CN109888376B - Sulfide sodium ion solid electrolyte and preparation method thereof - Google Patents
Sulfide sodium ion solid electrolyte and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a sulfide sodium ion solid electrolyte and a preparation method thereof, wherein the chemical formula of the sulfide sodium ion solid electrolyte is Na4‑x‑z[Sn1‑yMy]1‑xNxS4‑zXzWherein M is at least one of Si or Ge, N is at least one of P or Sb, and X is at least one of Cl, Br and I; x is more than or equal to 0 and less than or equal to 0.6, y is more than or equal to 0.30 and less than or equal to 0.35, and z is more than or equal to 0 and less than or equal to 0.1. The crystal structure of the sulfide sodium ion solid electrolyte has I41Space group of/acd, isolated [ Sn/M]S4And [ Sn/M/N]S4The tetrahedra form the framework, and sodium ions fill the six unoccupied crystal sites. When x is 0, the ionic conductivity is more than 10‑ 5S/cm；0<When x is less than or equal to 0.6, the ionic conductivity is 10‑4S/cm～10‑3Of the order of S/cm. The solid electrolyte material provided by the invention has high ionic conductivity and good air stability, and the material has wide sources of raw materials used in synthesis, relatively low price and certain advantages in use cost.
Description
Technical Field
The invention relates to the field of all-solid-state sodium ion batteries, in particular to a sulfide sodium ion solid electrolyte and a preparation method thereof.
Background
Lithium batteries have been rapidly developed since their discovery in 1970. Among them, lithium ion batteries first developed by snoy corporation in 1990 have been widely used in portable electronic devices such as mobile phones and computers due to their advantages of high energy density, long cycle life, high operating voltage, and no memory effect. Along with the demand of lithium ion batteries in power automobiles and energy storage systems, the limitation of the storage capacity of lithium resources in the earth crust makes the lithium ion batteries tested in the aspects of cost and popularization range, and the development of novel secondary batteries becomes an inevitable trend.
The sodium element and the lithium element are in the same main group and have similar physical and chemical properties. In recent years, development of a secondary battery using sodium instead of lithium has started to be completely open and remarkable in effect. The anode and cathode electrode materials are various in types, and a mature research system is formed. Similar to lithium ion batteries, the safety performance of electrolyte materials as an important component of sodium ion batteries is always controversial due to the characteristics of liquid state and organic combustibility, and the rise of fast ion conductors seems to provide a trigger for improving the problem. The development of sodium ion solid electrolyte is a necessary link for realizing a solid sodium ion battery, and becomes a key and point of research.
Since 1970s, the research on inorganic sodium ion solid electrolytes mainly includes Na-Beta-Al2O3Solid electrolytes, NACICON type solid electrolytes, sodium sulfide ion solid electrolytes, and sodium borohydride ion solid electrolytes. The sulfide sodium ion solid electrolyte has the advantages of high room-temperature ionic conductivity, simple preparation, small grain boundary impedance, easy forming and the like, and has attracted people's attention in recent years. Solid-state batteries based on solid-state electrolytes have become an important development direction for future large-scale industrial energy storage. In the solid-state sodium battery, the ionic conductivity, stability, compatibility with electrode materials and the like of electrolyte materials are key factors for the success of the solid-state sodium ion battery technology. Compared with all-solid-state lithium ion batteries, the high ionic conductivity (> 10) for sodium ion all-solid-state batteries is reported at present-3S/cm), and many sulfide sodium ion solid electrolytes are often sensitive to air, and exposure to air easily generates sulfide hydrogen and causes failure of the solid electrolyte, which will limit the selection and application of sulfide solid electrolytes in all-solid-state sodium ion battery research.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problems that the prior sulfide solid electrolyte has few types with high ion conductivity, is sensitive to air and is easy to generate sulfide hydrogen when exposed to the air, so that the solid electrolyte is ineffective.
To achieve the above objects, in one aspect, the present invention providesA sodium sulfide ion solid electrolyte with a chemical formula of Na4-x-z[Sn1-yMy]1-xNxS4-zXzWherein M is at least one of Si or Ge, N is at least one of P or Sb, and X is at least one of Cl, Br or I; x is more than or equal to 0 and less than or equal to 0.6, y is more than or equal to 0.30 and less than or equal to 0.35, and z is more than or equal to 0 and less than or equal to 0.1.
Optionally, the crystal structure of the sulfide sodium ion solid electrolyte has I41Space group of/acd, isolated [ Sn/M]S4And [ Sn/M/N]S4The tetrahedra form the framework, and sodium ions fill the six unoccupied crystal sites.
Optionally, when x is 0, the ionic conductivity of the sodium sulfide ion solid electrolyte is greater than 10-5S/cm。
Alternatively, 0<When x is less than or equal to 0.6, the ion conductivity of the sulfide sodium ion solid electrolyte is 10-4S/cm～10-3Of the order of S/cm.
Alternatively, at 0< z ≦ 0.1, the activation energy of the sulfide sodium ion solid electrolyte is less than the activation energy at z ≦ 0.
On the other hand, the invention provides a preparation method of a sulfide sodium ion solid electrolyte, which comprises the following steps:
step (1), adding Na2S、MS2(M＝Ge,Si)、SnS2、P2S5、Sb2S3S, NaX (X ═ Cl, Br or I) as Na4-x-z[Sn1-yMy]1-xNxS4-zXzThe molar ratio of the raw materials is evenly mixed to obtain mixed raw materials, N is at least one of P, Sb, x is more than or equal to 0 and less than or equal to 0.6, y is more than or equal to 0.30 and less than or equal to 0.35, and z is more than or equal to 0 and less than or equal to 0.1;
step (2), the mixed raw materials are subjected to solid phase synthesis under the anaerobic condition of 400-650 ℃ to obtain Na4-x-z[Sn1-yMy]1-xNxS4-zXz。
Optionally, the crystal structure of the sulfide sodium ion solid electrolyte has I41Space group of/acd, isolated [ Sn/M]S4And [ Sn/M/N]S4The tetrahedra form the framework, and sodium ions fill the six unoccupied crystal sites.
Optionally, the solid phase synthesis time is 8-24 h.
Optionally, the oxygen-free condition is a vacuum condition of less than 100 Pa.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) the invention provides a structural template with higher tolerance and carries out further chemical doping on the basis, which proves that the structural template is favorable for realizing the purposes of improving the ionic conductivity, the electrochemistry and the chemical stability and the like through more chemical regulation. The invention partially replaces Na by carbon family element Si or Ge element4SnS4Sn in the electrolyte can obtain a novel solid electrolyte material Na with high ionic conductivity4Sn1-yMyS4Wherein when M is Si, y is 0.33, the ion conductivity (c) is obtained>10-5S/cm) relative to Na4SnS4(10-8S/cm) of the template, 3 orders of magnitude of material with a brand new structure is promoted, and the structure can be used as a template. The nitrogen group elements P and Sb are further introduced into the structural template, and the ion conductivity can be further improved by two orders of magnitude by introducing Na ion vacancies (>10-3S/cm) without changing the inherent crystal structure. The halogen is further introduced on the basis of the five-membered system, so that the pure structure can be still kept, and the activation energy of a synthesized sample can be reduced.
The solid electrolyte material has high ionic conductivity, flexible control of chemical proportion and good air stability, which is favorable for solving the problems that the sulfide solid electrolyte in the prior art has few types and is sensitive to air, and the like, and can effectively expand the selection range of the sulfide sodium ion solid electrolyte in the preparation of batteries.
(2) In the invention, Na is firstly added4SnS4Wherein part of Sn is replaced by Si or Ge element, when one third of Sn is usedWhen Si is substituted for Sn, a compound having I4 is obtained1Na of/acd space group4Sn0.67M0.33S4The structure has higher structure tolerance and can be further doped or substituted as a structure template. According to the chemical formula Na4-x[Sn0.67M0.33]1-xNxS4Further introducing nitrogen group elements P and Sb, wherein x is more than or equal to 0 and less than or equal to 0.6, the range of x is preferably more than or equal to 0.2 and less than or equal to 0.4, and the space group capable of ensuring high ionic conductivity of the final N production is I41Na of/acd4-x[Sn0.67M0.33]1-xNxS4But also can prevent the excessive N element from generating impurities; further introducing halogen on the basis of five-membered to obtain Na4-x-z[Sn1-yMy]1-xNxS4-zXzThe pure structure can be maintained and the activation energy of the resulting electrolyte sample can be reduced.
(3) The invention has crystal phases with various structures, uniform mixing is very important, and nonuniform mixing causes inconsistency of components and is easy to generate impurities; meanwhile, the refining process of the raw materials is also accompanied in the material mixing process, so that the synthesis of sulfide electrolyte in the later period is facilitated; the rotation speed of ball milling is 200 r/min-500 r/min during uniform mixing, and the ball milling time is 6 h-20 h, so that the raw materials are uniformly mixed.
Drawings
FIG. 1 shows Na provided by the present invention4-x-z[Sn1-yMy]1-xNxS4-zXz(x ═ 0.3, y ═ 0.33, and z ═ 0) schematic crystal structure;
FIG. 2 is a schematic comparison of the XRD of examples 1, 3, 6, 8, 9 of the present invention and that of comparative example 1;
FIG. 3 is a schematic XRD of example 1 of the present invention at 24 hours of air seed exposure;
fig. 4 is a schematic view of the charge and discharge curves of the all-solid-state sodium battery as a solid electrolyte in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Aiming at the defects or improvement requirements of the prior art, the invention provides a sodium ion solid electrolyte with high ionic conductivity and good air stability and a preparation method thereof, and provides a chance for solving the problems that in the prior art, a sulfide solid electrolyte is sensitive to air and is easy to generate sulfide hydrogen when exposed in the air, so that the solid electrolyte is ineffective and the like. In addition, the raw materials used in the synthesis of the material have wide sources and relatively low price, and have certain advantages in use cost.
To achieve the above objects, according to one aspect of the present invention, there is provided an air-stable sulfide sodium ion solid electrolyte having a chemical formula of Na4-x-z[Sn1-yMy]1-xNxS4-zXzWherein M is at least one of Si or Ge, N is at least one of P or Sb, and X is at least one of Cl, Br and I; x is more than or equal to 0 and less than or equal to 0.6, y is more than or equal to 0.30 and less than or equal to 0.35, and z is more than or equal to 0 and less than or equal to 0.1. Further, the crystal structure of the sulfide sodium ion solid electrolyte has I41Space group of/acd, isolated [ Sn/M]S4Or [ Sn/M/N]S4The tetrahedra form the framework, and sodium ions fill the six unoccupied crystal sites.
Further, the sulfide sodium ion solid electrolyte is used for preparing an all-solid-state battery.
Further, in terms of price and structural purity, M is preferably Si, and y is preferably 0.33.
Further, from the viewpoint of chemical stability, conductivity advantage, N is preferably P, and the range of x is preferably 0. ltoreq. x.ltoreq.0.6, and the range of x is more preferably 0.2. ltoreq. x.ltoreq.0.4.
According to another aspect of the present invention, there is provided a method for preparing an air-stable sulfide sodium ion solid electrolyte, comprising:
(1) na is added2S,MS,(M＝Ge,Si),SnS2,P2S,(N＝P,Sb),Sb2S3S, NaX, (X ═ Cl, Br, I) as Na4-x-z[Sn1-yMy]1-xNxS4-zXzUniformly mixing the raw materials according to the molar ratio to obtain a mixed raw material;
(2) carrying out solid phase synthesis on the mixed raw materials under the anaerobic condition of 400-650 ℃ to obtain Na4-x-z[Sn1- yMy]1-xNxS4-zXzThe crystal structure of which satisfies I41A/acd space group; the oxygen-free condition is a vacuum condition of less than 100 Pa.
Wherein M is at least one of Si or Ge, N is at least one of P or Sb, and X is at least one of Cl, Br and I; x is more than or equal to 0 and less than or equal to 0.6, y is more than or equal to 0.30 and less than or equal to 0.35, and z is more than or equal to 0 and less than or equal to 0.1.
Further, the time of solid phase synthesis is 8-24 h. The high temperature is beneficial to the preparation reaction of the sulfide solid electrolyte, and the crystallinity of the crystalline material is improved, so that the ionic conductivity of the sulfide solid electrolyte is improved; however, excessive temperatures tend to cause the sulfide solid electrolyte to produce sulfur vacancy defects. Therefore, the temperature for solid phase synthesis is preferably 450 ℃ to 550 ℃.
Further, the method for uniformly mixing in the step (1) is planetary ball milling or vibration ball milling. Preferably, the sample obtained by planetary ball milling has better crystallinity and high ionic conductivity.
Further, when the materials are uniformly mixed in the step (1), the rotation speed of ball milling is 200 r/min-500 r/min, and the ball milling time is 6 h-20 h.
Further, the method also comprises the following steps between the step (1) and the step (2): the mixed raw materials are pressed into sheets, so that the components in the mixed raw materials are contacted more closely and the reaction is more sufficient.
In addition, Na is4-x-z[Sn1-yMy]1-xNxS4-zXzIs a novel crystal structure, and the crystal structure belongs to I41A group of/acd spaces, the junctionIn which the Sn/M atoms form isolated [ Sn/M ]]S4The tetrahedron forms a framework structure, with Sn/M/N atoms forming isolated [ Sn/M/N]S4The tetrahedra form the framework structure, while the Na ions are randomly distributed in the remaining tetrahedral and octahedral gaps, as shown in fig. 1.
Accordingly, in an XRD pattern obtained by X-ray diffraction measurement using CuK α rays, at least peaks appear at positions of diffraction angles 2 θ of 11.10 ° ± 0.50 °, 12.80 ° ± 0.50 °, 14.70 ° ± 0.50 °, 18.18 ° ± 0.50 °, 21.32 ° ± 0.50 °, 22.38 ° ± 0.50 °, 25.16 ° ± 0.50 °, 25.75 ° ± 0.50 °, 26.76 ° ± 0.50 °, 28.46 ° ± 0.50 °, 31.88 ° ± 0.50 °, 32.62 ° ± 0.50 °, 33.80 ° ± 0.50 °, 35.31 ° ± 0.50 °, 37.04 ° ± 0.50 °, 38.69 ° ± 0.50 °, 40.02 ° ± 0.50 °, 42.25 ° ± 0.50 °, 43.18 ° ± 0.50 °, wherein a relatively strong peak is present at 18.18.18 ° ± 0.04 ° ± 0.50 °.
Firstly, the invention replaces Na with M element (Si or Ge)4SnS4Part of Sn element can obtain a structure different from Na4SnS4The novel solid electrolyte material of (1), wherein in the formula Na4-x[Sn1-yMy]1-xNxS4When M is Si, x is 0 and y is 0.33, Na is obtained4Sn0.67M0.33S4Ion conductivity thereof (>10-5S/cm) relative to Na4SnS4(10-8S/cm) is improved by 3 orders of magnitude, and meanwhile, the material has a brand new structure which can be used as a template to further introduce a nitrogen group element P or Sb, and Na is introduced+Vacancies further increase ionic conductivity by two orders of magnitude (>10-3S/cm) without changing the inherent crystal structure. In addition, the sulfide solid electrolyte has good air stability. Further introducing halogen on the basis of five-membered to obtain Na4-x-z[Sn1-yMy]1-xNxS4-zXzThe pure structure can be maintained and the activation energy of the resulting electrolyte sample can be reduced.
The substitution of the M element can promote the generation of a new structure, and the new structure with high ionic conductivity is generated, but when x is too small, the essential change of the structure cannot be generated sufficiently, and when y is too large, other impurities are easily generated; therefore, y is preferably 0.33.
Further doping of N element can introduce Na+Vacancies, which improve the ionic conductivity of the material, but x is preferably 0.2. ltoreq. x.ltoreq.0.4 because of the limitation of the crystal structure, and impurities are easily generated when the value of x is too large.
Further doping of the element X lowers the crystal activation energy and thus the temperature-dependent change of the material, but due to the limitation of the crystal structure, when the value of z is too small, the change is too weak, and when the value of z is too large, impurities are easily generated, so that z is preferably 0.1 or less.
The preparation method of the cubic phase sulfide comprises the following steps: mixing Na2S、SnS2、P2S5、Sb2S3、SiS2、GeS2S, NaX (X ═ Cl, Br, I) with Na4-x-z[Sn1-yMy]1-xNxS4-zXzThe molar ratio of the components is weighed in inert atmosphere, evenly mixed and then calcined for 8 to 24 hours at 400 to 650 ℃ under the vacuum degree of less than 100Pa so as to prevent the reaction of the reactants and oxygen or moisture in the air from generating impurities.
While in the Na-Sn-M-N-S-X system, crystal phases with various structures exist, uniform mixing is very important, and nonuniform mixing causes inconsistency of components and is easy to generate impurities; meanwhile, the refining process of the raw materials is also accompanied in the material mixing process, so that the synthesis of sulfide electrolyte in the later period is facilitated; the method of uniform mixing can be selected from mechanical grinding methods such as vibration grinding, turbine grinding, ball milling and the like; for example, when the mixture is mixed by a ball milling method, the mixture can be ball milled for 6 to 20 hours at a rotating speed of 200 to 500 r/min.
The high temperature is beneficial to the preparation reaction of the sulfide solid electrolyte, and the crystallinity of the crystalline material is improved, so that the ionic conductivity of the sulfide solid electrolyte is improved; however, excessive temperatures tend to cause the sulfide solid electrolyte to produce sulfur vacancy defects. The temperature of calcination is therefore preferably from 450 ℃ to 550 ℃.
Example 1
Under argonThe glove box is filled with Na2S、P2S5、SnS2、SiS2With Na3.7[Sn0.67Si0.33]0.7P0.3S4Weighing the components according to the molar ratio, and mixing the components to obtain raw materials;
the raw materials and zirconia balls are put into a ball milling tank with a zirconia substrate, the container is sealed, ball milling and mixing are carried out at the rotating speed of 360r/min, and mixed powder is obtained after 18 hours;
and taking out the mixed powder in a glove box, forming under the pressure of 150MPa by using a powder tablet press, putting into a glass/quartz tube, vacuumizing until the vacuum degree is less than 100Pa, sealing, and putting into a muffle furnace. The temperature rise speed of the muffle furnace is 100 ℃/h, then solid phase reaction is carried out for 24h at 550 ℃, natural cooling is carried out, and the product Na is obtained4-x[Sn1-yMy]1-xNxS4In this example, the product is Na3.7[Sn0.67Si0.33]0.7P0.3S4。
The resultant was taken out from the sealed glass tube in a glove box and crushed and ground in a mortar to obtain a powdery sample having a particle size of 10 to 20 μm. A predetermined amount of a sample was weighed in a glove box and put in a PET tube having an inner diameter of 10mm, and the sample was sandwiched vertically by stainless steel powder molding tools and pressed by a uniaxial press under a pressure of 160MPa to form an electrolyte sheet having an arbitrary thickness of 10mm in diameter. And respectively placing gold powder on two surfaces of the electrolyte sheet to uniformly disperse the gold powder on the surface of the electrolyte sheet, and forming under the pressure of 360MPa to form the blocking electrode. The blocking electrode was placed in an argon-protected closed electrochemical cell at 25 ℃ for ac impedance testing. The amplitude of the applied alternating current is 20mV, and the frequency range is 10 Hz-1 MHz. The room-temperature ionic conductivity of the conductive paste is 1.3 mS/cm.
Comparative example 1
According to Na4SnS4Composition formula, Na is respectively weighed in an argon-protected glove box2S，SnS2And mixing as raw materials;
the raw materials and zirconia balls are put into a ball milling tank with a zirconia substrate, the container is sealed, ball milling and mixing are carried out at the rotating speed of 360r/min, and mixed powder is obtained after 18 hours;
and taking out the mixed powder in a glove box, forming the mixed powder under a powder tablet press, putting the formed mixed powder into a glass/quartz tube, vacuumizing until the vacuum degree is less than 100Pa, sealing, and putting the sealed mixed powder into a muffle furnace. The temperature rise speed of the muffle furnace is 100 ℃/h, then solid phase reaction is carried out for 10h at 550 ℃, natural cooling and temperature reduction are carried out, and a product Na is obtained4SnS4。
The resultant was taken out from the sealed glass tube in a glove box and crushed and ground in a mortar to obtain a powdery sample having a particle size of 10 to 20 μm. A predetermined amount of a sample was weighed in a glove box and put in a PET tube having an inner diameter of 10mm, and the sample was sandwiched vertically by stainless steel powder molding tools and pressed by a uniaxial press under a pressure of 160MPa to form an electrolyte sheet having an arbitrary thickness of 10mm in diameter. And respectively placing gold powder on two surfaces of the electrolyte sheet to uniformly disperse the gold powder on the surface of the electrolyte sheet, and forming under the pressure of 360MPa to form the blocking electrode. The blocking electrode was placed in an argon-protected closed electrochemical cell at 25 ℃ for ac impedance testing. The amplitude of the applied alternating current is 20mV, and the frequency range is 10 Hz-1 MHz. The room temperature ionic conductivity is 6.8 multiplied by 10-8S/cm. Na of newer structure4-x[Sn1-yMy]1-xNxS4Is 4 to 5 orders of magnitude lower (6.8X 10)-8S/cm vs.1.3×10-3S/cm)。
For simplicity of description, the preparation parameters of examples 2 to 20 and the properties of the product are shown in Table 1, and the parameters not shown in the table are the same as those of example 1.
Table 1 preparation parameters and product properties of example 2-example 20
Analysis of Experimental results
(1) Determination of the conductivity
Comparing the ionic conductivities of examples 1 to 20 with that of comparative example 1, it can be seen that Na having a new structure4-x[Sn1-yMy]1-xNxS4-zXzThe sulfide solid electrolyte shows relatively high ionic conductivity, and the difference is 3-5 orders of magnitude.
(2) X-ray diffraction measurement
X-ray diffraction measurement of CuK α rays was performed for examples 1 to 20, and it was found that there was a peak appearing at a position of 11.10 ° ± 0.50 °, 12.80 ° ± 0.50 °, 14.70 ° ± 0.50 °, 18.18 ° ± 0.50 °, 21.32 ° ± 0.50 °, 22.38 ° ± 0.50 °, 25.16 ° ± 0.50 °, 25.75 ° ± 0.50 °, 26.76 ° ± 0.50 °, 28.46 ° ± 0.50 °, 31.88 ° ± 0.50 °, 32.62 ° ± 0.50 °, 33.80 ° ± 0.50 °, 35.31 ° ± 0.50 °, 37.04 ° ± 0.50 °, 38.69 ° ± 0.50 °, 40.02 ° ± 0.50 °, 42.25 ° ± 0.50 °, 43.18 ° ± 0.50 °, wherein a relatively strong peak of 18.18.18 ° ± 0.04 ° ± 0.50 ° was present.
As shown in fig. 2, which is a comparative graph of XRD of examples 1, 3, 6, 8, and 9 and XRD of comparative example 1, it can be seen from fig. 2 that the diffraction peak in comparative example 1 is completely different from that of example because they have different crystal structures, which also determines their difference of 4 orders of magnitude in ionic conductivity.
(3) Air exposure stability test
Electrolyte (Na) in example 1 was measured3.7[Sn0.67Si0.33]0.7P0.3S4) The XRD pattern after 24 hours exposure to air (humidity-35%) was compared with the XRD pattern of the sample stored in the glove box after synthesis, and the results are shown in FIG. 3. It can be seen that there was no significant change in the XRD pattern after the material was exposed to air for 24 hours, indicating that it remained structurally stable in air.
(4) All-solid-state battery charging and discharging
The sulfide solid electrolyte (Na) obtained in example 3 was used3.7[Sn0.67Si0.33]0.7P0.3S4) With TiS of particle size 5um2By TiS2The sulfide solid electrolyte material is mixed according to the weight ratio of 1:1 to obtain the anode composite material. Then, Na or Na-Sn alloy is used as a negative electrode material, and a sulfide solid electrolyte Na is used3.7[Sn0.67Si0.33]0.7P0.3S4Forming a solid electrolyte layer to manufacture the all-solid-state battery. For the prepared all-solid-state battery, constant-current charge and discharge measurement is carried out in the range of 1V to 2.5V, the charge and discharge multiplying power is 0.1C, and the temperature is 25 ℃. The results are shown in FIG. 4 as TiS2As a positive electrode material, Na and Na-Sn alloy are used as a negative electrode, and the prepared example 3 is used as a solid electrolyte to assemble an all-solid-state battery, the discharge capacity of the first circle can reach 100mAh/g, and the TiS reported by the literature2The actual specific discharge capacity of the cathode material at 0.1C multiplying power is consistent, and the all-solid-state battery prepared from the sulfide solid electrolyte has good performance.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. The sulfide sodium ion solid electrolyte is characterized in that the chemical formula of the sulfide sodium ion solid electrolyte is Na4-x-z[Sn1-yMy]1-xNxS4-zXzWherein M is at least one of Si or Ge, N is at least one of P or Sb, and X is at least one of Cl, Br or I; x is more than or equal to 0 and less than or equal to 0.6, y is more than or equal to 0.30 and less than or equal to 0.35, and z is more than or equal to 0 and less than or equal to 0.1;
the crystal structure of the sulfide sodium ion solid electrolyte has I41Space group of/acd, isolated [ Sn/M]S4And [ Sn/M/N]S4The tetrahedra form the framework, and sodium ions fill the six unoccupied crystal sites.
2. According to the claimsThe sodium sulfide ion solid electrolyte according to claim 1, wherein when x is 0, the ionic conductivity of the sodium sulfide ion solid electrolyte is greater than 10-5S/cm。
3. The sulfide sodium ion solid electrolyte according to claim 1, wherein 0 is<When x is less than or equal to 0.6, the ion conductivity of the sulfide sodium ion solid electrolyte is 10-4S/cm～10-3Of the order of S/cm.
4. The sulfide sodium ion solid electrolyte according to claim 1, wherein at 0< z ≦ 0.1, the activation energy of the sulfide sodium ion solid electrolyte is less than the activation energy at z ≦ 0.
5. The preparation method of the sulfide sodium ion solid electrolyte is characterized by comprising the following steps of:
step (1), adding Na2S、MS2(M＝Ge,Si)、SnS2、P2S5、Sb2S3S, NaX (X ═ Cl, Br or I) as Na4-x-z[Sn1-yMy]1-xNxS4-zXzThe molar ratio of the raw materials is evenly mixed to obtain mixed raw materials, N is at least one of P, Sb, x is more than or equal to 0 and less than or equal to 0.6, y is more than or equal to 0.30 and less than or equal to 0.35, and z is more than or equal to 0 and less than or equal to 0.1;
step (2), the mixed raw materials are subjected to solid phase synthesis under the anaerobic condition of 400-650 ℃ to obtain Na4-x-z[Sn1- yMy]1-xNxS4-zXz；
The crystal structure of the sulfide sodium ion solid electrolyte has I41Space group of/acd, isolated [ Sn/M]S4And [ Sn/M/N]S4The tetrahedra form the framework, and sodium ions fill the six unoccupied crystal sites.
6. The method for preparing the sulfide sodium ion solid electrolyte according to claim 5, wherein the time for the solid phase synthesis is 8 to 24 hours.
7. The method for producing a sulfide sodium ion solid electrolyte according to claim 5 or 6, wherein the oxygen-free condition is a vacuum condition of less than 100 Pa.
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