's Se (99.999%) weighs in molar ratio, and puts into vitreous carbon crucible; Afterwards crucible is put into the quartz ampoule that one end is closed, be evacuated to 0.1Pa, burn envelope quartz ampoule.Putting into Muffle furnace by burning the closed quartz tube of being honored as a queen again, being heated to 850 DEG C with the heating rate of 0.2 DEG C/min, being incubated 24 hours, finally take out water-cooled to room temperature.Cooled block is taken out from quartz ampoule, puts into glove box mortar manually by its pulverize.The sample prepared is the Na of pure Emission in Cubic through X-ray diffraction test 3pSe 4.Adopt the ac impedance measurement method described in embodiment 1, show that its room-temperature conductivity is 1.8 × 10 -4s/cm.
Embodiment 6:
By simple substance Na (>99%), P (red phosphorus, 99.999%), in glove box, Na:P:Se=3:1:4.1's Se (99.999%) weighs in molar ratio, and puts into alumina crucible; Crucible is put into the quartz ampoule that one end is closed, be evacuated to 0.1Pa, burn envelope quartz ampoule.Putting into Muffle furnace by burning the closed quartz tube of being honored as a queen again, being heated to 760 DEG C with the heating rate of 0.2 DEG C/min, being incubated 24 hours, finally take out in stove and be cooled to room temperature.Cooled block is taken out from quartz ampoule, puts into glove box mortar manually by its pulverize.The sample prepared is the Na of pure Emission in Cubic through X-ray diffraction test 3pSe 4.Adopt the ac impedance measurement method described in embodiment 1, show that its room-temperature conductivity is 2.1 × 10 -4s/cm.

Claims (4)

1. a Fast ion conductor Na 3pSe 4, it is characterized in that: it is a kind of conductor with the Emission in Cubic structure of macroion conductive characteristic.
2. Fast ion conductor Na according to claim 1 3pSe 4preparation method, it is characterized in that:
(1) raw material is selected: the simple substance Na, the purity that adopt business-like purity to be greater than 99% be 99.999% red phosphorus, purity be the selenium of 99.999%;
(2) ratio of Na:P:Se=3:0.9 ~ 1.1:3.9 ~ 4.1 in molar ratio, raw material at gloves weighed inside oven is put into crucible, crucible is put into the quartz ampoule that one end is closed, be evacuated to 0.1Pa, burn envelope quartz ampoule, then put into Muffle furnace by burning the closed quartz tube of being honored as a queen, be heated to 750 ~ 900 DEG C with the heating rate of 0.2 DEG C/min, be incubated 24 hours, be finally cooled to room temperature;
(3) cooled block is taken out from quartz ampoule, be ground into powder.
3. the Fast ion conductor Na for solid electrolyte according to claim 2 3pSe 4preparation method, it is characterized in that: described cooler environment is cooling, water-cooled or oil cooling in cooling, stove outer air in stove.
4. the Fast ion conductor Na for solid electrolyte according to claim 2 3pSe 4preparation method; it is characterized in that: described grinding carries out ball milling, drum's speed of rotation 150 revs/min, ball milling 6 hours with mortar hand-ground or employing ball mill in glove box; ball grinder and abrading-ball are preferably stainless steel, ball milling under 99.999% high-purity argon gas protection.
CN201510282131.8A 2015-05-28 2015-05-28 Na fast-ion conductor Na3PSe4 and preparation method thereof Pending CN104900912A (en)

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Cited By (5)

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CN105355971A (en) * 2015-11-27 2016-02-24 燕山大学 Sodium fast ion conductor material used for solid electrolyte and preparation method of sodium fast ion conductor material
CN105845976A (en) * 2016-04-12 2016-08-10 燕山大学 Tetragonal phase Na3SbS4 sodium fast ion conductor and preparation method thereof
CN106532023A (en) * 2016-12-02 2017-03-22 燕山大学 Sodium fast ion conductor and preparation method therefor
CN108493479A (en) * 2018-04-03 2018-09-04 燕山大学 A kind of sulfide solid electrolyte and preparation method thereof based on oxygen doping
CN108328589B (en) * 2018-01-11 2021-07-20 三峡大学 PSe negative electrode material with high coulombic efficiency for the first time and preparation method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105355971A (en) * 2015-11-27 2016-02-24 燕山大学 Sodium fast ion conductor material used for solid electrolyte and preparation method of sodium fast ion conductor material
CN105845976A (en) * 2016-04-12 2016-08-10 燕山大学 Tetragonal phase Na3SbS4 sodium fast ion conductor and preparation method thereof
CN106532023A (en) * 2016-12-02 2017-03-22 燕山大学 Sodium fast ion conductor and preparation method therefor
CN106532023B (en) * 2016-12-02 2019-02-22 燕山大学 A kind of Fast ion conductor and preparation method thereof
CN108328589B (en) * 2018-01-11 2021-07-20 三峡大学 PSe negative electrode material with high coulombic efficiency for the first time and preparation method thereof
CN108493479A (en) * 2018-04-03 2018-09-04 燕山大学 A kind of sulfide solid electrolyte and preparation method thereof based on oxygen doping
CN108493479B (en) * 2018-04-03 2020-09-11 燕山大学 Sulfide solid electrolyte based on oxygen doping and preparation method thereof

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Application publication date: 20150909