CN111710902B - Glass-ceramic type sulfide electrolyte and preparation method and application thereof - Google Patents

Glass-ceramic type sulfide electrolyte and preparation method and application thereof Download PDF

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CN111710902B
CN111710902B CN202010486758.6A CN202010486758A CN111710902B CN 111710902 B CN111710902 B CN 111710902B CN 202010486758 A CN202010486758 A CN 202010486758A CN 111710902 B CN111710902 B CN 111710902B
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ceramic type
sulfide electrolyte
type sulfide
lithium metal
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孙学良
赵斐鹏
张淑敏
梁剑文
王建涛
赵尚骞
杨容
张立
黄欢
黄倬
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University of Western Ontario
China Automotive Battery Research Institute Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
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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
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention provides a glass-ceramic type sulfide electrolyte, a preparation method and application thereof, wherein the glass-ceramic type sulfide electrolyte has a composition formula of Li3+xP1‑xSnxS4Wherein x is 0.175. ltoreq.<0.23; in the X-ray diffraction measurement using CuK α rays, a peak was observed at a position where 2 θ was 29.58 ° ± 0.50 ° and the diffraction peak intensity was I1, and a peak was also observed at a position where 2 θ was 27.33 ° ± 0.50 ° and the diffraction peak intensity was I2, and the value satisfying I2/I1 was greater than 0.5. The glass-ceramic sulfide electrolyte has good lithium ion conductivity, air stability and lithium metal compatibility, and can be applied to an all-solid-state lithium metal battery, so that the all-solid-state lithium metal battery can show very excellent cycling stability under the condition of not needing a negative electrode interlayer or protecting a lithium metal negative electrode, and great commercial application value is reflected.

Description

Glass-ceramic type sulfide electrolyte and preparation method and application thereof
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a glass-ceramic sulfide electrolyte and a preparation method and application thereof.
Background
In order to solve the problems of low energy density and low safety of the lithium ion battery based on the liquid electrolyte, researchers propose and develop a novel all-solid-state lithium metal battery based on sulfide electrolyte.
However, there are two major problems currently hindering the further development of sulfide electrolytes. First, lithium metal negative electrodes are poorly compatible. Almost all reported sulfide electrolytes are reduced by metallic lithium. In addition, lithium dendrites are also generated due to unstable lithium deposition at the sulfide/metallic lithium interface, causing the battery to fail. Secondly, air instability. Since phosphorus (P) having a positive pentavalent valence in the sulfide electrolyte has a very strong affinity for oxygen (O) in the air, the sulfide electrolyte can react with water in the air, thereby emitting toxic hydrogen sulfide (H)2S) gas.
At present, the prior art reports a class of high crystallinity sulfide electrolytes (e.g., Li-Sn-S system) based on the Li-Sn-S system4SnS4And Li2SnS3) Can exist stably in the air, but the room temperature ionic conductivity is only 10-5The S/cm level, which is difficult to apply. Sulfide electrolytes with higher ionic conductivity have also been reported, but have poor stability to metallic lithium. Therefore, the synthesis has good room temperature ionic conductivity (not less than 10)-3S/cm) while having good lithium metal compatibility and good air stability is a significant challenge.
Disclosure of Invention
The invention provides a glass-ceramic sulfide electrolyte and a preparation method and application thereof, and the lithium ion conductivity, the air stability and the lithium metal compatibility of the electrolyte are improved by doping tin element which is isovalent to phosphorus element, so that the electrolyte can be applied to an all-solid-state lithium metal battery.
In a first aspect, embodiments of the present disclosure provide a glass-ceramicThe ceramic sulfide electrolyte has a composition formula of Li3+ xP1-xSnxS4Wherein x is 0.175. ltoreq.<0.23；
In the X-ray diffraction measurement using CuK α rays, there is a peak at a position where 2 θ is 29.58 ° ± 0.50 ° and the diffraction peak intensity is I1, and there is also a peak at a position where 2 θ is 27.33 ° ± 0.50 ° and the diffraction peak intensity is I2, and the value satisfying I2/I1 is greater than 0.5, preferably greater than 0.6.
The glass-ceramic sulfide electrolyte has good room temperature lithium ion conductivity (not less than 10)-3S/cm), air stability and lithium metal compatibility.
The diffraction peak at I1 indicates that the crystal structure is biased toward tetragonal (e.g., Li)10GeP2S12Type), and the diffraction peak at I2 is believed to be structurally biased toward orthorhombic (e.g.,. beta. -Li)3PS4Type), generally, when I2/I1 is greater than 0.5, the crystal structure of the material as a whole can be considered to belong to the orthorhombic system. XRD (CuK alpha ray) test result shows that Sn doped glass ceramic type Li3+xP1-xSnxS4The electrolyte has the obvious characteristic that I2/I1 is more than 0.5, namely, the material structure at the moment can be considered to be well belonging to an orthorhombic system (namely, beta-Li)3PS4Phase). Thus, the improvement in ionic conductivity, air stability and lithium metal stability to which the present invention relates is only emphasized for β -Li-containing3PS4Phase glass-ceramic electrolytes, without involving other phase structures with high ionic conductivity (e.g. Li)10GeP2S12Etc.).
Preferably, x is 0.2, i.e., the sulfide electrolyte composition formula is Li3.2P0.8Sn0.2S4At this time, the lithium ion conductivity reached the highest value, 1.2 mS/cm.
The glass-ceramic sulfide electrolyte according to the present invention has a crystal structure of a crystal portion of (Sn/P) S4Tetrahedra and Li ions, the crystal form of which belongs to the orthorhombic system. All P, Sn, S contribute to the formation of the above tetrahedral structure. The unit cell parameters are:
Figure BDA0002519409100000021
Figure BDA0002519409100000022
preferably, the crystal structure is associated with β -Li3PS4The structure is the same.
In a second aspect, an embodiment of the present invention provides a method for preparing the above glass-ceramic sulfide electrolyte, including amorphizing a raw material composition containing lithium, phosphorus, tin, and sulfur to obtain a glassy precursor, and then partially crystallizing to obtain a target product.
Preferably, the raw material composition includes Li2S、P2S5And SnS2。
As a preferred embodiment of the present invention, the preparation method specifically comprises: with Li2S、P2S5And SnS2The raw materials are subjected to ball milling and calcining processes in sequence.
Wherein, a planetary ball mill can be adopted during ball milling; the ball milling tank can be made of zirconia, tungsten carbide or stainless steel. The calcination is preferably carried out under vacuum conditions, and can be carried out in a vacuum-sealed quartz tube or a common glass tube.
The doping amount of Sn is controlled by controlling SnS2The feed ratio of (a) is controlled.
More preferably, the ball milling time is 2-30 hours, and the rotating speed is 150-500 rpm. The main purpose is to mix the reactants homogeneously and to amorphize them.
In a preferred embodiment of the present invention, the raw materials are first ball milled at 150rpm for 2 hours to mix them uniformly, and then ball milled at 500rpm for 20 hours to amorphize them.
Further preferably, the calcining temperature is 150-300 ℃ and the calcining time is 2-10 hours. The main purpose is to partially crystallize a glassy sulfide electrolyte precursor to produce a glass-ceramic type sulfide electrolyte.
In a third aspect, embodiments of the present invention provide an application of the glass-ceramic type sulfide electrolyte in an all-solid-state metal lithium battery.
The cathode of the all-solid-state metal lithium battery is lithium metal; the positive electrode active material includes, but is not limited to, lithium cobaltate, lithium iron phosphate, lithium nickel manganese oxide, and the like.
Preferably, the all-solid-state lithium metal battery is a secondary battery and has a rechargeable cycle property.
Compared with the prior art, the invention has the beneficial effects that:
the method utilizes the aliovalent element tin to partially replace the problematic element phosphorus in the traditional glass-ceramic type sulfide electrolyte, thereby improving the air stability and the lithium metal compatibility of the sulfide electrolyte on the basis of ensuring the improvement of the lithium ion conductivity of the sulfide electrolyte. The sulfide electrolyte is applied to the all-solid-state lithium metal battery, and the all-solid-state lithium metal battery can show excellent cycling stability under the condition that a negative electrode interlayer is not needed or a metal lithium negative electrode is not needed to be protected, so that the all-solid-state lithium metal battery embodies great commercial application value.
Drawings
FIG. 1 shows glass state and glass-ceramic type Li3.2P0.8Sn0.2S4XRD contrast pattern of sulfide electrolyte
Figure BDA0002519409100000041
FIG. 2 is a glass-ceramic type Li3.2P0.8Sn0.2S4A crystal structure schematic of a sulfide electrolyte;
FIG. 3 is a glass-ceramic type Li3+xP1-xSnxS4(x ═ 0, 0.05, 0.1, 0.2, 0.4) XRD contrast pattern of sulfide electrolyte
Figure BDA0002519409100000042
FIG. 4 is a glass-ceramic type Li3+xP1-xSnxS4(x ═ 0, 0.05, 0.1, 0.15, 0.175, 0.2, 0.25, 0.3, 0.4) the room temperature ionic conductivity of the sulfide electrolyte;
FIG. 5 is a glass-ceramic type Li3.2P0.8Sn0.2S4XRD pattern of sulfide electrolyte
Figure BDA0002519409100000043
FIG. 6 (a) glass-ceramic type Li3.2P0.8Sn0.2S4Tendency of change in quality of sulfide electrolyte and comparative example in dry air; (b) glass-ceramic type Li3.2P0.8Sn0.2S4XRD contrast patterns of sulfide electrolytes before and after exposure to dry air and 5% humidity air; (c) glass-ceramic type Li3.2P0.8Sn0.2S4Arrhenius curves before and after exposure of sulfide electrolyte in a 5% humidity environment; (d) comparative example arrhenius curves before and after exposure to a 5% humidity environment;
FIG. 7 shows Li// Li3.2P0.8Sn0.2S4// Li symmetrical cell and comparative example symmetrical cell (Li// Li)3PS4Performance diagram of// Li) (room temperature, 0.1mA cm-2/0.1mAh cm-2)；
FIG. 8 shows Li// Li3.2P0.8Sn0.2S4The structure schematic diagram of the LCO all-solid-state lithium metal battery;
fig. 9 is a charge and discharge curve (room temperature, 0.05C) of the all solid-state lithium metal battery obtained in example 7;
fig. 10 is a graph showing the cycle stability (room temperature, 0.1C) of the all solid-state lithium metal battery obtained in example 7.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are not indicated as conventional products available to the manufacturer from regular distributors.
Example 1 preparation of glass-ceramic type Li3.2P0.8Sn0.2S4VulcanizationPhysical electrolyte
Mixing Li in stoichiometric ratio2S，P2S5，SnS21g of the raw materials are firstly put into a ball milling tank of zirconia, ball milling is carried out for 2 hours at the speed of 150rpm, the raw materials are uniformly mixed, then ball milling is carried out for 20 hours at the speed of 500rpm to make the raw materials amorphous, and the obtained precursor material is subjected to vacuum calcination for 4 hours at the temperature of 260 ℃ to obtain the target electrolyte material.
At an X-ray wavelength of
Figure BDA0002519409100000051
Separately measuring glass state and glass-ceramic type Li3.2P0.8Sn0.2S4The XRD pattern of the sulfide electrolyte, as shown in fig. 1, shows the evolution of the electrolyte from amorphous to glass-ceramic state during the preparation process.
Measurement of the obtained glass-ceramic type Li3.2P0.8Sn0.2S4The crystal structure of the crystalline portion in the sulfide electrolyte is shown in FIG. 2, and the results of the refinement by XRD show that the crystal structure of the crystalline portion belongs to an orthorhombic system, and the Sn portion replaces the PS portion4P in tetrahedron, a new (Sn/P) S is formed4A tetrahedral structure. All P, Sn, S contribute to the formation of the above tetrahedral structure. The unit cell parameters are:
Figure BDA0002519409100000052
example 2 glass-ceramic type Li3+xP1-xSnxS4(x ═ 0, 0.05, 0.1, 0.2, 0.4) the structure of the crystalline portion in the sulfide electrolyte changed as the amount of tin substitution increased
According to the preparation method in example 1, SnS is adjusted2The glass-ceramic type sulfide electrolytes with different tin replacement ratios are obtained according to the feeding ratio of the tin-ceramic type sulfide electrolytes. At an X-ray wavelength of
Figure BDA0002519409100000053
The XRD patterns of the obtained sulfide electrolytes are respectively measured, and the results are shown in figure 3, wherein the 2 theta on the right side in the figure is between 16 and 19As the amount of tin substitution increases, the crystal structure of the crystal portion is enlarged, the lithium ion concentration per unit crystal structure becomes larger, but the matrix phase structure still belongs to β -Li3PS4。
Example 3 glass-ceramic type Li3+xP1-xSnxS4(x ═ 0, 0.05, 0.1, 0.15, 0.175, 0.2, 0.25, 0.3, 0.4) room temperature ionic conductivity of sulfide electrolyte
Measurement of glass-ceramic type Li by AC impedance method3+xP1-xSnxS4The room temperature ionic conductivity of the sulfide electrolyte was as shown in FIG. 4, and it can be seen that when 0 is used<When x is less than or equal to 0.4, the ionic conductivity is more than 0.2mS/cm, and when x is less than or equal to 0.175<At 0.23, the ionic conductivity is above 1mS/cm, and when x is 0.2, the ionic conductivity is optimally up to 1.2mS/cm, that is, 20% is the preferred percentage of tin substitution. This is in combination with beta-Li3PS4The lattice tolerance of (a) is related to that when the doping amount is increased to a certain extent, although the crystal structure is further enlarged by further increasing the doping amount, the ion conductivity of the resulting electrolyte product is lowered by the impurity phase generated therewith.
Example 4 glass-ceramic type Li3.2P0.8Sn0.2S4The sulfide electrolyte has the obvious characteristic that I2/I1 is more than 0.5
When x is 0.2, Li3.2P0.8Sn0.2S4The ionic conductivity of the electrolyte reaches 1.2 mS/cm. From the results of X-ray measurement of CuK α (as shown in FIG. 5), a characteristic I2/I1 of greater than 0.5 was clearly observed, which indicates that the highly ion-conductive electrolyte still belongs to β -Li3PS4And (4) phase(s). By doping an appropriate amount of Sn, beta-Li can be doped3PS4The phase structure of (a) is effectively controlled so that the phase structure, which is generally regarded as relatively low ionic conductivity, can still result in excellent ionic conductivity. The reason for this is that: after appropriate Sn doping, the unit cell structure is reasonably enlarged without generating impurity phases, and the number of lithium ions available for conduction is increased.
Example 5 glass-ceramic type Li3.2P0.8Sn0.2S4Air stability of sulfide electrolyte (the test instruments include thermogravimetric analyzer: TA-SDT Q600, XRD analyzer: Bruker AXS D8, homemade constant temperature and humidity control box, etc.)
Mixing glass-ceramic type Li3.2P0.8Sn0.2S4Sulfide electrolyte and comparative example (glass-ceramic type Li)3PS4Electrolyte) were separately placed in a thermogravimetric analyzer (TGA) and exposed to dry air, and the tendency of the mass of the electrolyte with time was measured, and the results are shown in (a) of fig. 6, where Li is a glass-ceramic type3.2P0.8Sn0.2S4The mass change amplitude of the sulfide electrolyte is far less than that of glass-ceramic Li3PS4The electrolyte, i.e., the electrolyte has a high oxygen resistance (it is believed that nitrogen in dry air does not affect the sulfides).
Mixing glass-ceramic type Li3.2P0.8Sn0.2S4Sulfide electrolyte and comparative example (glass-ceramic type Li)3PS4Electrolyte) were exposed to air of 5% humidity, respectively, and glass-ceramic type Li was measured3.2P0.8Sn0.2S4XRD patterns of the sulfide electrolyte before and after subjecting it to dry air and 5% humidity air are shown in (b) of FIG. 6, and glass-ceramic type Li is measured3.2P0.8Sn0.2S4The arrhenius curves before and after exposure of the sulfide electrolyte and the comparative example to a 5% humidity environment are shown in fig. 6 (c) and (d). As can be seen from the above results, glass-ceramic type Li3.2P0.8Sn0.2S4The structure and ionic conductivity of the sulfide electrolyte did not change significantly, while the glass-ceramic type Li3PS4The ionic conductivity of the electrolyte drops sharply.
Example 6 glass-ceramic type Li3.2P0.8Sn0.2S4Lithium metal negative electrode compatibility of sulfide electrolytes
Mixing glass-ceramic type Li3.2P0.8Sn0.2S4Sulfide electrolyte and comparative example (glass-ceramic type Li)3PS4Electrolyte) were assembled into Li-Li symmetric cells, respectively, and constant current, constant capacity lithium deposition/de-deposition measurements (0.1mA cm) were performed at room temperature-2/0.1mAh cm-2) As a result, as shown in FIG. 7, it can be seen that glass-ceramic type Li3.2P0.8Sn0.2S4The sulfide electrolyte can stably perform lithium deposition/de-deposition for more than 600 hours, showing good lithium metal compatibility, while the glass-ceramic type Li of comparative example3PS4The electrolyte of the symmetrical cell was short-circuited after 146.5 hours of lithium deposition/de-deposition.
Example 7 based on glass-ceramic type Li3.2P0.8Sn0.2S4All-solid-state lithium metal battery with sulfide electrolyte
Mixing glass-ceramic type Li3.2P0.8Sn0.2S4Sulfide electrolyte as single electrolyte layer, LCO (lithium cobaltate)/Li3InCl6The positive electrode compound is a positive electrode layer, the metal lithium is a negative electrode layer, wherein the preparation process of the electrode is dry powder mixing, and no solvent is involved. The all solid-state lithium metal battery shown in fig. 8 was then obtained by layer-by-layer pressing.
The charge-discharge curve of the all solid-state lithium metal battery was measured under the conditions of 0.05C constant current charge-discharge and room temperature, and the result is shown in fig. 9; as a result of measuring the cycle stability of the all-solid-state lithium metal battery under the conditions of 0.1C constant current charge and discharge and room temperature, as shown in fig. 10, the average coulombic efficiency was maintained at 99.8% or more (the first efficiency was as high as 96.18%) during 40 consecutive charge and discharge cycles. The specific capacity is reduced from 118.4 to 100.3mAh g-1The capacity retention rate is close to 85%. From the above results, it is understood that the all-solid-state lithium metal battery can exhibit excellent cycle reversibility and cycle life at room temperature.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A glass-ceramic type sulfide electrolyte is characterized in that the composition formula is Li3+xP1-xSnxS4Wherein x is more than or equal to 0.175 and less than or equal to 0.2;
in an X-ray diffraction measurement using CuK α rays, a peak is present at a position of 2 θ =29.58 ° ± 0.50 ° and the diffraction peak intensity is I1, and also a peak is present at a position of 2 θ =27.33 ° ± 0.50 ° and the diffraction peak intensity is I2, and the value satisfying I2/I1 is greater than 0.5;
the crystal structure of the crystalline portion of the glass-ceramic type sulfide electrolyte is composed of (Sn/P) S4Tetrahedra and Li ions, the crystal form of which belongs to the orthorhombic system.
2. The glass-ceramic type sulfide electrolyte according to claim 1, wherein the value of I2/I1 is greater than 0.6.
3. The glass-ceramic type sulfide electrolyte according to claim 1, wherein x = 0.2.
4. The glass-ceramic type sulfide electrolyte according to any one of claims 1 to 3, wherein a crystal structure of a crystal portion of the glass-ceramic type sulfide electrolyte is in contact with β -Li3PS4The structure is the same.
5. The method for producing a glass-ceramic type sulfide electrolyte according to any one of claims 1 to 4, wherein the method comprises subjecting a raw material composition containing a lithium element, a phosphorus element, a tin element and a sulfur element to amorphization to obtain a glassy precursor, and then subjecting the precursor to partial crystallization to obtain the target product.
6. The preparation method according to claim 5, wherein the preparation method specifically comprises: to be provided withLi2S、P2S5And SnS2The raw materials are subjected to ball milling and calcining processes in sequence.
7. The preparation method of claim 6, wherein the ball milling time is 2-30 hours and the rotation speed is 150-500 rpm.
8. The method according to claim 6 or 7, wherein the calcination is carried out at a temperature of 150 to 300 ℃ for 2 to 10 hours.
9. Use of the glass-ceramic type sulfide electrolyte according to any one of claims 1 to 4 in an all-solid state lithium metal battery.
10. The use of claim 9, wherein the all-solid-state lithium metal battery is a secondary battery having a rechargeable cycle property.
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CN104185873A (en) * 2012-02-06 2014-12-03 丰田自动车株式会社 Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material
CN104937761A (en) * 2013-01-17 2015-09-23 国立大学法人东京工业大学 Solid electrolyte sulfide material, battery, and process for producing solid electrolyte sulfide material
WO2019239949A1 (en) * 2018-06-13 2019-12-19 三菱瓦斯化学株式会社 Lgps-based solid electrolyte and production method

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CN110085908B (en) * 2019-04-30 2021-09-17 国联汽车动力电池研究院有限责任公司 High-air-stability inorganic sulfide solid electrolyte and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN104081577A (en) * 2012-02-06 2014-10-01 丰田自动车株式会社 Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material
CN104185873A (en) * 2012-02-06 2014-12-03 丰田自动车株式会社 Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material
CN104937761A (en) * 2013-01-17 2015-09-23 国立大学法人东京工业大学 Solid electrolyte sulfide material, battery, and process for producing solid electrolyte sulfide material
WO2019239949A1 (en) * 2018-06-13 2019-12-19 三菱瓦斯化学株式会社 Lgps-based solid electrolyte and production method

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