CN106711448A - Ag3SI crystalline fast ion conductor material and preparation method thereof - Google Patents
Ag3SI crystalline fast ion conductor material and preparation method thereof Download PDFInfo
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- CN106711448A CN106711448A CN201611184726.0A CN201611184726A CN106711448A CN 106711448 A CN106711448 A CN 106711448A CN 201611184726 A CN201611184726 A CN 201611184726A CN 106711448 A CN106711448 A CN 106711448A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
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- 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
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Abstract
The invention relates to an Ag3SI crystalline fast ion conductor material and a preparation method thereof. The conductor material is prepared from the following method: (1) pre-loading grinding balls into a ball grinding pot, then mixing Ag2S and AgI in a glove box filled with an inert atmosphere according to a mole ratio of 1: 1, then adding a ball grinding adjuvant into the mixed raw materials, putting the mixed raw materials into the ball grinding pot for high-energy ball grinding reaction, and obtaining a sample subjected to ball grinding after the reaction is completed; (2) putting the sample subjected to ball grinding into a vacuum drying box for vacuum drying, and removing the grinding adjuvant to obtain a powder material; (3) annealing the powder material to obtain the Ag3SI crystalline fast ion conductor material. According to the preparation method provided by the invention, the process is simple, and the preparation period is short; furthermore, the thermal treatment temperature is low, and the manufacturing cost and the energy consumption are reduced; the prepared Ag3SI fast ion conductor crystal material is high in purity and high in ionic conductivity.
Description
Technical field
The invention belongs to solid ionic Material Field, and in particular to a kind of Ag3SI crystalline state fast ion conducting material and its system
Preparation Method.
Background technology
With the continuous popularization of domestic and international green energy resource, the field such as pure electric automobile is also got over to the performance requirement of energy-storage battery
Come higher.Widely used electrolyte is liquid electrolyte in current energy-storage battery, the shortcomings of its is volatile, flammable, perishable
Have impact on the service life of battery.By contrast, solid electrolyte uses safer reliability, it is to avoid a series of above-mentioned safety
Hidden danger.Fast-ionic conductor, also known as solid electrolyte, refers to have and the comparable height of liquid electrolyte in certain temperature range
One class solid material of ionic conductivity and low ion-activated energy, in many such as electrochemistry energy storage, electrochemical device, smart windows
Field has tempting application prospect.
Ag3One of fast-ionic conductor that SI is arranged as Ag families has been extensively studied, and it is primarily present three kinds of crystalline phases, i.e.,
α phases, β phases and γ phases.α phases belong to high-temperature-phase, can only in hot environment stable existence, its Ag+、S2-、I-All in unordered shape
State, therefore its ionic conductivity highest, up to 100S/cm；After temperature drops to 520K, i.e., it is β phases from α phase in version, β phases can
The stable existence in room temperature environment, but due to its S2-And I-In order state, only Ag+In disordered state, compared to α phases its
Ionic conductivity two orders of magnitude of reduction, are 10-2S/cm；When temperature continues to reduce, when reaching 157K, crystalline transformation is γ low temperature
Phase, all in order state, ionic conductivity also reaches minimum all ions in structure.Research at present uses relatively simple side
Method prepares the pure β-Ag of stable existence at ambient temperature3SI crystal is necessary.
Ag3SI is found jointly in 1960s by Takahashi and Yamamoto, and Ag is prepared at present3The side of SI crystal
Method is mainly fusion method and chemical synthesis.Fusion method is by AgI and Ag2S presses 1:1 dispensing is placed in being taken out in quartz glass tube
Vacuum, 5 days are incubated in 550 DEG C, and are annealed 2 days at 220 DEG C, or are incubated 17h in 550 DEG C in a sulfur vapor pressure ring border.Change
It is Boone Owen, G.R.Argue et al. by by a certain amount of Na to learn compositional rule2S and KI solution mixes, and adds certain dense
The AgNO of degree3Solution, filters after reaction 3h, to put the precipitate in and dry 60h in 200 DEG C of environment and obtain final crystalline material.
According to pertinent literature (S Hull, D A Keen, N J G Gardner and W Hayes.The crystal structures
of superionic Ag3SI.J.Phys.:Condens.Matter 13 (2001) 2295-2316) report, in room temperature condition
With β-AgI crystalline phase stable existences, its ionic conductivity is 10 to lower AgI-4S/cm；Ag2S is with β-Ag2S crystalline phase stable existences, its from
Electron conductivity is lower；Ag3SI crystal is at ambient temperature with β-Ag3SI crystalline phase stable existences, its ionic conductivity is 10-2-10- 3S/cm.By contrast, β-Ag at ambient temperature3SI is Ag fast ion conducting material intermediate ion electrical conductivity highest materials.Cause
This passes through AgI and Ag2S is the Ag of Material synthesis3It is residual if the final material purity for obtaining is not high in SI fast ion conducting materials
The AgI and Ag for staying2S will seriously reduce the ionic conductivity of material, consequently only that obtaining the Ag of high-purity3SI crystal can just be obtained
Obtain the fast ion conducting material of high ionic conductivity.
The content of the invention
The technical problems to be solved by the invention are directed to above shortcomings in the prior art, there is provided a kind of purity compared with
Ag high3SI crystalline state fast ion conducting materials and preparation method thereof.
In order to solve the above technical problems, the technical scheme that the present invention is provided is：
A kind of Ag is provided3SI crystalline state fast ion conducting materials, it is prepared by following methods：
1) mill ball is previously charged into ball grinder and then in the glove box full of inert atmosphere by Ag2S and AgI is massaged
You compare 1:1 carries out dispensing, and the raw material that then will be prepared adds ball-milling additive to be placed in carrying out high-energy ball milling reaction in ball grinder, instead
The good sample of ball milling is obtained after should terminating；
2) by step 1) the gained good sample of ball milling is placed in vacuum drying chamber and is vacuum dried, remove grinding aid and obtain
To dusty material；
3) by step 2) gained dusty material made annealing treatment, obtain Ag3SI crystalline state fast ion conducting materials.
By such scheme, step 1) mill ball be zirconium dioxide mill ball, material ball ratio is 15-30:1；The grinding
Auxiliary agent is normal heptane, per ball milling 1g material amounts 1.5-2mL.
By such scheme, step 1) the high-energy ball milling reaction time be 10-20h；Ball milling in high-energy ball milling course of reaction
Rotating speed is 600-800rpm, and it is 5min that mechanical milling process one is circularly set, each circulation work 2min, rest 3min.
By such scheme, step 2) the vacuum drying process conditions be 80 DEG C at be vacuum dried 4-6h.
By such scheme, step 3) process conditions of the annealing are：0.5-1h is processed at 160-175 DEG C.
The present invention also provides above-mentioned Ag3The preparation method of SI crystalline state fast ion conducting materials, its step is as follows：
1) mill ball is previously charged into ball grinder and then in the glove box full of inert atmosphere by Ag2S and AgI is massaged
You compare 1:1 carries out dispensing, and the raw material that then will be prepared adds ball-milling additive to be placed in carrying out high-energy ball milling reaction in ball grinder, instead
The good sample of ball milling is obtained after should terminating；
2) by step 1) the gained good sample of ball milling is placed in vacuum drying chamber and is vacuum dried, remove grinding aid and obtain
To dusty material；
3) by step 2) gained dusty material made annealing treatment, obtain Ag3SI crystalline state fast ion conducting materials.
Ag of the present invention3The preparation method of SI crystalline materials mainly comprising two processes, i.e. Process During High Energy Ball Milling and
Heat treatment process, the AgI and Ag in Process During High Energy Ball Milling2There is solid phase reaction in S, particle gradually refines to form nano particle, its
Apparent activation energy is raised, and solid phase reaction forms Ag more conducively between particle3SI crystal, but in further mechanical milling process,
Ag3There is the fracture of key in SI crystal, defect increases and gradually forms Ag in crystal in Process During High Energy Ball Milling3SI non-crystalline materials；With
New keys are gradually formed in annealing process afterwards, so that Ag3SI non-crystalline materials ultimately form pure Ag3SI crystal materials
Material.
In general, the reason for material purity is influenceed in this fast ion conducting material is exactly unreacted complete AgI and Ag2S,
The present invention causes that the particle diameter of particle reduces by mechanical milling process, and surface can increase so that AgI and Ag2Have between S enough
Energy is reacted, and forms amorphous Ag3SI, finally by heat treatment process so that amorphous Ag3SI is converted into crystal,
Obtain purity fast ion conducting material high.
The beneficial effects of the present invention are：Compared with the fusion method and chemical synthesis reported at present, the present invention is carried
The preparation method flow of confession is simple, short preparation period, and heat treatment temperature is low, reduces manufacturing cost and energy consumption；Prepared
Ag3SI fast-ionic conductor crystalline material purity is high, and ionic conductivity is high.
Brief description of the drawings
Fig. 1 is the step 1 of the embodiment of the present invention 1) good sample (curve a) and step 3) the gained Ag of gained ball milling3SI crystalline state
Fast ion conducting material (the XRD spectrum of curve b)；
Fig. 2 is the step 1 of embodiment 1) the good continuous heating and cooling of sample of institute's ball milling twice gained differential thermal analysis curve (curve c
And d) and step 3) obtained by Ag3Differential thermal analysis curve (the curve e) of SI crystalline state fast ion conducting materials；
Fig. 3 is the step 1 of embodiment 2) good sample (curve f) and step 3) the gained Ag of gained ball milling3The fast ion of SI crystalline state
Conductor material (the XRD spectrum of curve g)；
Fig. 4 is the step 2 of embodiment 2) the good continuous heating and cooling of sample of institute's ball milling twice gained differential thermal analysis curve (curve h
And i) and step 3) obtained by Ag3Differential thermal analysis curve (the curve j) of SI crystalline state fast ion conducting materials.
Specific embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made below in conjunction with the accompanying drawings into
One step is described in detail.
Embodiment 1
Prepare Ag3SI fast ion conducting materials, step is as follows：
1) 22.5g zirconium dioxides mill ball is previously charged into ball grinder, and (material ball ratio is 15:1), then full of nitrogen
By 0.7703g Ag in the glove box of atmosphere2S and 0.7297g AgI (mol ratios 1:1) mixing carries out dispensing, will then prepare
Raw material adds 3mL normal heptanes to be placed in ball grinder, in a nitrogen atmosphere, seals ball grinder, and the ball grinder of good seal is put into
In high energy ball mill (Fritsch Pulverisette 7), the rotating speed for adjusting ball mill is anti-for 800rpm carries out high-energy ball milling
Should, ball milling 10h sets a mechanical milling process circulation time for 5min, each circulation work 2min, rest 3min, it is ensured that instrument
Can fully radiate, reaction obtains the good sample of ball milling after terminating；
2) by step 1) the gained good sample of ball milling is placed in vacuum drying chamber and 4h is vacuum dried at 80 DEG C, removes grinding
Auxiliary agent obtains dusty material；
3) by step 2) gained dusty material is placed in vacuum drying chamber 0.5h made annealing treatment at 160 DEG C, obtains Ag3SI
Crystalline state fast ion conducting material.
Fig. 1 is the present embodiment step 1) good sample (curve a) and step 3) the gained Ag of gained ball milling3The fast ion of SI crystalline state
Conductor material (the X ray diffracting spectrum of curve b), it can be seen that after high-energy ball milling, is remained in gained sample
Fixed AgI, and Ag3The diffraction maximum of SI crystal thing phases is not obvious, but by after annealing, Ag being only existed in XRD spectrum3SI
The diffraction maximum of crystal, illustrates to ultimately form purer Ag3SI crystal.
Fig. 2 is the present embodiment step 1) the good sample (curve c and d) of gained ball milling and step 3) gained Ag3SI crystalline state is fast
(the DSC collection of illustrative plates of curve e), wherein curve c and curve d are respectively and the good sample of ball milling are warming up to from 50 DEG C ionic conductor material
270 DEG C continuously scan the DSC curve for obtaining twice, it is found that to scan do not only exist Ag in the curve for obtaining for the first time3SI's
Phase transformation peak, while also AgI and Ag2Why the phase transformation peak of S, exist in the XRD spectrum of ball milling sample this also explains in Fig. 1
The diffraction maximum of AgI crystalline phases；Secondary scanning curve is similar with the scanning curve of curve e, only exists an Ag3The phase transformation of SI
Peak, this explanation has obtained purer Ag by dynamic temperature-rise period and annealing process3SI crystalline phases.
Embodiment 2
Prepare Ag3SI fast ion conducting materials, step is as follows：
1) 22.5g zirconium dioxides mill ball is previously charged into ball grinder, and (material ball ratio is 15:1), then full of nitrogen
By 0.7703g Ag in the glove box of atmosphere2S and 0.7297g AgI (mol ratios 1:1) mixing carries out dispensing, will then prepare
Raw material adds 3mL normal heptanes to be placed in ball grinder, in a nitrogen atmosphere, seals ball grinder, and the ball grinder of good seal is put into
In high energy ball mill (Fritsch Pulverisette 7), the rotating speed for adjusting ball mill is anti-for 600rpm carries out high-energy ball milling
Should, ball milling 10h sets a mechanical milling process circulation time for 5min, each circulation work 2min, rest 3min, it is ensured that instrument
Can fully radiate, reaction obtains the good sample of ball milling after terminating；
2) by step 1) the gained good sample of ball milling is placed in vacuum drying chamber and 4h is vacuum dried at 80 DEG C, removes grinding
Auxiliary agent obtains dusty material；
3) by step 2) gained dusty material is placed in vacuum drying chamber 0.5h made annealing treatment at 160 DEG C, obtains Ag3SI
Crystalline state fast ion conducting material.
Fig. 3 is the present embodiment step 1) good sample (curve f) and step 3) the gained Ag of gained ball milling3The fast ion of SI crystalline state
(X ray diffracting spectrum of curve g), (curve a), the present embodiment ball milling is good compared with the ball milling sample of embodiment 1 for conductor material
(curve f) crystal diffractions peak is weaker, and non-crystallization degree is higher for sample.But by after annealing, still occurring in XRD spectrum
Ag3The diffraction maximum of SI crystal, illustrates to ultimately form Ag3SI crystal.
Fig. 4 is the present embodiment step 1) the good sample (curve h and i) of gained ball milling and step 3) gained Ag3SI crystalline state is fast
(the DSC collection of illustrative plates of curve j), wherein curve h and curve i are respectively the good sample of ball milling from 100 DEG C of intensifications ionic conductor material
The DSC curve for obtaining twice is continuously scanned to 270 DEG C, it is found that the curve difference that twice sweep is obtained is to sweep for the second time
The phase transformation peak for retouching AgI and Ag2S in curve disappears, and only exists Ag3The phase transformation peak of SI, and phase transition temperature has less skew, two
Curve after secondary scanning is similar to the curve j after annealing, illustrates finally to only exist Ag3SI crystal.
Claims (6)
1. a kind of Ag3SI crystalline state fast ion conducting materials, it is characterised in that：It is prepared by following methods：
1) mill ball is previously charged into ball grinder and then in the glove box full of inert atmosphere by Ag2S and AgI are in molar ratio
1:1 carries out dispensing, and the raw material that then will be prepared adds ball-milling additive to be placed in carrying out high-energy ball milling reaction, reaction knot in ball grinder
The good sample of ball milling is obtained after beam；
2) by step 1) the gained good sample of ball milling is placed in vacuum drying chamber and is vacuum dried, remove grinding aid and obtain powder
Powder material；
3) by step 2) gained dusty material made annealing treatment, obtain Ag3SI crystalline state fast ion conducting materials.
2. Ag according to claim 13SI crystalline state fast ion conducting materials, it is characterised in that：Step 1) mill ball is
Zirconium dioxide mill ball, material ball ratio is 15-30:1；The grinding aid is normal heptane, per ball milling 1g material amounts 1.5-2mL.
3. Ag according to claim 13SI crystalline state fast ion conducting materials, it is characterised in that：Step 1) high-energy ball milling
Reaction time is 10-20h；Rotational speed of ball-mill is 600-800rpm in high-energy ball milling course of reaction, and mechanical milling process one is circularly set
It is 5min, each circulation work 2min, rest 3min.
4. Ag according to claim 13SI crystalline state fast ion conducting materials, it is characterised in that step 2) vacuum drying
Process conditions to be vacuum dried 4-6h at 80 DEG C.
5. Ag according to claim 13SI crystalline state fast ion conducting materials, it is characterised in that step 3) annealing
Process conditions be：0.5-1h is processed at 160-175 DEG C.
6. according to any described Ag of claim 1-53The preparation method of SI crystalline state fast ion conducting materials, it is characterised in that step
It is rapid as follows：
1) mill ball is previously charged into ball grinder and then in the glove box full of inert atmosphere by Ag2S and AgI are in molar ratio
1:1 carries out dispensing, and the raw material that then will be prepared adds ball-milling additive to be placed in carrying out high-energy ball milling reaction, reaction knot in ball grinder
The good sample of ball milling is obtained after beam；
2) by step 1) the gained good sample of ball milling is placed in vacuum drying chamber and is vacuum dried, remove grinding aid and obtain powder
Powder material；
3) by step 2) gained dusty material made annealing treatment, obtain Ag3SI crystalline state fast ion conducting materials.
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| CN201611184726.0A CN106711448A (en) | 2016-12-20 | 2016-12-20 | Ag3SI crystalline fast ion conductor material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888377A (en) * | 2019-04-17 | 2019-06-14 | 宁波容百新能源科技股份有限公司 | A kind of high ionic conductivity sulfide solid electrolyte and preparation method thereof based on wet ball grinding |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104752756A (en) * | 2015-04-23 | 2015-07-01 | 武汉理工大学 | Preparation method of high-ion electrical conduction solid electrolyte material |
| CN104851473A (en) * | 2015-04-23 | 2015-08-19 | 武汉理工大学 | Novel amorphous fast ionic conductor material and preparation method thereof |
| CN106057276A (en) * | 2016-06-01 | 2016-10-26 | 武汉理工大学 | AgI-Ag2S-P2S5 amorphous fast ion conductor material and preparation method thereof |
-
2016
- 2016-12-20 CN CN201611184726.0A patent/CN106711448A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104752756A (en) * | 2015-04-23 | 2015-07-01 | 武汉理工大学 | Preparation method of high-ion electrical conduction solid electrolyte material |
| CN104851473A (en) * | 2015-04-23 | 2015-08-19 | 武汉理工大学 | Novel amorphous fast ionic conductor material and preparation method thereof |
| CN106057276A (en) * | 2016-06-01 | 2016-10-26 | 武汉理工大学 | AgI-Ag2S-P2S5 amorphous fast ion conductor material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| S. YAN ET AL.: "Rapid Fabrication and Thermal Performance of Ag3SI Super-ionic Conductor", 《CHALCOGENIDE LETTERS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888377A (en) * | 2019-04-17 | 2019-06-14 | 宁波容百新能源科技股份有限公司 | A kind of high ionic conductivity sulfide solid electrolyte and preparation method thereof based on wet ball grinding |
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Application publication date: 20170524 |