CN108390094A - A kind of air-stable sulfide sodion solid electrolytes and preparation method thereof - Google Patents
A kind of air-stable sulfide sodion solid electrolytes and preparation method thereof Download PDFInfo
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- CN108390094A CN108390094A CN201810125761.8A CN201810125761A CN108390094A CN 108390094 A CN108390094 A CN 108390094A CN 201810125761 A CN201810125761 A CN 201810125761A CN 108390094 A CN108390094 A CN 108390094A
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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Abstract
The invention discloses a kind of air-stable sulfide sodion solid electrolytes and preparation method thereof, the chemical formula of the sulfide sodion solid electrolytes is Na4‑xSn1‑xMxS4‑yOy, wherein at least one of M P, As, Sb, 0.05≤x≤0.5,0≤y≤0.5.The crystal structure of sulfide sodion solid electrolytes has I41/ acd space groups isolate [Sn/M]4Tetrahedron constitutes skeleton, and sodium ion fills five crystal positions not taken.Sulfide sodion solid electrolytes are used to prepare all-solid-state battery.The solid electrolyte material of the present invention has high ionic conductivity, and it is stable in the air, and then there are sulfide solid electrolytes to air-sensitive for the solution prior art, exposure easily generates sulfide hydrogen and also results in solid electrolyte failure in air, limits the application of sulfide solid electrolyte, increases the technical issues of making battery cost.
Description
Technical field
The invention belongs to all-solid sodium ion field of batteries, more particularly, to a kind of air-stable sulfide sodium ion
Solid electrolyte and preparation method thereof.
Background technology
Electrochemical energy storage technology the advantages such as is not limited due to simplicity, high efficiency, installation by place at present, is numerous energy storage skills
Most one of the technology of industrialization promotion foreground in art.Wherein, lithium ion battery energy density is big, has extended cycle life, works
Voltage height, memory-less effect, self discharge are small, and development is more mature, is the electrochemical energy storage technology being most widely used, portable
Domination advantage is occupied in formula electronic equipment market and electric powered motor field, is considered as the main selection of extensive energy-accumulating power station.
However, the cost is relatively high for lithium ion battery, global resources reserves are limited, it is impossible to while meeting power battery and extensive storage
It can widely applied demand.
Sodium and elemental lithium are in same main group, and the physics and chemical property of the two are closely similar, and electrode potential is suitable
(ENa+/Na=-2.71V, ELi+/Li=-3.02V, vs.SHE), it can be as the replacement of lithium.Meanwhile resourceful (the abundance ratio of sodium
High 4~5 orders of magnitude of lithium), it is of low cost, sodium-ion battery for extensive energy storage field have apparent economy and environment it is excellent
Gesture.On the other hand, organic electrolyte is replaced using inorganic solid electrolyte, battery is made to become all solid state sode cell, in battery not
Flammable organic solution is reused, safety device can be simplified, it is easy to produce, and reduce the manufacturing cost of battery.
In addition, solid electrolyte is single sodium ion conductor, the only movement of sodium ion inside it will not occur to be similar to electrolyte
Side reaction caused by the movement of middle anion occurs, it can be expected that the raising of safety and durability.
Sodion solid electrolytes are the critical materials of all solid state sode cell.In the current inorganic solid-state electrolysis reported
In matter, sulfide electrolyte is standby because of its higher ionic conductivity and good mechanical performance (being easy to eliminate the impedance of grain circle)
It is concerned.But sulfide solid electrolyte, often to air-sensitive, exposure easily generates sulfide hydrogen and leads simultaneously in air
Solid electrolyte failure is caused, this is by the application for limiting sulfide solid electrolyte or increases making battery cost.
Invention content
For the disadvantages described above or Improvement requirement of the prior art, the present invention provides a kind of air-stable sulfide sodium ions
Solid electrolyte and preparation method thereof, thus solving the prior art, there are sulfide solid electrolytes to air-sensitive, exposure
Sulfide hydrogen is easily generated in air and also results in solid electrolyte failure, is limited the application of sulfide solid electrolyte, is increased
The technical issues of making battery cost.
To achieve the above object, according to one aspect of the present invention, it is solid to provide a kind of air-stable sulfide sodium ion
The chemical formula of body electrolyte, the sulfide sodion solid electrolytes is Na4-xSn1-xMxS4-yOy, wherein in M P, As, Sb
At least one, 0.05≤x≤0.5,0≤y≤0.5.
Further, the crystal structure of sulfide sodion solid electrolytes has I41/ acd space groups isolate [Sn/M]4
Tetrahedron constitutes skeleton, and sodium ion fills five crystal positions not taken.
Further, sulfide sodion solid electrolytes are used to prepare all-solid-state battery.
Further, consider that M is preferably Sb from environmental protection, air stability.
Further, x ranges preferably from 0.05≤x≤0.4, and the range of the x is more preferably 0.1≤x≤0.3.
It is another aspect of this invention to provide that providing a kind of preparation side of air-stable sulfide sodion solid electrolytes
Method, including：
(1) by Na2S、Na2O、SnS2、M2S5According to Na4-xSn1-xMxS4-yOyMolar ratio uniformly mix, it is former to obtain mixing
Material；
(2) mixed raw material is subjected to synthesis in solid state under 400 DEG C~650 DEG C of oxygen free condition, obtains Na4-xSn1-xMxS4- yOy, crystal structure meets I41/ acd space groups；Oxygen free condition is the vacuum condition less than 100Pa.
Wherein, at least one of M P, As, Sb, 0.05≤x≤0.5,0≤y≤0.5.
Further, the time of synthesis in solid state is 8h~for 24 hours.It is anti-that high temperature is conducive to preparing for sulfide solid electrolyte
It answers, improves the crystallinity of crystallization based material, and then improve the ionic conductivity of sulfide solid electrolyte；However excessively high temperature
It is easy that sulfide solid electrolyte is made to produce sulphur vacancy defect.Therefore the temperature of synthesis in solid state is preferably 450 DEG C~550 DEG C.
Further, mixed uniformly method is planetary type ball-milling or vibratory milling in step (1).Preferably, planet
It is more preferable that formula ball milling obtains sample crystallization, and ionic conductivity is high.
Further, when uniformly being mixed in step (1), the rotating speed of ball milling is 200r/min~400r/min, ball milling when
Between be 10h~20h.
Further, further include between step (1) and step (2)：Mixed raw material is compressed to sheet so that mixed raw material
In each ingredient contact more closely, reaction it is more abundant.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect：
(1) present invention by P, As, Sb element by replacing Na4SnS4In Sn, can obtain a kind of new there is macroion electricity
The solid electrolyte material of conductance, ionic conductivity (＞ 10-4S/cm) relative to Na4SnS4(10-7S/cm 3 quantity) are promoted
Grade, while the material has a kind of completely new structure.Solid electrolyte material just because of the present invention has macroion conductance
Rate so that solid electrolyte material is stable in the air, and then there are sulfide solid electrolytes to air for the solution prior art
Very sensitive, exposure easily generates sulfide hydrogen and also results in solid electrolyte failure in air, limits sulfide solid electrolyte
Application, increase make battery cost the technical issues of.
(2) 0.05≤x≤0.5 in the present invention, x's ranges preferably from 0.05≤x≤0.4, and the range of x is more preferably 0.1
≤ x≤0.3 can guarantee that M replaces parent phase Na on a small quantity4SnS4In Sn and produce high ionic conductivity space group be I41/ acd's
Na4-xSn1-xMxS4-yOy, and M element excessively production impurity can be prevented.0≤y≤0.5, excessive oxygen element can reduce ionic conductance
Rate, a small amount of oxygen element can promote electrochemistry/chemical stability of solid electrolyte.
(3) there are the crystalline phases of various structures in the present invention, and uniform batch mixing is particularly significant, and batch mixing unevenness causes component not
Unanimously, impurity is easy tod produce；Be conducive to later stage sulfide electrolyte also along with the thinning process of raw material in mixing process simultaneously
Synthesis；The rotating speed of ball milling is 200r/min~400r/min when uniformly being mixed in the present invention, and the time of ball milling is 10h~20h,
So that raw material uniformly mixes.
Description of the drawings
Fig. 1 is Na of the present invention4-xSn1-xMxS4-yOyCrystal structure schematic diagram；
Fig. 2 is the XRD of the XRD and comparative example 1 of the embodiment of the present invention 1,4,6,9,12,14；
Fig. 3 is the XRD of the embodiment of the present invention 1 as a child in air kind exposure 24；
Fig. 4 is charging and discharging curve of the embodiment of the present invention 1 as solid electrolyte in all solid state sode cell.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
It does not constitute a conflict with each other and can be combined with each other.
The chemical formula of the cubic phase sulfide of the present invention is Na4-xSn1-xMxS4-yOy；Wherein, in the elements such as M P, As, Sb
It is one or more；Wherein, 0.05≤x≤0.5, y ＜ 0.5；
The Na4-xSnl-xMxS4-yOyFor a kind of novel crystal structure, crystal structure belongs to I41/ acd space groups, the structure
Middle Sn/M atoms are formed by isolated (Sn/M) S4Tetrahedron constitutes skeleton structure, and Na ions are randomly distributed over remaining four
In face body and octahedral interstice, as shown in Figure 1, therefore in the XRD spectrum obtained using the Alpha-ray X-ray diffraction measures of CuK
In, at least 2 θ=11.10 ° ± 0.50 ° of following angles of diffraction, 12.80 ± 0.50 °, 14.70 ° ± 0.50 °, 15.68 ° ±
0.50°、18.18°±0.50°、21.32°±0.50°、25.16°±0.50°、25.75°±0.50°、26.76°±0.50°、
28.33°±0.50°、31.73°±0.50°、32.53°±0.50°、33.72°±0.50°、36.87°±0.50°、38.51°
± 0.50 °, the peak that occurs of 39.87 ° ± 0.50 ° of position, wherein 18.18 ° ± 0.50 °, 36.86 ° ± 0.50 ° of peak it is opposite
It is relatively strong.
M element is instead of Na4SnS4In Sn, a kind of solid electrolytic material with brand new, such material can be obtained
With high sodium ion conductivity, ionic conductivity (＞ 10-4S/cm) relative to Na4SnS4(10-7S/cm 3 quantity) are promoted
Grade.The sulfide solid electrolyte is to air-stable.
M element substitution can promote to have the new construction of high ionic conductivity to generate, but as x >=0.4, due to crystal knot
The limitation of structure can cause to generate impurity, reduce the ionic conductivity of material instead；Therefore, x is preferably 0.1~0.3.
A small amount of doping of oxygen element can improve the stability of material, but due to oxygen and the stronger bonding action of sodium, can drop
Low ionic conductivity is preferably smaller than equal to 0.5 with this y.
The preparation method of above-mentioned cubic phase sulfide is：By Na2S、Na2O、SnS2、P2S5、As2S5、Sb2S5With Na4-xSn1- xMxS4-yOyInterior molar ratio weighs under an inert atmosphere, and uniformly mixes, then vacuum degree be less than 100Pa under 400 DEG C~
650 DEG C of calcining 8h~for 24 hours, in order to avoid reactant and the oxygen or reaction of moisture generation impurity in air；
And there are the crystalline phase of various structures in the system of Na-Sn-M-S-O, uniform batch mixing is particularly significant, and batch mixing is uneven
Cause the inconsistent of component, easy tos produce impurity；Be conducive to the later stage also along with the thinning process of raw material in mixing process simultaneously
The synthesis of sulfide electrolyte；Mixed uniformly method can select the mechanical grinding methods such as vibromill, turbine grinding, ball milling；
It, can be with 10~20h of rotating speed ball milling of 200~400r/min such as when being mixed with ball grinding method.
High temperature is conducive to the preparation reaction of sulfide solid electrolyte, improves the crystallinity of crystallization based material, and then improve
The ionic conductivity of sulfide solid electrolyte；However excessively high temperature is easy that sulfide solid electrolyte production sulphur vacancy is made to lack
It falls into.Therefore the temperature of calcining is preferably 450 DEG C~550 DEG C.
Embodiment 1
By Na in the glove box of argon gas protection2S、Sb2S5、SnS2With Na3.7Sn0.7Sb0.3S4Molar ratio weighing, and mix
Cooperation is raw material；
Raw material and zirconia ball are packed into the ball grinder of the zirconia substrate of capacity, container is sealed, with 350r/min's
Rotating speed carries out ball mill mixing, and mixed-powder is obtained after 15h；
By mixed-powder in glove box, take out, and 150MPa pressure formings under powder tablet press machine, be put into glass/
In quartz ampoule, it is evacuated to vacuum degree and is less than 100Pa, sealing is put into Muffle furnace.The heating rate of Muffle furnace be 100 DEG C/it is small
When, solid phase reaction is carried out at 550 DEG C later 24 hours, natural cooling cooling obtains product Na4-xSn1-xMxS4-yOy, this implementation
In example, product Na3.7Sn0.7Sb0.3S4。
In glove box, product is taken out from sealed glass tube, broken finely ground in mortar, it is 10 μm~20 to obtain granularity
μm powdered sample.It into a certain amount of sample is weighed in glove box, is encased in the PET pipes of internal diameter 10mm, uses up and down
The powder compacting tool of stainless steel is clamped, and using uniaxial compression machine, under the pressure of 160MPa, it is arbitrary to form diameter 10mm
The electrolyte sheet of thickness.Bronze end is placed respectively on electrolyte sheet two sides, and bronze end is made to be uniformly dispersed in electrolyte sheet surface,
360MPa forming under the pressure forms blocking electrode.Blocking electrode is put into the closed electrochemical cell of argon gas protection at 25 DEG C
In, carry out ac impedance measurement.The amplitude for applying alternating current is 20mV, frequency range 10Hz~1MHz.Its room-temperature ion conductance
Rate is 0.48mS/cm.
Comparative example 1
According to Na4SnS4Composition formula weighs Na respectively in the glove box of argon gas protection2S, SnS2And it mixes as raw material；
Raw material and zirconia ball are packed into the ball grinder of the zirconia substrate of capacity, container is sealed, with 280r/min's
Rotating speed carries out ball mill mixing, and mixed-powder is obtained after 20h；
It by mixed-powder in glove box, takes out, and be molded under powder tablet press machine, is put into glass/quartz pipe, take out
Vacuum to vacuum degree is less than 100Pa, and sealing is put into Muffle furnace.The heating rate of Muffle furnace is 100 DEG C/h, Zhi Hou
550 DEG C carry out solid phase reaction 10 hours, and natural cooling cooling obtains product Na4SnS4。
In glove box, product is taken out from sealed glass tube, broken finely ground in mortar, it is 10 μm~20 to obtain granularity
μm powdered sample.It into a certain amount of sample is weighed in glove box, is encased in the PET pipes of internal diameter 10mm, uses up and down
The powder compacting tool of stainless steel is clamped, and using uniaxial compression machine, under the pressure of 160MPa, it is arbitrary to form diameter 10mm
The electrolyte sheet of thickness.Bronze end is placed respectively on electrolyte sheet two sides, and bronze end is made to be uniformly dispersed in electrolyte sheet surface,
360MPa forming under the pressure forms blocking electrode.Blocking electrode is put into the closed electrochemical cell of argon gas protection at 25 DEG C
In, carry out ac impedance measurement.The amplitude for applying alternating current is 20mV, frequency range 10Hz~1MHz.Its room-temperature ion conductance
Rate is 3x10-7S/cm.Than the Na of new construction4-xSn1-xMxS4-yOyLow three orders of magnitude of ionic conductivity.
To simplify the description, the preparation parameter of embodiment 2- embodiments 15 and product characteristics are included in table 1, are not arranged in table
Parameter it is same as Example 1.
The preparation parameter and product characteristics of 1 embodiment 2- embodiments 15 of table
Analysis of experimental results
(1) measurement of conductivity
The ionic conductivity of embodiment 1-15 is compared with comparative example 1, it can be seen that the Na with new construction4- xSn1-xMxS4-yOySulfide solid electrolyte shows relatively high ionic conductivity.
(2) X-ray diffraction measure
The Alpha-ray X-ray diffraction measures of CuK have been carried out to embodiment 1-15, find to have 2 θ=11.10 ° ±
0.50°、12.80±0.50°、14.70°±0.50°、15.68°±0.50°、18.18°±0.50°、21.32°±0.50°、
25.16°±0.50°、25.75°±0.50°、26.76°±0.50°、28.33°±0.50°、31.73°±0.50°、32.53°
± 0.50 °, 33.72 ° ± 0.50 °, 36.87 ° ± 0.50 °, 38.51 ° ± 0.50 °, 39.87 ° ± 0.50 ° of position occurs
Peak, wherein 18.18 ° ± 0.50 °, 36.86 ° ± 0.50 ° of peak it is relatively strong
The diffraction maximum of diffraction maximum and embodiment in comparative example 1 is entirely different, because they have different crystal structures,
This also determines the gap of their 3 orders of magnitude in terms of ionic conductivity.
(3) air exposure stability test
Determine the electrolyte (Na in embodiment 13.7Sn0.7Sb0.3S4) exposure 24 hours in air (humidity~60%)
XRD spectra afterwards, and be stored in after synthesis in glove box compared with the XRD spectra of sample, the results are shown in Fig. 3.It can be found that
After material exposes 24 hours in air, XRD spectra does not have significant change, illustrates that it stablizes in air kind energy holding structure.
(4) all-solid-state battery charge and discharge
Sulfide solid electrolyte (the Na that will be obtained in embodiment 33.7Sn0.7Sb0.3S4) with the TiS of grain size~5um2With
TiS2: sulfide solid electrolyte material=7: 3 weight ratio is mixed, and anode composite material is obtained.Then, with Na or
Na-Sb alloys are as negative material, sulfide solid electrolyte Na3.7Sn0.7Sb0.3S4Solid electrolyte layer is formed, is made complete solid
State battery.For the all-solid-state battery of preparation, constant current charge-discharge measurement carries out in the range of 1V to 2.5V, and charge-discharge magnification is
0.1C, temperature are 25 DEG C.The results are shown in Figure 4, it is known that the all-solid-state battery prepared by sulfide solid electrolyte of the present invention
It can be good.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of air-stable sulfide sodion solid electrolytes, which is characterized in that the sulfide sodion solid electrolysis
The chemical formula of matter is Na4-xSn1-xMxS4-yOy, wherein at least one of M P, As, Sb, 0.05≤x≤0.5,0≤y≤
0.5。
2. a kind of air-stable sulfide sodion solid electrolytes as described in claim 1, which is characterized in that the vulcanization
The crystal structure of object sodion solid electrolytes has I41/ acd space groups isolate [Sn/M]4Tetrahedron constitutes skeleton, sodium ion
Fill five crystal positions not taken.
3. a kind of air-stable sulfide sodion solid electrolytes as claimed in claim 1 or 2, which is characterized in that described
Sulfide sodion solid electrolytes are used to prepare all-solid-state battery.
4. a kind of air-stable sulfide sodion solid electrolytes as claimed in claim 1 or 2, which is characterized in that the M
Preferably Sb.
5. a kind of air-stable sulfide sodion solid electrolytes as claimed in claim 1 or 2, which is characterized in that the x
Range preferably from 0.05≤x≤0.4, the range of the x is more preferably 0.1≤x≤0.3.
6. a kind of preparation method of air-stable sulfide sodion solid electrolytes according to any one of claims 1 to 5,
It is characterized in that, including：
(1) by Na2S、Na2O、SnS2、M2S5According to Na4-xSn1-xMxS4-yOyMolar ratio uniformly mix, obtain mixed raw material；
(2) mixed raw material is subjected to synthesis in solid state under 400 DEG C~650 DEG C of oxygen free condition, obtains Na4-xSn1-xMxS4-yOy,
Crystal structure meets I41/ acd space groups；
Wherein, at least one of M P, As, Sb, 0.05≤x≤0.5,0≤y≤0.5.
7. a kind of preparation method of air-stable sulfide sodion solid electrolytes as claimed in claim 6, feature exist
It is 8h~for 24 hours in the time of, the synthesis in solid state.
8. a kind of preparation method of air-stable sulfide sodion solid electrolytes as claimed in claim 6, feature exist
In mixed uniformly method is planetary type ball-milling or vibratory milling in the step (1).
9. a kind of preparation method of air-stable sulfide sodion solid electrolytes as claimed in claim 8, feature exist
In, when uniformly being mixed in the step (1), the rotating speed of ball milling is 200r/min~400r/min, time of ball milling be 10h~
20h。
10. a kind of preparation method of air-stable sulfide sodion solid electrolytes as claimed in claim 6, feature exist
In further including between the step (1) and step (2)：Mixed raw material is compressed to sheet so that each ingredient in mixed raw material
More closely, reaction is more abundant for contact.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888376A (en) * | 2019-03-29 | 2019-06-14 | 华中科技大学 | A kind of sulfide sodion solid electrolytes and preparation method thereof |
| WO2020022342A1 (en) * | 2018-07-24 | 2020-01-30 | 公立大学法人大阪 | Solid electrolyte for all-solid-state sodium battery, manufacturing method therefor, and all-solid-state sodium battery |
| CN112777632A (en) * | 2021-01-25 | 2021-05-11 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Sulfide lithium ion solid electrolyte and preparation method and application thereof |
| CN114447423A (en) * | 2022-01-29 | 2022-05-06 | 天目湖先进储能技术研究院有限公司 | Sulfide solid electrolyte with lithium supplement and moisture absorption functions |
| WO2022129339A1 (en) * | 2020-12-17 | 2022-06-23 | Umicore | A solid-state electrolyte for solid-state rechargeable sodium-ions batteries |
| CN115692830A (en) * | 2022-10-24 | 2023-02-03 | 黄冈师范学院 | Sodium ion sulfide electrolyte and preparation method thereof |
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| CN115692830A (en) * | 2022-10-24 | 2023-02-03 | 黄冈师范学院 | Sodium ion sulfide electrolyte and preparation method thereof |
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