CN115133112A - Surface oxygen-enriched sulfide solid electrolyte material and preparation method and application thereof - Google Patents
Surface oxygen-enriched sulfide solid electrolyte material and preparation method and application thereof Download PDFInfo
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 85
- 239000001301 oxygen Substances 0.000 title claims abstract description 85
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 43
- 239000002203 sulfidic glass Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002001 electrolyte material Substances 0.000 claims abstract description 45
- 239000003792 electrolyte Substances 0.000 claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 238000009828 non-uniform distribution Methods 0.000 claims abstract description 3
- 239000007784 solid electrolyte Substances 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 239000010410 layer Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000005303 weighing Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910005839 GeS 2 Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910020346 SiS 2 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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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
- 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
- H01M10/0562—Solid materials
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Physics & Mathematics (AREA)
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Abstract
The invention belongs to the technical field of lithium batteries, and particularly relates to a sulfide solid electrolyte material with an oxygen-rich surface, and a preparation method and application thereof. The sulfide solid state electrolyte material contains lithium ions and anions containing at least elemental sulfur, and the sulfide solid state electrolyte material also contains elemental oxygen, which is present in a non-uniform distribution so that the elemental oxygen is substantially enriched in the outer surface of the sulfide solid state electrolyte material. Compared with the prior art, the surface oxygen-enriched sulfide solid electrolyte material has the advantages that the oxygen element exists in a certain depth of the surface of the electrolyte particles, so that the doping amount can be greatly reduced, the air stability and the stability of the oxide anode are improved by oxygen doping, and the ion conductivity is not influenced.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a sulfide solid electrolyte material with an oxygen-rich surface, and a preparation method and application thereof.
Background
Since the early commercialization of the lithium ion secondary battery in the 90 s of the last century, the lithium ion secondary battery has been rapidly developed due to advantages such as high energy density and long service life. However, the lithium ion battery generally used at present is a liquid phase battery and contains a flammable organic electrolyte, so that a serious potential safety hazard exists. In recent years, the occurrence of frequent safety accidents on liquid-phase lithium ion power batteries has greatly restricted the further use of this system. The non-combustible inorganic solid material is used as the electrolyte of the lithium ion battery, so that potential safety hazards caused by leakage of organic electrolyte and thermal runaway inside the battery in the use process of the battery can be eliminated, and the lithium ion battery can be used under extreme conditions of high temperature, low temperature and the like. Further improving the value of the lithium secondary battery and expanding the application field of the lithium secondary battery. Therefore, the development of a solid electrolyte material having high stability and high ion conductivity is a key element for promoting the commercialization of a solid battery.
Among solid electrolytes, sulfide-based solid electrolytes have attracted attention as a solid electrolyte having a very high lithium ion conductivity. A wide variety of P-S groups are present in sulfide solid electrolytes, which react with H upon exposure to air 2 O reaction to produce toxic H 2 S gas, in the same wayResulting in a decrease in the ion conductivity of the solid electrolyte. Non-patent literature shows that (J.solid State electrochem.,2013,17,2551-2557.), O doping can effectively reduce H 2 The amount of S gas generated. Another problem with sulfide solid-state electrolytes is that they have poor compatibility with oxide anodes, and O-doped sulfide solid-state electrolytes have better compatibility with oxide anodes because the space charge layer can be confined. The non-patent literature shows (J. alloys Compd.,2014,591,247- + The mobility of (a) reduces the conductivity of the electrolyte, which is disadvantageous for practical use of sulfide solid-state electrolytes. Therefore, in order to improve the performance of the sulfide solid electrolyte without lowering its ion conductivity, it is necessary to control the O doping amount.
The traditional O-doped sulfide solid electrolyte material has the following defects: 1) the O element is uniformly distributed in the electrolyte, and the concentration of the O element on the surface of the electrolyte particle is consistent with that of the O element in the electrolyte particle, so that the doping amount is difficult to reduce; 2) the surface is coated with an O-containing layer, although the concentration of the whole element of O is reduced, the preparation method is complex, the control difficulty is high, and the surface coating layer is easy to generate shelling in the using process.
Chinese patent CN201910534210.1 reports that the structure contains [ PS 3 O]The ionic conductivity and stability of the sulfide solid electrolyte of the unit are improved. The addition amount of the oxidant is up to 0.1 wt% -5 wt%, and because the O element is distributed in the whole solid electrolyte, the concentration of the O element has a further optimized space; meanwhile, elements other than O in the solid oxidizer adversely affect the performance of the solid electrolyte.
Chinese patent CN201910648164.8 reports a sulfide solid electrolyte with a three-layer core-shell structure, the structure of the material is too complex to realize industrial application, and P 2 S 5 And O 2 The addition of (b) significantly reduces the ion conductivity of the starting material, which may be due to the difficulty of the preparation method to control the complete reaction of the two reactants, resulting in the presence of a low ion conductivity hetero-phase in the electrolyte material.
Chinese patent No. cn201811018312.x reports a sulfide solid state electrolyte material comprising an oxide layer on the surface, the oxygen-containing compound layer containing lithium, phosphorus, halogen and oxygen-containing oxide. The scheme is essentially that the surface is doped with oxides, O element does not enter the crystal lattice of the sulfide solid electrolyte, the extra added oxides cause the ion conduction of the solid electrolyte body to be reduced, the preparation difficulty of the core-shell structure material is very high, and the shelling risk exists in the charge and discharge cycle process.
Chinese patent CN201980004437.3 improves the contact state between the solid electrolyte and the positive electrode active material particles or the negative electrode active material particles by increasing the oxygen concentration on the surface of the solid electrolyte particles and reducing the halogen concentration, thereby improving the rate characteristics and cycle characteristics. The disadvantage of this method is the severe drop in ion conductance of the sulfide solid electrolyte (3.0 → 1.5mS/cm, 2.7 → 1.5mS/cm, 5.7 → 1.9mS/cm) because it uses exposure of the original sulfide solid electrolyte in humid air for surface enrichment, which is essentially hydrolysis, failure of the electrolyte surface particles. Another disadvantage of this process is that the extent of the hydrolysis reaction and the depth in the electrolyte particles is difficult to control and the production of toxic hydrogen sulfide gas is hazardous to the environment and to the operator.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a high-stability and high-ion-conductivity sulfide solid electrolyte material with oxygen enriched surface, a preparation method thereof and application of the obtained material in a solid lithium secondary battery.
The surface oxygen-enriched sulfide solid electrolyte material only has O element in a certain depth of the surface of the electrolyte particles, the surface O doping improves the air stability and the stability to the anode of the oxide of the sulfide solid electrolyte material, the surface O doping also reduces the overall O concentration in the electrolyte, avoids the reduction of ion conduction, and does not influence the ion conduction while utilizing the O doping function. The preparation method of the surface oxygen-enriched sulfide solid electrolyte material is simple and effective, is combined with the crushing process of the electrolyte material, and is low in production cost. Therefore, the surface oxygen-enriched sulfide solid electrolyte material and the preparation method thereof provided by the invention are expected to solve the problem of large-scale use of the sulfide solid electrolyte material.
Specifically, the invention firstly provides a sulfide solid state electrolyte material with an oxygen-rich surface, wherein the sulfide solid state electrolyte material comprises lithium ions and anions at least containing sulfur element;
the sulfide solid state electrolyte material further contains an oxygen element, and the oxygen element is present in a non-uniform distribution so that the oxygen element is substantially enriched in the outer surface of the sulfide solid state electrolyte material.
The research of the invention finds that the surface oxygen enrichment can greatly improve the air stability of the sulfide solid electrolyte material and the stability of the sulfide solid electrolyte material to an oxide anode, and simultaneously, the integral oxygen concentration in the electrolyte is greatly reduced, and the reduction of ion conductivity is avoided.
The term "the oxygen element is substantially enriched in the outer surface layer of the sulfide solid state electrolyte material" described herein means that 90% or more, and further preferably 95% or more, of the oxygen element is substantially enriched in the outer surface layer of the sulfide solid state electrolyte material.
Preferably, L/D ≦ 10%, where L represents a thickness of an outer surface oxygen-rich layer of the sulfide solid state electrolyte material, and D represents a particle diameter of the sulfide solid state electrolyte material.
More preferably, L/D is 1% to 5%, and L is 5nm or more. By adopting the conditions, the oxygen element is enriched in a certain depth (namely the thickness of the oxygen-enriched layer) on the outer surface of the electrolyte particle, so that the excellent air stability and the stability to the oxide anode can be both considered, and the oxygen doping amount can be further reduced.
The invention also provides a preparation method of the surface oxygen-enriched sulfide solid electrolyte material, which is simple and effective, is combined with the crushing process of the electrolyte material, is suitable for large-scale production and has low production cost. The method specifically comprises the following steps:
1) providing a sulfide solid state electrolyte material substantially free of oxygen elements; the term "sulfide solid state electrolyte material substantially free of an oxygen element" described herein means that the content of the oxygen element in the sulfide solid state electrolyte material is 100ppm or less, further preferably 50ppm or less;
2) crushing the sulfide solid electrolyte material obtained in the step 1) in an oxygen-free medium;
3) crushing the sulfide solid electrolyte material treated in the step 2) in an oxygen-containing medium;
4) carrying out heat treatment on the sulfide solid electrolyte material treated in the step 3).
The method of the present invention for providing a sulfide solid state electrolyte material substantially free of an oxygen element is arbitrary. Can be purchased or manufactured. Here, an example of a method for producing the raw material solid electrolyte particles will be described. However, the method for producing the raw material solid electrolyte particles is arbitrary.
For example, Li may be used 2 S、LiCl、P 2 S 5 And weighing, mixing and carrying out heat treatment according to the proportion to obtain the oxygen-free sulfide solid electrolyte material.
Preferably, the oxygen-free medium in step 2) is an inert gas free of oxygen, more preferably nitrogen, argon or a nitrogen/argon mixture. The present invention performs the crushing treatment under the above-described atmosphere, with the object of activating the electrolyte material to enhance the reactivity of the electrolyte material with oxygen in the subsequent step.
Preferably, the crushing treatment in the step 2) is ball milling treatment, the rotating speed is 200-500 rpm, and the time is 5-24 h.
Preferably, the oxygen-containing medium in step 3) is an inert gas containing oxygen, more preferably nitrogen, argon or a nitrogen/argon mixture containing oxygen.
Preferably, the concentration of oxygen in the oxygen-containing medium in the step 3) is 100 to 5000ppm, and further preferably, the concentration of oxygen is 3000 to 5000 ppm. The ball milling treatment is carried out under the oxygen concentration, and the obtained sulfide solid electrolyte material can further better give consideration to high air stability, stability to an oxide anode and ion conduction.
Preferably, the crushing treatment in the step 3) is ball milling treatment, the rotating speed is 100-300 rpm, and the time is 2-12 h, and further preferably, the rotating speed is 150-250 rpm, and the time is 8-12 h. Under the ball milling condition, the obtained sulfide solid electrolyte material can better give consideration to high air stability, stability to an oxide anode and ion conduction.
Preferably, the temperature of the heat treatment in the step 4) is 250-350 ℃, the time of the heat treatment is 3-48h, and the protective gas of the heat treatment is inert gas.
The invention also provides the application of the sulfide solid electrolyte material with oxygen-enriched surface in the preparation of the solid lithium secondary battery.
Specifically, the present invention provides a positive electrode layer for a solid-state battery, which is prepared from the above-described surface oxygen-rich sulfide solid-state electrolyte material or the above-described surface oxygen-rich sulfide solid-state electrolyte material prepared by the above-described preparation method, a positive electrode material, and a conductive agent.
The invention provides an electrolyte layer for a solid-state battery, which is prepared from the surface oxygen-enriched sulfide solid-state electrolyte material or the surface oxygen-enriched sulfide solid-state electrolyte material prepared by the preparation method. The invention further provides a solid-state lithium secondary battery, which comprises a positive electrode layer, an electrolyte layer and a negative electrode layer, wherein the positive electrode layer is the positive electrode layer for the solid-state battery provided by the scheme, and the electrolyte layer is the electrolyte layer for the solid-state battery provided by the scheme.
Compared with the prior art, the surface oxygen-enriched sulfide solid electrolyte material has the advantages that the doping amount can be greatly reduced because O element exists in a certain depth on the surface of electrolyte particles, and the air stability and the stability of an oxide anode are improved by utilizing O doping without influencing ion conduction. Meanwhile, the invention also provides a simple and efficient preparation method. The material is simple to prepare and low in production cost; meanwhile, the obtained surface oxygen-enriched sulfide solid electrolyte material has controllable ionic conductivity and excellent performance when being used as an electrolyte material in an all-solid-state lithium battery.
The invention has the beneficial effects that:
1) according to the surface oxygen-enriched sulfide solid electrolyte material and the preparation method thereof, provided by the invention, the O doping is controlled within a certain depth range of the surface of the electrolyte, so that the concentration of O element can be greatly reduced, and the adverse effect of the O doping on the ion conduction of the sulfide solid electrolyte is reduced.
2) The surface oxygen-enriched sulfide solid electrolyte material and the preparation method thereof provided by the invention can be realized in the crushing process of the sintered electrolyte, no additional step and equipment are needed, and the influence on the cost in large-scale production can be ignored.
Drawings
Fig. 1 is XPS peaks of surface O1s of the surface oxygen-rich sulfide electrolyte obtained in example 1 and the oxygen-free sulfide electrolyte obtained in comparative example 1.
FIG. 2 is the XPS peak of O1s at different depths from the surface of the surface oxygen-rich sulfide electrolyte obtained in example 1.
Fig. 3 is an XRD spectrum of the surface oxygen-rich sulfide electrolyte material obtained in example 1 and the oxygen-free sulfide electrolyte obtained in comparative example 1.
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 specify particular techniques or conditions, and are to be construed in accordance with the description of the art in the literature or with the specification of the product. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
Raw material solid electrolyte preparation
In a glove box, various raw materials are respectively weighed according to the proportion of the chemical formula in the table 1, the total weight of the raw materials is kept unchanged at 5g, the raw materials are placed in a 50ml zirconia ball milling tank, and 50g of zirconia balls with the diameter of 5mm are added. And (3) placing the sealed ball milling tank on a ball mill, setting the rotating speed to be 400rpm, and carrying out ball milling for 12 h. And collecting the ball-milled sample, and sealing the ball-milled sample in a vacuum quartz tube for calcination. The calcination temperature is controlled by temperature programming, and the temperature is naturally reduced to 50 ℃ after sintering is finished, so that the raw material solid electrolyte can be obtained.
Wherein:
examples 1-5, comparative example 1: according to Li 6 PS 5 Weighing Li according to element proportion in Cl 2 S，P 2 S 5 ，LiCl；
Example 6, comparative example 2: according to Li 5.5 PS 4.5 Cl 1.5 In the element proportion, Li is weighed 2 S，P 2 S 5 ，LiCl；
Example 7, comparative example 3: according to 70Li 2 S-30P 2 S 5 In the element proportion, Li is weighed 2 S，P 2 S 5 ；
Example 8, comparative example 4: according to Li 10 GeP 2 S 12 Weighing Li in proportion of elements 2 S，P 2 S 5 ，GeS 2 ；
Example 9, comparative example 5: according to Li 9.54 Si 1.74 P 1.44 S 11.7 I 0.3 Weighing Li in proportion of elements 2 S，P 2 S 5 ，SiS 2 ，LiI；
Comparative examples 6, 7, 8: respectively according to Li 6 PS 4.95 O 0.05 Cl、Li 6 PS 4.9 O 0.1 Weighing Li according to element proportion in Cl 2 S，P 2 S 5 ，LiCl，Li 2 O；
Raw material solid electrolyte crushing
In a glove box, the raw solid electrolyte was collected, placed in a 50ml zirconia ball mill jar, and 50g of zirconia pellets 5mm in diameter were added. And (3) placing the sealed ball milling tank on a ball mill, setting the rotating speed according to the ball milling speed 1 in the table 1, and setting the time according to the ball milling time 1 to crush the raw material solid electrolyte.
Surface rich oxidation treatment
In the ball mill jar which finishes the crushing, O is introduced according to the requirements in Table 1 2 N of (A) 2 And setting the rotating speed according to the ball milling speed 2 and setting the time according to the ball milling time 2, and carrying out crushing surface rich oxidation treatment on the solid electrolyte.
Thermal treatment
Carrying out heat treatment on the electrolyte material subjected to surface oxidation treatment, setting the temperature rise speed to be 3 ℃/min, raising the temperature to 320 ℃, and keeping the temperature for 10h, wherein the protective gas is N 2 。
Solid electrolyte material air stability test
The surface oxygen-enriched solid electrolyte materials obtained in examples 1 to 9 and comparative examples 1 to 8 were subjected to an air stability test. In a glove box, 300mg of the solid electrolyte material was weighed into a 5ml open glass bottle. The glass bottle was then placed in a reaction box through which a stream of air of a specific humidity was passed and allowed to stand at room temperature for 24 hours. The relative humidity of the dry air was 10% and the air flow rate was 100 ml/min. And after standing, taking out the sample for ion conduction testing.
Simulated battery assembly
The surface oxygen-rich sulfide solid electrolyte materials obtained in examples 1 to 9 and comparative examples 1 to 8 were used as a positive electrode material (LiNi) 0.6 Co 0.2 Mn 0.2 O 2 NCM622, electrolyte material, acetylene carbon 70:30:1 (mass ratio), 3 materials were weighed and ground in a glove box for 20min to mix well. The mixture is used as positive electrode powder, a metal Li sheet is used as a negative electrode, and the electrolyte materials prepared in the examples 1 to 9 and the comparative examples 1 to 8 are used as electrolyte layers to assemble the all-solid-state secondary battery.
Fig. 1 is XPS peaks of O1s on the surface of the surface oxygen-rich sulfide electrolyte obtained in example 1 and the oxygen-free sulfide electrolyte obtained in comparative example 1. As can be seen from the figure, the surface oxygen-rich sulfide electrolyte obtained in example 1 has a distinct O signal peak indicating that the electrolyte surface has been successfully O-doped. While almost no O signal peak was observed on the surface of the sulfide electrolyte obtained in comparative example 1, indicating that the electrolyte surface was not doped with O.
Fig. 2 is an XPS peak of O1s at a different depth from the surface for the surface oxygen-rich sulfide electrolyte obtained in example 1. As can be seen from the figure, the surface oxygen-rich sulfide electrolyte obtained in example 1 has strong O signal peaks at 0nm and 10nm from the surface, indicating that the electrolyte has been successfully O-doped and has a certain depth. While almost no O signal peak was observed at 50nm from the surface, indicating that the electrolyte was O-doped only in the surface layer.
Fig. 3 is an XRD spectrum of the surface oxygen-enriched sulfide electrolyte material obtained in example 1 and the oxygen-free sulfide electrolyte obtained in comparative example 1. As can be seen from the figure, the surface oxygen-enriched sulfide electrolyte obtained in example 1 and the sulfide electrolyte obtained in comparative example 1 have no significant difference in XRD diffraction patterns, and the crystal structures thereof all meet JCPDS standard (34-0688, Li) 7 PS 6 ) It is shown that the surface O doping does not have an influence on the crystal structure of the electrolyte material.
Table 1 summarizes data of initial ion conductivity, exposed ion conductivity, first cycle specific discharge capacity of the simulated battery, and specific discharge capacity after 100 cycles of the electrolyte material of examples 1 to 9 and comparative examples 1 to 8, and experimental results show that the surface oxygen-enriched sulfide solid electrolyte material provided by the invention has high ion conductivity and high stability, and has good stability for an oxide cathode material.
TABLE 1 compaction Density and stability data for examples 1-9 and comparative examples 1-8
The surface oxygen-enriched sulfide solid electrolyte material and the preparation method thereof have the advantages of simple composition, easily obtained raw materials, simple preparation method, low production cost and better stability, and are expected to solve the problem of large-scale use of the sulfide solid electrolyte material.
The above examples are only for describing the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (10)
1. A sulfide solid state electrolyte material that is oxygen-rich in surface, the sulfide solid state electrolyte material containing lithium ions and anions that contain at least elemental sulfur, characterized in that an oxygen element is further contained in the sulfide solid state electrolyte material, the oxygen element being present in a non-uniform distribution so that the oxygen element is substantially enriched in an outer surface of the sulfide solid state electrolyte material.
2. The surface oxygen-rich sulfide solid state electrolyte material according to claim 1, characterized in that L/D ≦ 10%, wherein L represents a thickness of an outer surface oxygen-rich layer of the sulfide solid state electrolyte material, and D represents a particle diameter of the sulfide solid state electrolyte material;
preferably, L/D is more than or equal to 1% and less than or equal to 5%, and L is more than or equal to 5 nm.
3. A preparation method of a sulfide solid electrolyte material with oxygen-enriched surface is characterized by comprising the following steps:
1) providing a sulfide solid state electrolyte material substantially free of oxygen elements;
2) crushing the sulfide solid electrolyte material obtained in the step 1) in an oxygen-free medium;
3) crushing the sulfide solid electrolyte material treated in the step 2) in an oxygen-containing medium;
4) carrying out heat treatment on the sulfide solid electrolyte material treated in the step 3).
4. The method according to claim 3, wherein the oxygen-free medium in step 2) is an inert gas free of oxygen, preferably nitrogen, argon or a nitrogen/argon mixture;
and/or, the crushing treatment in the step 2) is ball milling treatment, the rotating speed is 200-500 rpm, and the time is 5-24 hours.
5. The method according to claim 3 or 4, wherein the oxygen-containing medium in step 3) is an inert gas containing oxygen, preferably nitrogen, argon or a nitrogen/argon mixture gas containing oxygen;
and/or the concentration of oxygen in the oxygen-containing medium in the step 3) is 100-5000 ppm, and preferably the concentration of oxygen is 3000-5000 ppm.
6. The preparation method according to any one of claims 3 to 5, wherein the crushing treatment in step 3) is ball milling treatment at a rotation speed of 100 to 300rpm for 2 to 12 hours, preferably at a rotation speed of 150 to 250rpm for 8 to 12 hours.
7. The method according to any one of claims 3 to 6, wherein the heat treatment temperature in step 4) is 250 ℃ to 350 ℃, the heat treatment time is 3 to 48 hours, and the protective gas is an inert gas.
8. A positive electrode layer for a solid-state battery, characterized by being produced from the surface-oxygen-rich sulfide solid-state electrolyte material according to any one of claims 1 to 2 or the surface-oxygen-rich sulfide solid-state electrolyte material produced by the production method according to any one of claims 3 to 7, a positive electrode material and a conductive agent.
9. An electrolyte layer for a solid-state battery, characterized by being produced from the surface-oxygen-rich sulfide solid-state electrolyte material according to any one of claims 1 to 2 or the surface-oxygen-rich sulfide solid-state electrolyte material produced by the production method according to any one of claims 3 to 7.
10. An all-solid-state lithium secondary battery comprising a positive electrode layer, a negative electrode layer and a solid electrolyte layer, wherein the positive electrode layer is the positive electrode layer according to claim 8, and the solid electrolyte layer is the electrolyte layer according to claim 9.
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