CN111244534A - Sulfur oxide solid electrolyte, preparation method and application thereof - Google Patents

Sulfur oxide solid electrolyte, preparation method and application thereof Download PDF

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CN111244534A
CN111244534A CN202010114844.4A CN202010114844A CN111244534A CN 111244534 A CN111244534 A CN 111244534A CN 202010114844 A CN202010114844 A CN 202010114844A CN 111244534 A CN111244534 A CN 111244534A
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solid electrolyte
sulfur oxide
oxide solid
sulfur
acid
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王雪锋
王兆翔
陈立泉
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Institute of Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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 provides a sulfur oxide solid electrolyte, which contains two anions of sulfur and oxygen and has a general formula AxMySz‑uOuAlso provides a preparation method and application thereof. The electrolyte system is prepared by directly oxidizing an existing sulfide solid electrolyte with an oxidant, wherein the oxidant comprises dry air. The sulfur oxide solid electrolyte of the present invention efficiently binds sulfurThe advantages of high conductivity, excellent mechanical properties and good air and chemical stability of oxide solid electrolytes are achieved while avoiding their disadvantages. The sulfur oxide solid electrolyte enables the operation of the sulfide solid electrolyte in a dry room and the assembly of an all-solid-state battery thereof. The sulfur oxide solid electrolyte provided by the invention is expected to be applied to next-generation high-specific-energy batteries, and is applied to actual life in preference to the sulfide solid electrolyte and the oxide solid electrolyte.

Description

Sulfur oxide solid electrolyte, preparation method and application thereof
Technical Field
The invention belongs to the field of chemical power sources, and particularly relates to preparation of a sulfur oxide solid electrolyte and application of the sulfur oxide solid electrolyte in an all-solid-state battery.
Background
At present, most of commercial secondary ion batteries adopt liquid electrolyte to realize the transfer of anions and cations between a positive electrode and a negative electrode. Since the liquid electrolyte contains flammable organic solvents, such batteries have potential safety problems such as electrolyte leakage, poor thermal stability, and battery ignition or even explosion. In order to improve the safety of batteries, solid electrolytes have been used instead of liquid electrolytes to construct and realize next-generation all-solid batteries with high specific energy and high safety.
The solid electrolyte can be roughly classified into a polymer electrolyte, an inorganic ceramic electrolyte, and a composite electrolyte in which the above two are combined. The inorganic ceramic electrolyte has higher room temperature ionic conductivity than the polymer electrolyte. Inorganic ceramic electrolytes are further classified into oxide solid electrolytes and sulfide solid electrolytes. Compared with oxide solid electrolyte materials, the sulfide solid electrolyte has higher ionic conductivity and better mechanical ductility and flexibility, can be synthesized at normal temperature or low temperature (<500 ℃) to prepare a compact electrolyte sheet and a composite electrode of the electrolyte sheet and a positive electrode material and a negative electrode material by a cold pressing method. However, most sulfide solid electrolytes are sensitive to air and easily react with air to generate toxic and harmful hydrogen sulfide gas; and the electrolyte is easy to chemically react with a high-voltage oxide positive electrode material to generate byproducts which obstruct ion transmission and electron conduction, thereby increasing the polarization of the battery and deteriorating the performance of the battery; these disadvantages limit the practical application of existing sulfide solid electrolytes. In contrast, oxide solid electrolytes have better chemical stability to air and to high voltage oxide positive electrode materials.
In order to effectively combine the advantages of high conductivity and excellent mechanical property of sulfide solid electrolyte and high chemical stability of oxide solid electrolyte and avoid the respective disadvantages, the invention provides a preparation method of sulfur oxide solid electrolyte and application of the sulfur oxide solid electrolyte in an all-solid-state battery. The sulfur oxide solid electrolyte is prepared by directly oxidizing the existing sulfide solid electrolyte by an oxidant; the preparation method is simple and efficient, and can be used for batch production. The prepared sulfur oxide solid electrolyte has high conductivity and excellent mechanical property, improves the air and chemical stability of the original sulfide solid electrolyte, and realizes the processing operation of the sulfide electrolyte in a battery drying room and the assembly of all-solid batteries. The all-solid-state battery based on the sulfur oxide solid electrolyte has the advantages of high capacity, low polarization and long service life.
Disclosure of Invention
Therefore, the present invention aims to overcome the defects in the prior art and provide a preparation method of a sulfur oxide solid electrolyte and an application of the sulfur oxide solid electrolyte in an all-solid-state battery.
In order to achieve the above object, a first aspect of the present invention provides a sulfur oxide solid electrolyte containing both anions of sulfur and oxygen and having a general formula axMySz- uOu(ii) a Wherein:
a is a metal ion; preferably, a is selected from one or more of: lithium, sodium, potassium, magnesium, calcium, aluminum, zinc;
m is metal ion and/or non-metal ion; preferably, M is selected from one or more of: lithium, boron, carbon, nitrogen, fluorine, sodium, magnesium, aluminum, silicon, phosphorus, chlorine, potassium, calcium, scandium, titanium, vanadium, copper, zinc, gallium, germanium, zirconium, arsenic, selenium, bromine, strontium, yttrium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, cadmium, indium, tin, antimony, tellurium, iodine, tantalum, tungsten, lead, bismuth, lanthanum, cerium, samarium, europium;
s is sulfur and O is oxygen;
the value ranges of x, y, z and u are 0-20 respectively, and z is larger than u.
The sulfur oxide solid electrolyte according to the first aspect of the invention, wherein the sulfur oxide solid electrolyte is obtained by directly oxidizing a sulfide solid electrolyte with an oxidizing agent;
preferably, the sulfide solid electrolyte has a general formula AxMySz。
The sulfur oxide solid electrolyte according to the first aspect of the invention, wherein the oxidizing agent is an oxidizing gas or liquid;
preferably, the oxidant is selected from one or more of: oxygen, dry air, ozone, sulfur dioxide, sulfur trioxide, nitrogen dioxide, dinitrogen tetroxide, carbon monoxide, carbon dioxide, hydrogen peroxide, chloric acid, hypochlorous acid, nitric acid, sulfuric acid, sulfurous acid, bromic acid, hypobromous acid, iodic acid, hypoiodic acid and metaperiodic acid;
more preferably, the oxidizing agent is selected from oxygen, dry air, ozone, nitric acid, sulfur dioxide, and/or sulfuric acid.
The sulfur oxide solid electrolyte according to the first aspect of the invention, wherein the degree of oxidation of the sulfur oxide solid electrolyte is bulk oxidation, step oxidation, or surface oxidation.
The sulfur oxide solid electrolyte according to the first aspect of the invention, wherein the ion conductance of the sulfur oxide solid electrolyte is more than 10-7S/cm; and/or the electronic conductance of the sulfur oxide solid electrolyte is less than 10-7S/cm。
The sulfur oxide solid electrolyte according to the first aspect of the present invention, wherein the sulfide electrolyte is preferably selected from one or more of: li10GeP2S12、Li7GePS8,Li9.54Si1.74P1.44S11.7Cl0.3、Li6PS5Cl、Li6PS5Br、Li6PS5I、Li4SnS4、Li2SnS3、Li3PS4、Li7P3S11、Li2S·GeS2、Li2S·P2S5、Li2S·P2S5·LiI、Li2S·As2S5·SnS2、Li7P2S8I、Li4PS4I、Li7P2.9S10.85Mo0.01、Li2CuPS4、(Li2S)9(P2S5)3(Ni3S2)、Li7P2.9Mn0.01S10.7I0.3、Li10.35Sn0.27Si1.08P1.65S12、Na3PS4、Na3SbS4、Na3SnS4、Na11Sn2PS12、Na3.75Sn0.75Sb0.25S4、Na3.1Sn0.1P0.9S4、Na4SiS4、Na2.375PS3.375Cl0.625、Na3P0.62As0.38S4、Na3PSe4、Na10GeS2P12、Na10SnS2P12、Na10SiS2P12、Na2S、K2S、Al2S3、ZnS、K3PS4。
The sulfur oxide solid electrolyte according to the first aspect of the invention, wherein the method comprises the steps of:
putting the sulfide solid electrolyte into a sealed container, and introducing a gas oxidant to obtain the sulfur oxide solid electrolyte;
preferably, the flow velocity of the gas oxidant is 10-100 cm3A/min is preferably 20-50 cm3Min; and/or the oxidation reaction time is 10-100 min, preferably 20-60 min.
A second aspect of the present invention provides the method for producing a sulfur oxide solid electrolyte according to the first aspect, comprising the steps of:
putting the sulfide solid electrolyte into a sealed container, and introducing a gas oxidant to obtain the sulfur oxide solid electrolyte;
preferably, the flow velocity of the gas oxidant is 10-100 cm3A/min is preferably 20-50 cm3Min; and/or the oxidation reaction time is 10-100 min, preferably 20-60 min.
A third aspect of the present invention provides the method for producing a sulfur oxide solid electrolyte according to the first aspect, comprising the steps of:
putting the sulfide solid electrolyte into a sealed container, and introducing a liquid oxidant by taking inert gas as carrier gas to obtain the sulfur oxide solid electrolyte;
preferably, the inert gas is selected from one or more of: argon, nitrogen, hydrogen, helium; preferably argon;
more preferably, the flow velocity of the gas oxidant is 10-100 cm3A/min is preferably 20-50 cm3Min; and/or the oxidation reaction time is 10-100 min, preferably 20-60 min.
A fourth aspect of the invention provides an all-solid battery including the sulfur oxide solid electrolyte according to the first aspect.
A fifth aspect of the invention provides use of the sulfur oxide solid electrolyte of the first aspect for producing a chemical power source product; preferably, the chemical source of electrical energy is an all-solid-state battery.
The sulfur oxide electrolyte has better air stability and chemical stability than the existing sulfur materialized electrolyte.
The sulfur oxide solid electrolyte effectively combines the advantages of high conductivity, excellent mechanical property, good air stability and chemical stability of the sulfide solid electrolyte, the oxide solid electrolyte and the like, and simultaneously avoids the defects of the sulfide solid electrolyte and the oxide solid electrolyte. The sulfur oxide solid electrolyte realizes the operation of the sulfide electrolyte in a battery drying room and the assembly of the all-solid-state battery, and the sulfur oxide solid electrolyte is prepared in situ and applied to the all-solid-state battery. The sulfur oxide solid electrolyte provided by the invention is expected to be applied to next-generation high-specific-energy batteries, and is applied to actual life in preference to the sulfide solid electrolyte and the oxide solid electrolyte.
The sulfur oxide solid electrolyte system of the present invention may have, but is not limited to, the following beneficial effects:
the invention provides a novel sulfur oxide solid electrolyte system. The sulfur oxide solid electrolyte effectively combines the advantages of high conductivity, excellent mechanical property, good air stability and chemical stability of the sulfide solid electrolyte and the oxide solid electrolyte, and the like, and simultaneously avoids the defects of the sulfide solid electrolyte and the oxide solid electrolyte. The sulfur oxide solid electrolyte can be prepared by oxidizing the existing sulfide electrolyte with dry air, so that the existing sulfide electrolyte can be operated in a dry room of a battery and an all-solid-state battery of the battery is assembled, and the sulfur oxide solid electrolyte is prepared in situ and applied to the all-solid-state battery. The preparation method of the sulfur oxide solid electrolyte is simple, easy to operate and suitable for mass production. The sulfur oxide solid electrolyte improves the chemical stability of the existing sulfide electrolyte to air, high-voltage oxide anode materials and cathode materials, and has smaller anode and cathode interface resistance. The sulfur oxide solid electrolyte provided by the invention is expected to be applied to next-generation high-specific-energy batteries, and is applied to actual life in preference to the sulfide solid electrolyte and the oxide solid electrolyte.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 shows a production method for producing a sulfur oxide solid electrolyte by directly oxidizing a sulfide solid electrolyte with an oxidizing agent; wherein fig. 1(a) shows the production of a sulfur oxide solid electrolyte by direct oxidation of a sulfide solid electrolyte by an oxidizing gas; fig. 1(b) shows the production of a sulfur oxide solid electrolyte by direct oxidation of a sulfide solid electrolyte by an oxidizing liquid; fig. 1(c) shows an all-solid-state battery in which a sulfide solid electrolyte is directly oxidized by dry air in a battery dry room to prepare and assemble a sulfur oxide-containing solid electrolyte.
Fig. 2 shows three typical oxidation levels and oxygen distributions for a sulfur oxide solid electrolyte.
Fig. 3 shows a first-cycle characteristic voltage profile of the sulfur oxide solid electrolyte contained in example 1.
Fig. 4 shows a first-cycle characteristic voltage profile of the sulfur oxide solid electrolyte contained in example 2.
Fig. 5 shows a first-cycle characteristic voltage profile of the sulfur oxide solid electrolyte contained in example 3.
Fig. 6 shows a first-cycle characteristic voltage profile of the sulfur oxide solid electrolyte contained in example 4.
Fig. 7 shows a first-cycle characteristic voltage profile of the sulfur oxide solid electrolyte contained in example 5.
Fig. 8 shows a first-cycle characteristic voltage profile of the sulfur oxide solid electrolyte contained in example 6.
Fig. 9 shows a first-cycle characteristic voltage profile of the sulfur oxide solid electrolyte contained in example 7.
Fig. 10 shows a first-cycle characteristic voltage profile of the sulfur oxide solid electrolyte contained in comparative example 1.
Detailed Description
The invention is further illustrated by the following specific examples, which, however, are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
This section generally describes the materials used in the testing of the present invention, as well as the testing methods. Although many materials and methods of operation are known in the art for the purpose of carrying out the invention, the invention is nevertheless described herein in as detail as possible. It will be apparent to those skilled in the art that the materials and methods of operation used in the present invention are well within the skill of the art, provided that they are not specifically illustrated.
The reagents and instrumentation used in the following examples are as follows:
reagent:
lithium metal foil, oxygen, ozone, sodium metal foil, LiNi0.8Mn0.1Co0.1O2Lithium indium alloy, silicon, nitric acid, sulfur dioxide, sulfuric acid, NaCrO2，TiS2，LiNi0.81Co0.15Al0.05O2Purchased from Sigma.
Sulfide solid electrolyte Li6PS5Cl，Li10GeP2S12，Li9.54Si1.74P1.44S11.7Cl0.3，Li3PS4，Na3.75Sn0.75Sb0.25S4，Na2.375PS3.375Cl0.625Purchased from NEI corporation.
The instrument comprises the following steps:
chemical element analyzer, available from ThermoFisher Scientific model FlashSmart ElementalAnalyzer.
Focused two-beam scanning electron microscope (FIB-SEM) from ThermoFisher Scientific model Helios5 CX.
Example 1
This example illustrates the preparation and use of the novel sulfur oxide solid electrolyte of the present invention.
(1) The existing sulfide solid electrolyte adopts Li6PS5And Cl, wherein the oxidant adopts oxygen.
(2) The preparation process of the sulfur oxide solid electrolyte comprises the following steps: mixing Li6PS5Cl was placed in a sealed container (as shown in FIG. 1a), then high purity oxygen was introduced, the gas flow was controlled at 50 cc/min, and the reaction time was 30 minutes.
(3) Confirmation of the composition of the sulfur oxide solid electrolyte as Li by chemical element analysis6PS4.5O0.5And (4) Cl. The oxidation degree and oxygen distribution of the sulfur oxide solid electrolyte were confirmed to be overall oxidation and uniform oxygen distribution by focused double-beam scanning electron microscope electron energy scattering spectroscopy (FIB-SEM-EDS), in which the oxygen content was 3 wt%. The ion conductance of the oxysulfide solid electrolyte is 4 x 10-3S/cm, electron conductance of 2X 10-10S/cm。
(4) The positive electrode adopts LiNi0.8Mn0.1Co0.1O2The electrolyte adopts Li6PS4.5O0.5And Cl, assembling the all-solid-state battery in a glove box by adopting lithium indium alloy as a negative electrode.
(5) Fig. 3 is a first-cycle characteristic voltage curve of the sulfur oxide-containing solid electrolyte. The hybrid battery has a reversible capacity of 150 mAh/g.
Example 2
This example illustrates the preparation and use of the novel sulfur oxide solid electrolyte of the present invention.
(1) The existing sulfide solid electrolyte adopts Li6PS5And Cl, wherein dry air is adopted as the oxidant.
(2) The in-situ preparation process of the sulfur oxide solid electrolyte and the assembly of the all-solid-state battery are as follows: in a battery drying room, Li6PS5Cl is pressed into an electrolyte thin sheet to be connected with the positive electrode LiNi0.8Mn0.1Co0.1O2And assembling the cathode lithium-indium alloy into an all-solid-state battery. During the above operation, the sulfide solid electrolyte reacts with dry oxygen in the dry room to form a sulfur oxide solid electrolyte.
(3) Confirmation of the composition of the sulfur oxide solid electrolyte as Li by chemical element analysis6PS4.75O0.25And (4) Cl. The oxidation degree and oxygen distribution of the sulfur oxide solid electrolyte were confirmed by FIB-SEM-EDS surface scanning as stepwise oxidation and oxygen stepwise distribution in which the content of sulfur of oxygen at the surface was about 3 wt%, and the content gradually decreased from the surface to the inside to 0 wt%. . The ion conductance of the oxysulfide solid electrolyte is 8 x 10-4S/cm, electron conductance of 3X 10-10S/cm。
(4) Fig. 4 is a first-cycle characteristic voltage curve of the sulfur oxide-containing solid electrolyte. The hybrid battery has a reversible capacity of 127 mAh/g.
Example 3
This example illustrates the preparation and use of the novel sulfur oxide solid electrolyte of the present invention.
(1) Existing sulfide solid electrolytesWith Li9.54Si1.74P1.44S11.7Cl0.3The oxidant is ozone.
(2) The preparation process of the sulfur oxide solid electrolyte comprises the following steps: mixing Li9.54Si1.74P1.44S11.7Cl0.3Placing into a sealed container (as shown in figure 1a), introducing high-purity ozone, controlling the air flow to be 30 cubic centimeters per minute, and reacting for 60 minutes.
(3) Confirmation of the composition of the sulfur oxide solid electrolyte as Li by chemical element analysis9.54Si1.74P1.44S10O1.7Cl0.3. The oxidation degree and oxygen distribution of the sulfur oxide solid electrolyte were confirmed by FIB-SEM-EDS surface scan as surface oxidation and oxygen surface local distribution, in which the content of oxygen at the surface 50 was about 6 wt% and the internal content was 0 wt%. The ion conductance of the oxysulfide solid electrolyte is 6 x 10-4S/cm, electron conductance of 3X 10-9S/cm。
(4) The positive electrode adopts LiNi0.81Co0.15Al0.05O2The electrolyte adopts Li9.54Si1.74P1.44S10O1.7Cl0.3And the cathode adopts silicon, and the all-solid-state battery is assembled in a battery drying room.
(5) Fig. 5 is a first-cycle characteristic voltage curve of the sulfur oxide-containing solid electrolyte. The hybrid battery has a reversible capacity of 126 mAh/g.
Example 4
This example illustrates the preparation and use of the novel sulfur oxide solid electrolyte of the present invention.
(1) The existing sulfide solid electrolyte adopts Li10GeP2S12The oxidant is pure nitric acid.
(2) The preparation process of the sulfur oxide solid electrolyte comprises the following steps: mixing Li10GeP2S12Placing into a sealed container (as shown in figure 1b), introducing nitric acid with argon as carrier gas, controlling the gas flow at 20 cubic centimeters per minute, and reacting for 20 minutes.
(3) Confirmation by chemical elemental analysisThe component of the sulfur oxide solid electrolyte is Li10GeP2S10O2. The oxidation degree and oxygen distribution of the sulfur oxide solid electrolyte were confirmed by FIB-SEM-EDS surface scanning as stepwise oxidation and oxygen stepwise distribution in which the content of sulfur of oxygen at the surface was about 10 wt%, and the content gradually decreased from the surface to the inside to 0 wt%. The ion conductance of the sulfur oxide solid electrolyte is 1 x 10-3S/cm, electron conductance of 7X 10-10S/cm。
(4) The positive electrode adopts LiCoO2The electrolyte adopts Li10GeP2S10O2And the negative electrode adopts graphite, and the all-solid-state battery is assembled in a battery drying room.
(5) Fig. 6 is a first-cycle characteristic voltage curve of the sulfur oxide-containing solid electrolyte. The hybrid battery has a reversible capacity of 150 mAh/g.
Example 5
This example illustrates the preparation and use of the novel sulfur oxide solid electrolyte of the present invention.
(1) The existing sulfide solid electrolyte adopts Li3PS4And dry air is used as the oxidant.
(2) The in-situ preparation process of the sulfur oxide solid electrolyte and the assembly of the all-solid-state battery are as follows: in a battery drying room, Li3PS4Pressing into electrolyte thin sheet, and assembling with anode elemental sulfur and cathode metal lithium into the all-solid-state battery. During the above operation, the sulfide solid electrolyte reacts with dry oxygen in the dry room to form a sulfur oxide solid electrolyte.
(3) Confirmation of the composition of the sulfur oxide solid electrolyte as Li by chemical element analysis3PS3.75O0.25. The oxidation degree and oxygen distribution of the sulfur oxide solid electrolyte were confirmed by FIB-SEM-EDS surface scan as surface oxidation and oxygen surface local distribution, in which the content of oxygen at the surface 50 was about 6.5 wt% and the internal content was 0 wt%. . The ion conductance of the sulfur oxide solid electrolyte is 9 x 10-4S/cm, electron conductance of 1X 10-9S/cm。
(4) Fig. 7 is a first-cycle characteristic voltage curve of the sulfur oxide-containing solid electrolyte. The hybrid battery has a reversible capacity of 800 mAh/g.
Example 6
This example illustrates the preparation and use of the novel sulfur oxide solid electrolyte of the present invention.
(1) The existing sulfide solid electrolyte adopts Na3.75Sn0.75Sb0.25S4The oxidant is sulfur dioxide.
(2) The preparation process of the sulfur oxide solid electrolyte comprises the following steps: mixing Na3.75Sn0.75Sb0.25S4The reaction mixture was placed in a sealed container (see FIG. 1a), and high purity sulfur dioxide was introduced, with a gas flow controlled at 20 cc/min, and a reaction time of 35 minutes.
(3) The component of the sulfur oxide solid electrolyte was confirmed to be Na by chemical element analysis3.75Sn0.75Sb0.25S3.5O0.5. The oxidation degree and oxygen distribution of the sulfur oxide solid electrolyte were confirmed to be overall oxidation and uniform oxygen distribution by FIB-SEM-EDS surface scan, wherein the oxygen content was 2.5 wt%. The ion conductance of the oxysulfide solid electrolyte is 5 x 10-3S/cm, electron conductance of 8X 10-10S/cm。
(4) The anode adopts NaCrO2The electrolyte adopts Na3.75Sn0.75Sb0.25S3.5O0.5And the cathode adopts metal sodium, and an all-solid-state battery is assembled in a glove box.
(5) Fig. 8 is a first-cycle characteristic voltage curve of the sulfur oxide-containing solid electrolyte. The hybrid battery had a reversible capacity of 89 mAh/g.
Example 7
This example illustrates the preparation and use of the novel sulfur oxide solid electrolyte of the present invention.
(1) The existing sulfide solid electrolyte adopts Na2.375PS3.375Cl0.625The oxidant is sulfuric acid.
(2) The preparation process of the sulfur oxide solid electrolyte comprises the following steps: mixing Na2.375PS3.375Cl0.625Putting in a secretThe vessel was sealed (see fig. 1b), then sulfuric acid was introduced with argon as a carrier gas, the gas flow was controlled at 25 cc/min, and the reaction time was 25 minutes.
(3) The component of the sulfur oxide solid electrolyte was confirmed to be Na by chemical element analysis2.375PS3O0.375Cl0.625. The oxidation degree and oxygen distribution of the sulfur oxide solid electrolyte were confirmed by FIB-SEM-EDS surface scanning as stepwise oxidation and oxygen stepwise distribution in which the content of sulfur of oxygen at the surface was about 5.5 wt%, and the content gradually decreased from the surface to the inside to 0 wt%. . The ion conductance of the oxysulfide solid electrolyte is 4 x 10-4S/cm, electron conductance of 2X 10-9S/cm。
(4) The positive electrode adopts TiS2The electrolyte adopts Na2.375PS3O0.375Cl0.625And the cathode adopts metal tin, and the all-solid-state battery is assembled in a battery drying room.
(5) Fig. 9 is a first-cycle characteristic voltage curve of the sulfur oxide-containing solid electrolyte. The hybrid battery has a reversible capacity of 98 mAh/g.
Comparative example 1
The other conditions were the same as in example 1 except that the existing sulfide solid electrolyte Li was used6PS5Cl instead of oxysulfide solid electrolyte Li6PS4.5O0.5Cl serves as the solid electrolyte of the all-solid battery. Fig. 10 is a first-cycle characteristic voltage curve of the sulfur oxide-containing solid electrolyte. The hybrid battery has a reversible capacity of 60 mAh/g.
Test example 1
With the existing sulfide solid electrolyte Li6PS5Cl vs Li prepared in example 16PS4.5O0.5Cl has better air and chemical stability. Mixing Li6PS5Cl and Li6PS4.5O0.5Cl while exposed to air for half an hour, Li6PS5Ionic conductivity of Cl is from 2X 10-3S/cm is reduced to 1 × 10-4S/cm; and Li6PS4.5O0.5Ionic conductivity of Cl from 4×10-3S/cm is reduced to 1 × 10-3S/cm. Further, example 1 employs Li6PS4.5O0.5All-solid-state battery using Cl as solid electrolyte and adopting Li in comparison ratio 16PS5All-solid-state batteries in which Cl is a solid electrolyte have higher reversible capacity.
Although the present invention has been described to a certain extent, it is apparent that appropriate changes in the respective conditions may be made without departing from the spirit and scope of the present invention. It is to be understood that the invention is not limited to the described embodiments, but is to be accorded the scope consistent with the claims, including equivalents of each element described.

Claims (10)

1. A solid electrolyte of sulfur oxide, characterized in that it contains both sulfur and oxygen anions, and the general formula of the solid electrolyte of sulfur oxide is AxMySz-uOu(ii) a Wherein:
a is a metal ion; preferably, a is selected from one or more of: lithium, sodium, potassium, magnesium, calcium, aluminum, zinc;
m is metal ion and/or non-metal ion; preferably, M is selected from one or more of: lithium, boron, carbon, nitrogen, fluorine, sodium, magnesium, aluminum, silicon, phosphorus, chlorine, potassium, calcium, scandium, titanium, vanadium, copper, zinc, gallium, germanium, zirconium, arsenic, selenium, bromine, strontium, yttrium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, cadmium, indium, tin, antimony, tellurium, iodine, tantalum, tungsten, lead, bismuth, lanthanum, cerium, samarium, europium;
s is sulfur and O is oxygen;
the value ranges of x, y, z and u are 0-20 respectively, and z is larger than u.
2. The sulfur oxide solid electrolyte according to claim 1, wherein the sulfur oxide solid electrolyte is obtained by directly oxidizing a sulfide solid electrolyte with an oxidizing agent;
preferably, the sulfide solid electrolyte has a general formula AxMySz。
3. The sulfur oxide solid electrolyte according to claim 2, wherein the oxidizing agent is an oxidizing gas or liquid;
preferably, the oxidant is selected from one or more of: oxygen, dry air, ozone, sulfur dioxide, sulfur trioxide, nitrogen dioxide, dinitrogen tetroxide, carbon monoxide, carbon dioxide, hydrogen peroxide, chloric acid, hypochlorous acid, nitric acid, sulfuric acid, sulfurous acid, bromic acid, hypobromous acid, iodic acid, hypoiodic acid and metaperiodic acid;
more preferably, the oxidizing agent is selected from oxygen, dry air, ozone, nitric acid, sulfur dioxide, and/or sulfuric acid.
4. The sulfur oxide solid electrolyte according to any one of claims 1 to 3, characterized in that the degree of oxidation of the sulfur oxide solid electrolyte is bulk oxidation, step oxidation or surface oxidation.
5. The sulfur oxide solid electrolyte according to any one of claims 1 to 4, wherein an ion conductance of the sulfur oxide solid electrolyte is more than 10-7S/cm; and/or the electronic conductance of the sulfur oxide solid electrolyte is less than 10-7S/cm。
6. The sulfur oxide solid electrolyte according to any one of claims 2 to 5, wherein the sulfide electrolyte is preferably selected from one or more of: li10GeP2S12、Li7GePS8,Li9.54Si1.74P1.44S11.7Cl0.3、Li6PS5Cl、Li6PS5Br、Li6PS5I、Li4SnS4、Li2SnS3、Li3PS4、Li7P3S11、Li2S·GeS2、Li2S·P2S5、Li2S·P2S5·LiI、Li2S·As2S5·SnS2、Li7P2S8I、Li4PS4I、Li7P2.9S10.85Mo0.01、Li2CuPS4、(Li2S)9(P2S5)3(Ni3S2)、Li7P2.9Mn0.01S10.7I0.3、Li10.35Sn0.27Si1.08P1.65S12、Na3PS4、Na3SbS4、Na3SnS4、Na11Sn2PS12、Na3.75Sn0.75Sb0.25S4、Na3.1Sn0.1P0.9S4、Na4SiS4、Na2.375PS3.375Cl0.625、Na3P0.62As0.38S4、Na3PSe4、Na10GeS2P12、Na10SnS2P12、Na10SiS2P12、Na2S、K2S、Al2S3、ZnS、K3PS4。
7. The method for producing the sulfur oxide solid electrolyte according to any one of claims 1 to 6, characterized by comprising the steps of:
putting the sulfide solid electrolyte into a sealed container, and introducing a gas oxidant to obtain the sulfur oxide solid electrolyte;
preferably, the flow velocity of the gas oxidant is 10-100 cm3A/min is preferably 20-50 cm3Min; and/or the oxidation reaction time is 10-100 min, preferably 20-60 min.
8. The method for producing the sulfur oxide solid electrolyte according to any one of claims 1 to 6, characterized by comprising the steps of:
putting the sulfide solid electrolyte into a sealed container, and introducing a liquid oxidant by taking inert gas as carrier gas to obtain the sulfur oxide solid electrolyte;
preferably, the inert gas is selected from one or more of: argon, nitrogen, hydrogen, helium; preferably argon;
more preferably, the flow velocity of the gas oxidant is 10-100 cm3A/min is preferably 20-50 cm3Min; and/or the oxidation reaction time is 10-100 min, preferably 20-60 min.
9. An all-solid battery characterized by comprising the sulfur oxide solid electrolyte according to any one of claims 1 to 6.
10. Use of the sulfur oxide solid electrolyte according to any one of claims 1 to 6 for producing a chemical power product; preferably, the chemical source of electrical energy is an all-solid-state battery.
CN202010114844.4A 2020-02-25 2020-02-25 Sulfur oxide solid electrolyte, preparation method and application thereof Pending CN111244534A (en)

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