CN108238616A - A kind of cubic phase sulfide and preparation method thereof - Google Patents
A kind of cubic phase sulfide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of cubic phase sulfide and preparation method thereof.The chemical formula of the cubic phase sulfide is LiyMxP1- xS6；Wherein, M be Group IIIA or IVA races element, chemical valence be+a, 0<X≤0.4, y=7+5x-ax.The sulfide of Group IIIA or IVA races element by being replaced the part P in raw material by the present invention2S5, the sulfide solid electrolyte prepared can be made still to be maintained cubic phase at room temperature, while there is the ionic conductivity of more than 0.31mS/cm；The preparation method does not need to quenching processing, so as to simplify preparation process, has saved production cost；It is more suitable for all-solid-state battery.
Description
Technical field
The invention belongs to solid lithium battery field, more particularly, to a kind of cubic phase sulfide and preparation method thereof.
Background technology
In recent years as the massaging devices such as computer, camera and mobile phone and the quick of communication device are popularized, for as these
The exploitation of the battery of installation's power source is increasingly paid attention to by industry.In addition, in automobile industry field, pure electric automobile or mixing
The battery of the required high power density of electric vehicle and high power capacity is also just in Devoting Major Efforts To Developing.In current multiple battery system,
Lithium ion battery receives all circles' concern due to its high-energy density.
Lithium ion battery currently on the market, as electrolyte, results in the need for installing due to the use of flammable organic solution
Reply short circuit causes the raised device of temperature and improves construction and material to prevent short circuit.Utilize inorganic solid electrolyte generation
For organic electrolyte, battery is made to become all-solid-state battery, flammable organic solution is not used in battery, safety can be simplified
Device, it is easy to produce, and reduce the manufacturing cost of battery.In addition, solid electrolyte is single ionic conductor, in it
Portion only has the movement of Li ions, will not occur to be similar to side reaction generation caused by the movement of anion in electrolyte, it is expected that
Safety and the raising of durability.
Solid electrolyte is the critical material of all-solid-state battery.In the current inorganic solid electrolyte reported, sulphur
Compound electrolyte is concerned because of its higher ionic conductivity and good mechanical performance (being easy to eliminate the impedance of grain circle).
For this solid electrolyte applied in all-solid lithium-ion battery, need high ionic conductivity, high electrification
/ chemical stability and low cost of material.
For example, non-patent literature (Chemistry A European Journal, Vol.10, p.5138-5147,2010)
In disclose it is a kind of have compared with high ionic conductivity, compared with the sulfide solid electrolyte Li of high electrochemical stability7PS6；The vulcanization
Cubic phase is presented in object solid electrolyte at high temperature, and orthorhombic phase is presented at room temperature), and ionic conductivity is also therewith with larger
Variation.Wherein, cubic phase argyrodite type Li7PS6With higher ionic conductivity, but only it is stable in the presence of temperature and is higher than
200 DEG C of temperature range；And the ionic conductivity of rectangle phase structure is only~10-6S cm-1；Such as macroion conductance to be obtained
Cubic phase generally requires to carry out quenching processing, this greatly hinders the Li of high ionic conductivity7PS6It prepares and uses.
Invention content
For the disadvantages described above or Improvement requirement of the prior art, the present invention provides a kind of cubic phase sulfide and its preparations
Method its object is to carry out part doping to sulfide electrolyte, is thus provided and is stablized at room temperature and with macroion conductance
The cubic phase argyrodite type lithium ion solid electrolyte of rate.
To achieve the above object, one side according to the invention, provides a kind of cubic phase sulfide, and chemical formula is
LiyMxP1-xS6；Wherein, M be Group IIIA or IVA races element, chemical valence be+a, 0<X≤0.4, y=7+5x-ax.
Preferably, it is one or more in M B, Al, Si, Ge or Sn.
Preferably, 0.1≤x≤0.3 cubic phase sulfide to be inhibited to be changed into tetragonal phase at room temperature, while avoids standing
Square phase sulfide generates impurity.
As it is further preferred that ionic conductivity of the cubic phase sulfide at 25 DEG C for 0.31mS/cm~
1.31mS/cm。
Preferably, in the x-ray diffractogram of powder of the cubic phase sulfide, at least in following 2 θ of the angle of diffraction：15.44°±
0.50°、17.84°±0.50°、25.35°±0.50°、29.82°±0.50°、31.16°±0.50°、39.45°±0.50°、
Diffraction maximum is shown at 44.57 ° ± 0.50 °, 39.45 ° ± 0.50 ° and 47.48 ° ± 0.50 ° of degree, and the X-ray powder spreads out
It is the collection of illustrative plates obtained with CuK alpha rays to penetrate figure.
Preferably, M be Group IIIA element, a=3；Or M be IVA races element, a=2.
It is another aspect of this invention to provide that additionally providing the preparation method of above-mentioned cubic phase sulfide, include the following steps：
(1) by Li2S、M2Sa、P2S5With y:x:The molar ratio of (1-x) is uniformly mixed as raw material；
(2) raw material under 400 DEG C~650 DEG C of oxygen free condition is subjected to synthesis in solid state, obtains LiyMxP1-xS6；Wherein, 0<
X≤0.4, y=7+5x-ax.
Preferably, mixed uniformly method is in the step (1), by Li2S、M2Sa、P2S5After mixing with 220r/min~
The rotating speed ball milling 15h of 320r/min~for 24 hours.
Preferably, the oxygen free condition in the step (2) is the vacuum condition less than 100Pa.
Preferably, the temperature of synthesis in solid state is 450 DEG C~500 DEG C in the step (2).
Preferably, the time of synthesis in solid state is 8h~18h in the step (2).
Preferably, it between the step (1) and the step (2), further includes：Raw material is compressed to sheet, so that
Li in raw material2S、M2Sa、P2S5Ingredient contact is more close, and reaction is more abundant.
It is another aspect of this invention to provide that a kind of all-solid-state battery is additionally provided, the solid electrolytic of the all-solid-state battery
The material of matter layer is above-mentioned cubic phase sulfide.
In general, by the above technical scheme conceived by the present invention compared with prior art, have below beneficial to effect
Fruit：
1st, the present invention is by by the sulfide M of Group IIIA or IVA races element2SaReplace the part P in sulfide2S5, can make
The sulfide prepared is still maintained cubic phase at room temperature, while has the ionic conductivity of more than 0.31mS/cm；
2nd, the Li that the present invention synthesizes7+yMxP1-xS6Quenching processing is not needed to, so as to simplify preparation process, has saved production
Cost；Solid electrolyte is more suitable as all-solid-state battery.
Description of the drawings
Fig. 1 is Li of the present inventionyMxP1-xS6Typical crystal structure；
Fig. 2 is 5-8 of the embodiment of the present invention and the XRD spectrums of comparative example 1；
Fig. 3 is the XRD spectrums of the embodiment of the present invention 10 at different temperatures；
Fig. 4 is Li in the embodiment of the present invention 107.2Ge0.2P0.8S6Cyclic voltammetry curve；
Fig. 5 is Li in the embodiment of the present invention 107.2Ge0.2P0.8S6The all-solid-state battery made as solid electrolyte fills
Discharge curve.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is 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 cubic phase sulfide provided by the invention is LiyMxP1-xS6；Wherein, the Group IIIAs element such as M B, Al,
It is or one or more in the IVA such as Si, Ge and Sn races element；Wherein, M is Group IIIA or IVA races element, and chemical valence is+a；
When M is Group IIIA element, a=3；When M is IVA races element, a=2,0<X≤0.4, y=7+5x-ax；
The crystal structure of the cubic phase sulfide belongs to F-43m space groups, and P/M atoms are formed by isolated in the structure
(P/M)S4Tetrahedron forms skeleton structure, and Li ions are randomly distributed in remaining tetrahedral interstice, as shown in Figure 1.Cause
This is in the XRD spectrum that the Alpha-ray X-ray diffraction measures of CuK is used to obtain, and the cubic phase sulfide is at least in following angles of diffraction
2θ：15.44°±0.50°、17.84°±0.50°、25.35°±0.50°、29.82°±0.50°、31.16°±0.50°、
39.45 ° ± 0.50 °, show diffraction maximum at 44.57 ° of ± 0.50 °, 39.45 ± 0.50 ° ° and 47.48 ° ± 0.50 ° of degree.
Since in cubic phase sulfide, M element is instead of part P element, it is suppressed that cubic phase sulfide is at room temperature
It is changed into reduction of the tetragonal phase so as to cause conductivity at room temperature；But as x >=0.4, due to the limitation of crystal structure, meeting
The cubic phase sulfide of generation is caused to contain Li2The impurity such as S reduce the ionic conductivity of material instead；And the atom of M element is got over
Greatly, the generation of impurity is more apparent, and therefore, x is preferably 0.1~0.3.Since the cubic phase sulfide remains to keep vertical at normal temperatures
Square phase argyrodite type structure, conductivity at room temperature are 0.31mS/cm~1.31mS/cm, can be as all-solid-state battery
Solid electrolytic layer.
The preparation method of above-mentioned cubic phase sulfide is：By Li2S、M2Sa、P2S5With y:x:The molar ratio of (1-x) is in inertia
Atmosphere lower-weighing, and uniformly mix, raw material is subjected to synthesis in solid state 8h~18h under 400 DEG C~650 DEG C of oxygen free condition, with
Exempt from reactant and the oxygen in air or reaction of moisture generation impurity, until reaction completely, generates LiyMxP1-xS6；Oxygen free condition
Can be the inert gases such as vacuum or nitrogen, argon gas less than 100Pa.
And in raw material Li2S-M2Sa- P2S5System in there are various structures crystalline phase, uniform batch mixing is particularly significant,
Batch mixing unevenness causes the inconsistent of component, easily generates impurity；Have in mixing process also along with the thinning process of raw material simultaneously
Conducive to the synthesis of later stage sulfide electrolyte；Mixed uniformly method can select the mechanical grindings such as vibromill, turbine grinding, ball milling
Mill method；It, can be with the rotating speed ball milling 15h of 220r/min~320r/min~for 24 hours such as when being mixed with ball grinding method；It is uniformly mixed
After conjunction, also using equipment such as powder tablet press machines by raw material compression moulding, so that the Li in raw material2S、M2Sa、P2S5Into tap
Tactile more close, reaction is more abundant；
High temperature is conducive to the preparation reaction of sulfide solid electrolyte, improves the crystallinity of crystallization based material, and then improves
The ionic conductivity of sulfide solid electrolyte；However excessively high temperature easily lacks sulfide solid electrolyte production sulphur vacancy
It falls into.Therefore the temperature of synthesis in solid state is preferably 450 DEG C~500 DEG C.Embodiment 1
By Li in the glove box of argon gas protection2S、M2Sa、P2S5With (7+5x-ax):x:The molar ratio weighing of (1-x),
And it mixes as raw material；In the present embodiment, chemical valences of a for M, M B, x 0.1；
Raw material and zirconia ball are packed into the ball grinder of the zirconia substrate of capacity, container is sealed, with 220r/min's
Rotating speed carries out ball mill mixing, obtains mixed-powder afterwards for 24 hours；
By mixed-powder in glove box, take out, and 150MPa pressure formings under powder tablet press machine, be put into glass/
In quartz ampoule, vacuum degree is evacuated to less than 100Pa, sealing is put into Muffle furnace.The heating rate of Muffle furnace for 100 DEG C/it is small
When, solid phase reaction is carried out at 400 DEG C 18 hours, natural cooling cooling obtains product Li later(7+5x-ax)MxP1-xS6, this implementation
In example, product Li7.2B0.1P0.9S6。
In glove box, product is taken out from sealed glass tube, broken finely ground in mortar, it is 20 μm~50 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, forms the electricity of diameter 10mm
Solve matter piece.It places bronze end respectively on electrolyte sheet two sides, bronze end is made to be uniformly dispersed in electrolyte sheet surface, 360MPa pressures
It is molded under power, forms blocking electrode.Blocking electrode is put into the closed electrochemical cell of argon gas protection at 25 DEG C, is handed over
Flow impedance is tested.The amplitude for applying alternating current is 20mV, frequency range 10Hz~10MHz.Measuring its conductivity at room temperature is
0.60mS/cm。
To simplify the description, the preparation parameter of embodiment 2- embodiments 20 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 20 of table
Embodiment 21
First, in the glove box of argon gas protection, by Li2S、B2S3、Al2S3、P2S5With 7.4:0.1:0.1:0.9 mole
Than weighing, and mix as raw material；
Raw material and zirconia ball are packed into the ball grinder of the zirconia substrate of capacity, container is sealed, with 300r/min's
Rotating speed carries out ball mill mixing, and mixed-powder is obtained after 18h；
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
400 DEG C carry out solid phase reaction 18 hours, and natural cooling cooling obtains product Li7.4B0.1Al0.1P0.8S6。
In glove box, product is taken out from sealed glass tube, broken finely ground in mortar, it is 20 μm~50 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.It places bronze end respectively on electrolyte sheet two sides, 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~10MHz.Measure its room-temperature ion
Conductivity is 0.66mS/cm.
Comparative example 1
According to Li7PS6Composition formula, with 7 in the glove box of argon gas protection:1 molar ratio Li2S, P2S5It weighs and mixes respectively
Cooperate 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 Li7PS6。
In glove box, product is taken out from sealed glass tube, broken finely ground in mortar, it is 20 μm~50 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.It places bronze end respectively on electrolyte sheet two sides, 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~10MHz.Measure its room-temperature ion
Conductivity is 0.03mS/cm.
Analysis of experimental results
(1) measure of conductivity
The ionic conductivity of embodiment 2- embodiments 20 and comparative example 1 in embodiment 1, embodiment 21 and table 1 are carried out
It compares, it can be seen that compared with comparative example 1, Li7+xGexP1-xS6Be sulfide solid electrolyte show it is relatively high from
Electron conductivity.
(2) X-ray diffraction measure
The Alpha-ray X-ray diffraction measures of CuK are carried out to embodiment 5- embodiments 8, find EXAMPLE Example 5- embodiments
8 have 2 θ=15.44 ° ± 0.50 °, 17.84 ± 0.50 °, 25.35 ° ± 0.50 °, 29.82 ° ± 0.50 °, 31.16 ° ±
0.50 °, 39.45 ° ± 0.50 °, 44.57 ° ± 0.50 °, the peak that occurs of 47.48 ° ± 0.50 ° of position, are originated from 111,
The diffraction maximum of 200,220,311,222,311,422,511 crystal faces illustrates to generate cubic phase argyrodite type Li7+xSixP1- xS6；Wherein, 25.35 ° ± 0.50 °, 29.82 ° ± 0.50 °, 31.16 ° ± 0.50 ° of peak it is relatively strong.
Peak in comparative example 1 is relative to embodiment Li7+xSixP1-xS6In peak there are swarming phenomenon, this is because cube
Mutually switch to orthorhombic phase to cause.In embodiment 5-8, as the amount for mixing Si elements increases, Li2S impurity starts to occur.From this two
From the aspect of x preferably be 0<x≤0.4.
(3) object phase heat stability testing
Determine the electrolyte (Li in embodiment 107.2Ge0.2P0.8S6) under room temperature (25 DEG C) and low temperature (- 60 DEG C)
X-ray diffraction spectrum, the results are shown in Fig. 3.It can be found that even if at -60 DEG C, cubic phase Li7.2Ge0.2P0.8S6Also do not occur
Phase transition generates tilted direction, can stablize holding cube showing the sulfide solid electrolyte of the present invention even if at -60 DEG C
Phase, so as to high ionic conductivity.
(4) electrochemical stability
To the sulfide solid electrolyte material (Li obtained in embodiment 107.2Ge0.2P0.8S6) carry out cyclic voltammetric survey
Amount, to evaluate its electrochemical stability.The monocell of Li/ sulfide solid electrolyte materials/Au configurations is as the single electricity of evaluation
Pond.In the evaluation and test monocell, Li is as reference electrode and to electrode, and Au is as working electrode.Electrical potential scan rate is
1mV/s, potential range are -0.5V to 5V.As a result it is shown in Figure 4.As shown in Figure 4, confirm in addition to corresponding to Li near 0V
Dissolving/precipitation oxidationreduction electric current outside, there is no the redox electric current of electrolyte to be observed.Therefore, the solid-state
Electrolyte has to the electrochemical window of 5V.
(5) all-solid-state battery charge and discharge
Sulfide solid electrolyte (the Li that will be obtained in embodiment 107.2Ge0.2P0.8S6) with the LiNbO of thickness 10nm3Cladding
LiCoO2With LiCoO2:Sulfide solid electrolyte material=7:3 weight ratio is mixed, and obtains anode composite material.It connects
It, using Li-In alloys as negative material, sulfide solid electrolyte Li7.2Ge0.2P0.8S6Solid electrolyte layer is formed, is made
All-solid-state battery.For the all-solid-state battery of preparation, constant current charge-discharge measurement carries out in the range of 1.9V to 3.6V, charge and discharge
Multiplying power is 0.1C, and temperature is 25 DEG C.The results are shown in Figure 5.
To remaining embodiment crop phase heat stability testing, electrochemical stability test and all-solid-state battery charge and discharge electrical measurement
Examination, can also obtain result similar to Example 3.
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 any modification, equivalent and improvement made all within the spirits and principles of the present invention etc., should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of cubic phase sulfide, which is characterized in that its chemical formula is LiyMxP1-xS6；Wherein, M is Group IIIA or IVA races member
Element, chemical valence be+a, 0<X≤0.4, y=7+5x-ax.
2. cubic phase sulfide as described in claim 1, which is characterized in that one kind or more in M B, Al, Si, Ge or Sn
Kind.
3. cubic phase sulfide as described in claim 1, which is characterized in that 0.1≤x≤0.3.
4. cubic phase sulfide as described in claim 1, which is characterized in that ion of the cubic phase sulfide at 25 DEG C
Conductivity is 0.31mS/cm~1.31mS/cm.
5. the preparation method of cubic phase sulfide as described in any one in claim 1-4, which is characterized in that including following step
Suddenly：
(1) by Li2S、M2Sa、P2S5With y:x:The molar ratio of (1-x) is uniformly mixed as raw material；
(2) raw material under 400 DEG C~650 DEG C of oxygen free condition is subjected to synthesis in solid state, obtains LiyMxP1-xS6；Wherein, 0<x≤
0.4, y=7+5x-ax.
6. preparation method as claimed in claim 5, which is characterized in that mixed uniformly method is in the step (1), will
Li2S、M2Sa、P2S5With the rotating speed ball milling 15h of 220r/min~320r/min~for 24 hours after mixing.
7. preparation method as claimed in claim 5, which is characterized in that the temperature of synthesis in solid state is 450 DEG C in the step (2)
~500 DEG C.
8. preparation method as claimed in claim 5, which is characterized in that in the step (2) time of synthesis in solid state for 8h~
18h。
9. preparation method as claimed in claim 5, which is characterized in that between the step (1) and the step (2), also
Including：Raw material is compressed to sheet.
10. a kind of all-solid-state battery of cubic phase sulfide described in any one in 1-4 including claim.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| WO2021194262A1 (en) * | 2020-03-27 | 2021-09-30 | Samsung Sdi Co., Ltd. | Solid ion conductor compound, solid electrolyte including the same, electrochemical cell including the same, and method of preparing the same |
| CN113937351A (en) * | 2021-10-08 | 2022-01-14 | 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） | Geranite type sulfide lithium ion solid electrolyte and preparation method and application thereof |
| JP2022041968A (en) * | 2020-08-31 | 2022-03-11 | 三星エスディアイ株式会社 | Sulfurized solid electrolyte for all-solid-state secondary battery, manufacturing method of sulfurized solid electrolyte, and all-solid-state secondary battery including sulfurized solid electrolyte |
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| CN114728803A (en) * | 2019-11-20 | 2022-07-08 | 索尔维公司 | Preparation method of lithium thiophosphate |
| WO2021194262A1 (en) * | 2020-03-27 | 2021-09-30 | Samsung Sdi Co., Ltd. | Solid ion conductor compound, solid electrolyte including the same, electrochemical cell including the same, and method of preparing the same |
| US11799129B2 (en) | 2020-03-27 | 2023-10-24 | Samsung Sdi Co., Ltd. | Solid ion conductor compound, solid electrolyte including the same, electrochemical cell including the same, and method of preparing the same |
| CN111908437A (en) * | 2020-08-21 | 2020-11-10 | 中南大学 | Preparation method of sulfide solid electrolyte |
| JP2022041968A (en) * | 2020-08-31 | 2022-03-11 | 三星エスディアイ株式会社 | Sulfurized solid electrolyte for all-solid-state secondary battery, manufacturing method of sulfurized solid electrolyte, and all-solid-state secondary battery including sulfurized solid electrolyte |
| JP7284225B2 (en) | 2020-08-31 | 2023-05-30 | 三星エスディアイ株式会社 | Sulfide-based solid electrolyte for all-solid secondary battery, method for producing the same, and all-solid secondary battery including the same |
| US11955601B2 (en) | 2020-08-31 | 2024-04-09 | Samsung Sdi Co., Ltd. | Sulfide solid electrolyte for all-solid secondary battery, method of preparing same, and all-solid secondary battery including the same |
| CN113937351A (en) * | 2021-10-08 | 2022-01-14 | 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） | Geranite type sulfide lithium ion solid electrolyte and preparation method and application thereof |
| CN113937351B (en) * | 2021-10-08 | 2023-09-22 | 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） | Sulfur silver germanium ore type sulfide lithium ion solid electrolyte and preparation method and application thereof |
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