CN110931847A - Method for treating solid electrolyte and method for testing element content in solid electrolyte - Google Patents
Method for treating solid electrolyte and method for testing element content in solid electrolyte Download PDFInfo
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- CN110931847A CN110931847A CN201911295462.XA CN201911295462A CN110931847A CN 110931847 A CN110931847 A CN 110931847A CN 201911295462 A CN201911295462 A CN 201911295462A CN 110931847 A CN110931847 A CN 110931847A
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- solid electrolyte
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- sodium hydroxide
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000012360 testing method Methods 0.000 title claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 78
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000002253 acid Substances 0.000 claims abstract description 41
- 239000010936 titanium Substances 0.000 claims abstract description 40
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011574 phosphorus Substances 0.000 claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 168
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 55
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 15
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 12
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims description 10
- 238000002798 spectrophotometry method Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical group [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000010998 test method Methods 0.000 claims description 3
- 229910014217 MyO4 Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 39
- 239000011521 glass Substances 0.000 description 20
- 229910052759 nickel Inorganic materials 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 18
- 238000005303 weighing Methods 0.000 description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000012086 standard solution Substances 0.000 description 8
- QATHNKNPUVVKHK-UHFFFAOYSA-N 4-[(1,5-dimethyl-3-oxo-2-phenylpyrazol-4-yl)methyl]-1,5-dimethyl-2-phenylpyrazol-3-one Chemical compound O=C1N(C=2C=CC=CC=2)N(C)C(C)=C1CC(C1=O)=C(C)N(C)N1C1=CC=CC=C1 QATHNKNPUVVKHK-UHFFFAOYSA-N 0.000 description 6
- 229960005070 ascorbic acid Drugs 0.000 description 6
- 235000010323 ascorbic acid Nutrition 0.000 description 6
- 239000011668 ascorbic acid Substances 0.000 description 6
- 239000012085 test solution Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229940026189 antimony potassium tartrate Drugs 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910006210 Li1+xAlxTi2-x(PO4)3 Inorganic materials 0.000 description 1
- 229910006209 Li1+xAlxTi2−x Inorganic materials 0.000 description 1
- 229910006212 Li1+xAlxTi2−x(PO4)3 Inorganic materials 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- AVTYONGGKAJVTE-UHFFFAOYSA-L potassium tartrate Chemical compound [K+].[K+].[O-]C(=O)C(O)C(O)C([O-])=O AVTYONGGKAJVTE-UHFFFAOYSA-L 0.000 description 1
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
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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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Immunology (AREA)
- Electrochemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Plasma & Fusion (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of batteries, and discloses a method for processing a solid electrolyte and a method for testing the content of elements in the solid electrolyte. The method comprises the following steps: (1) carrying out first contact on a solid electrolyte and an alkaline substance to obtain a first contact material, wherein the temperature of the first contact is 500-1000 ℃; (2) carrying out second contact on the first contact material and a solvent to obtain a first contact material solution; (3) and carrying out third contact on the first contact material solution and acid to obtain a solid electrolyte solution. The method provided by the invention can be used for testing the content of elements such as lithium, aluminum, titanium, phosphorus and the like in the solid electrolyte, and is simple, good in test result reproducibility and high in accuracy.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a method for processing a solid electrolyte and a method for testing the content of elements in the solid electrolyte.
Background
In recent years, the increasing prominence of energy crisis and environmental pollution problems has prompted the rapid development of new energy technologies. The lithium ion battery has the outstanding advantages of high voltage, large energy density, good cycle performance, small self-discharge, no memory effect and the like, and is widely applied to the fields of portable electric tools, electronic equipment, electric automobiles, energy storage and the like. However, with the popularization of lithium ion batteries, the safety performance and the driving range of the lithium ion batteries become the focus of wide attention, and how to improve the energy density of the lithium ion batteries and simultaneously improve the safety performance and the cycle performance of the lithium ion batteries becomes a key problem to be solved urgently.
In order to solve the problems, two methods are currently researched, namely, the surface coating modification is carried out on the positive electrode material so as to relieve the problems of large interface resistance and lithium ion transmission resistance of the positive electrode material in the charging and discharging processes; and secondly, the solid electrolyte replaces the traditional electrolyte.
For example, CN109755512A discloses a high-nickel long-life multi-element cathode material and a preparation method thereof. In the patent document, a layer of nano-scale lithium aluminum titanium phosphate solid electrolyte is coated on the surface of the multielement material. The residual lithium carbonate content on the surface of the high nickel material is effectively reduced through intermolecular force, the interface impedance of the battery in the charging and discharging process is obviously reduced, and a lithium ion channel is constructed, so that the material has higher energy density and longer cycle life.
Lithium aluminum titanium phosphate is an NASICON-type inorganic solid electrolyte, and is used for surface coating of a positive electrode material or as a solid electrolyte of a lithium ion battery due to its stable structure and high ionic conductivity.
The molecular formula of the lithium aluminum titanium phosphate is Li1+xAlxTi2-x(PO4)3(LATP), wherein x is more than or equal to 0 and less than 2.
As the main element of the LATP, the content of phosphorus indicates whether the whole structure of the LATP is complete, and the low or high content of phosphorus indicates that the crystal structure of the material may have certain defects. The lithium to phosphorus content ratio also indicates whether the structural "skeleton" is intact. The actual amount of aluminum introduced is of great importance, since the unit size of the NASICON framework can be reduced by replacing titanium with a certain amount of aluminum, thereby increasing the conductivity.
However, solid-state electrolytes, as an emerging field of research, currently have no relevant methods and literature for testing the composition of LATP. The LATP is very stable in structure after high-temperature sintering, and in addition, titanium and phosphorus element compounds are not easy to dissolve in common acid, alkali and the like, so that the LATP is very difficult to dissolve, a good dissolving method is not available at present, and due to the defect of a testing method, the amount of each element in the LATP is generally calculated only by the input amount and is difficult to meet the actual situation.
Therefore, it is necessary to research a chemical analysis method for a solid electrolyte of a lithium ion battery, which can detect the content of elements such as lithium, phosphorus, titanium, and aluminum in the solid electrolyte.
Disclosure of Invention
The invention aims to overcome the defect that the solid electrolyte lithium titanium aluminum phosphate in the prior art is difficult to dissolve so that the components of the solid electrolyte lithium titanium aluminum phosphate are difficult to quantitatively analyze.
In order to achieve the above object, a first aspect of the present invention provides a method of treating a solid electrolyte, the method comprising:
(1) carrying out first contact on a solid electrolyte and an alkaline substance to obtain a first contact material, wherein the temperature of the first contact is 500-1000 ℃;
(2) carrying out second contact on the first contact material and a solvent to obtain a first contact material solution;
(3) and carrying out third contact on the first contact material solution and acid to obtain a solid electrolyte solution.
In a second aspect, the present invention provides a method of testing the elemental content of a solid electrolyte, the method comprising: sequentially dissolving the solid electrolyte and fixing the volume to obtain a solution to be detected;
and (b) testing the element content in the liquid to be tested by adopting the following mode (a) and/or mode (b):
(a) testing the content of lithium and/or aluminum in the liquid to be tested by using an inductively coupled plasma atomic emission spectrometry;
(b) testing the content of titanium and/or phosphorus in the solution to be tested by a spectrophotometry method;
wherein the dissolution treatment is carried out by the method of the first aspect.
The method for processing the solid electrolyte solves the problem of difficult dissolution of the solid electrolyte, so that the solid electrolyte can be further used for element quantitative analysis.
The method for testing the content of the elements in the solid electrolyte is simple by dissolving the solid electrolyte and then testing the content of the elements such as lithium, aluminum, titanium, phosphorus and the like in the solid electrolyte by using an inductively coupled plasma atomic emission spectrometry and/or a spectrophotometry, and further provides necessary technical support for the research and industrialization of the solid electrolyte.
Additional features and advantages of the invention will be described in detail in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously mentioned, a first aspect of the invention provides a method of treating a solid state electrolyte, the method comprising:
(1) carrying out first contact on a solid electrolyte and an alkaline substance to obtain a first contact material, wherein the temperature of the first contact is 500-1000 ℃;
(2) carrying out second contact on the first contact material and a solvent to obtain a first contact material solution;
(3) and carrying out third contact on the first contact material solution and acid to obtain a solid electrolyte solution.
Preferably, the solid electrolyte contains at least one element selected from lithium, aluminum, titanium and phosphorus.
Preferably, the method according to the first aspect of the present invention, further comprises: in the step (1), before the first contact, the solid electrolyte and the alkaline substance are mixed at 350 ℃ and 300 ℃, and then the mixed material obtained by mixing is subjected to the first contact.
In order to make the reaction and dissolution of the solid electrolyte in the prepared solid electrolyte solution more complete, it is preferable that the mixing at 350 ℃ of 300-. The layered mixing may be, for example, first taking a proper amount of the alkaline substance on the bottom layer, then spreading the solid electrolyte on the alkaline substance on the bottom layer, then spreading the rest alkaline substance on the solid electrolyte, and covering and wrapping the solid electrolyte to achieve layered mixing; for example, a part of the alkaline substance may be placed on the bottom layer, then the solid electrolyte is mixed with a proper amount of the alkaline substance by dry powder, the mixed dry powder is spread on the alkaline substance on the bottom layer, then the rest alkaline substance is spread on the mixed dry powder, and the mixed dry powder is covered and wrapped to realize layered mixing. And heating the materials obtained after the layering and mixing at the temperature of 300-350 ℃ to enable the alkaline substances to be molten and wrap the solid electrolyte to obtain the mixed material.
The time of the mixing is not particularly limited in the present invention as long as the solid electrolyte and the alkaline substance can be sufficiently mixed.
Preferably, according to the method of the first aspect of the present invention, in step (1), the time of the first contact is 5 to 30 min.
Preferably, the weight ratio of the alkaline substance to the solid electrolyte is 3-50: 1.
further preferably, the weight ratio of the alkaline substance to the solid electrolyte is 5-30: 1.
preferably, the alkaline substance is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium peroxide.
Further preferably, the alkaline substance is sodium hydroxide.
Preferably, according to the process of the first aspect of the present invention, in step (2), the solvent is selected from deionized water and/or distilled water.
In the present invention, the specific amount of the solvent is not particularly limited as long as the first contact material can be sufficiently dissolved in the solvent.
In order to promote dissolution of the first contact material, according to the method of the first aspect of the present invention, in step (2), preferably, the conditions of the second contact include: the temperature is 60-100 ℃.
In order to enable the first contact material solution and the acid to react sufficiently, preferably, in the step (3), the conditions of the third contact include: the temperature is 60-100 deg.C, and the time is 5-60 min.
Preferably, according to the method of the first aspect of the present invention, in the step (3), the acid is at least one selected from hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
More preferably, the acid is a mixed acid of hydrochloric acid and sulfuric acid.
Further preferably, the acid is a mixed acid formed by hydrochloric acid with the concentration of 8-14mol/L and sulfuric acid with the concentration of 16-20 mol/L.
Still more preferably, in the mixed acid, the volume ratio of the hydrochloric acid with the concentration of 8-14mol/L to the sulfuric acid with the concentration of 16-20mol/L is 3-10: the inventor unexpectedly finds that the third contact is carried out by using the mixed acid obtained by mixing the hydrochloric acid and the sulfuric acid with specific concentration and proportion and the first contact solution, so that the first contact can be dissolved more fully, and the test result, particularly the test result of Ti element, is higher in accuracy when the obtained solid electrolyte solution is used for the subsequent element component test.
In the present invention, the amount of the acid used is not particularly limited as long as the solid electrolyte can be sufficiently dissolved.
As previously mentioned, a second aspect of the invention provides a method of testing the elemental content of a solid state electrolyte, the method comprising: sequentially treating the solid electrolyte and fixing the volume to obtain a liquid to be detected;
and (b) testing the element content in the liquid to be tested by adopting the following mode (a) and/or mode (b):
(a) testing the content of lithium and/or aluminum in the liquid to be tested by using an inductively coupled plasma atomic emission spectrometry;
(b) testing the content of titanium and/or phosphorus in the solution to be tested by a spectrophotometry method;
wherein the treatment is carried out by the method of the first aspect.
The method according to the first aspect has been described in detail above, and the method according to the first aspect will not be described in detail in the second aspect of the present invention, and those skilled in the art should not be construed as limiting the present invention.
Preferably, the solid electrolyte is lithium aluminum titanium phosphate Li1+xAlxTi2-x(P1-yMyO4)3Wherein x is more than or equal to 0 and less than 2, y is more than or equal to 0 and less than 1, and M is selected from Si, Ge and Sn.
In the present invention, the specific form of the constant volume is not particularly limited, and for example, a solid electrolyte solution obtained by dissolving the solid electrolyte with water may be contained in a 200.0mL volumetric flask.
In order to more accurately determine the content of the element in the solution to be measured obtained by the method of the present invention, a person skilled in the art may dilute the obtained solution to be measured by a certain factor during or after preparing the solution to be measured and before using inductively coupled plasma atomic emission spectrometry (ICP-AES) and spectrophotometry, which are well known to the person skilled in the art, and the present invention is not described herein in detail, and the person skilled in the art should not be construed as a limitation to the present invention.
Meanwhile, in order to more accurately determine the content of the element in the solution to be detected obtained by the method of the present invention, when a spectrophotometry method is used for testing, the solution to be detected needs to be subjected to color development treatment known in the art, which is well known to those skilled in the art, and the present invention is not described herein again, and those skilled in the art should not be construed as limiting the present invention.
In the present invention, the operation parameters, instruments, containers, and the like used in the ICP-AES test and the spectrophotometry test are not particularly limited, and may be those conventionally used in the art.
The following provides a preferred specific procedure to illustrate the specific steps of the ICP-AES test and spectrophotometry test of the present invention:
(a) ICP-AES test
1. And (3) preparing a lithium standard working curve: transferring 10.00mL of 1000 mu g/mL lithium solution into a 1000mL volumetric flask, fixing the volume with water to obtain 10.00 mu g/mL lithium standard solution, transferring 0.00mL, 2.00mL, 4.00mL, 6.00mL, 8.00mL and 10.00mL lithium standard solution into 6 volumetric flasks with 50.00mL, fixing the volume with water to obtain 6 lithium solutions to be detected, and testing the lithium amount at 670.784nm characteristic spectral line to obtain a lithium standard working curve;
2. and (3) making an aluminum standard working curve: transferring 10.00mL of 1000 mug/mL aluminum solution into a 1000mL volumetric flask, fixing the volume with water to obtain 10.00 mug/mL aluminum standard solution, transferring 0.00mL, 2.00mL, 4.00mL, 6.00mL, 8.00mL and 10.00mL aluminum standard solution into another 6 volumetric flasks with 50.00mL, fixing the volume with water to obtain 6 aluminum solutions to be tested, and testing the aluminum amount at 396.153nm characteristic spectral line to obtain an aluminum standard working curve.
(b) Spectrophotometric method
3. Making a titanium standard working curve: 10g of Diantipyrylmethane (DAPM) is weighed into a beaker, 50.0mL of water is added, and 30mL of sulfuric acid (15mL of H) is added2O +15mL of 18.4mol/L H2SO4) Stirring until the solution is completely dissolved, placing the solution in a 1000mL volumetric flask, cooling, and fixing the volume with water to obtain a DAPM solution;
transferring 10.00mL of 1000-microgram/mL titanium solution into a 1000-mL volumetric flask, fixing the volume with water for standby use to obtain 10.00-microgram/mL titanium standard solution, transferring 0.00mL, 1.00mL, 2.00mL, 3.00mL, 4.00mL and 5.00mL titanium standard solution into a 25.00-mL colorimetric tube respectively, adding 3.50mL of 12mol/L HCl and 10.00mL DAPM solution, fixing the volume with water, standing for 20min, and using an ultraviolet visible spectrophotometer (the model used in the invention is TU-PC, but not limited thereto), measuring the absorbance at 380m by using a cuvette with a light path of 1cm to obtain a titanium standard working curve;
4. standard operating curve of phosphorus: weighing 1g of ascorbic acid in a beaker, adding 50.0mL of water to dissolve the ascorbic acid, transferring the ascorbic acid into a 100.0mL brown glass volumetric flask, adding water to a constant volume, and uniformly mixing to obtain an ascorbic acid solution;
0.65g of ammonium molybdate was weighed into beaker A and dissolved by adding 50.0mL of water. 0.17g of antimony potassium tartrate was weighed into a beaker B, and 50.0mL of water was added to dissolve it. To beaker C was added 75.0mL of water and 75.0mL of 18.4mol/L sulfuric acid was added along the wall of the beaker with stirring to give 150.0mL of sulfuric acid. Adding the ammonium molybdate solution in the beaker A into a beaker C under stirring, adding the antimony tartrate potassium solution in the beaker B into the beaker C, uniformly mixing, and storing in a brown reagent bottle to obtain an ammonium molybdate-antimony tartrate potassium solution;
transferring 10.00mL of phosphorus solution with the concentration of 1000 mug/mL into a 1000mL glass volumetric flask, adding water to a constant volume to obtain 10.00 mug/mL phosphorus standard solution, adding 0.00mL, 0.50mL, 1.00mL, 1.50mL, 2.00mL and 3.00mL of phosphorus standard solution with the concentration of 10.00 mug/mL into a 25.00mL colorimetric tube respectively, adding water to a constant volume, adding 1.00mL of ascorbic acid solution, mixing for 30s to fully mix, adding 2.00mL of ammonium molybdate-antimony potassium tartrate solution, standing for 15-30 min, and testing absorbance at 706.6m by using an ultraviolet visible spectrophotometer (the model used in the invention is TU-1810PC, but not limited thereto), a cuvette with the optical path of 1cm to obtain a phosphorus standard working curve.
In the present invention, unless otherwise specified, a solution means a solution or a suspension or a glue solution in a liquid form.
The present invention will be described in detail below by way of examples.
In the following examples, all the raw materials used are commercially available ones unless otherwise specified.
Unless otherwise specified, only reagents identified as analytically pure or guaranteed to be of superior purity and distilled or deionized water or water of comparable purity are used in the analysis.
In the following examples:
in examples 1 to 9: the acid is a mixed acid of hydrochloric acid with the concentration of 12mol/L and sulfuric acid with the concentration of 18.4mol/L, wherein the mixing volume ratio of the hydrochloric acid to the sulfuric acid is 3: 1;
in example 10: the acid is hydrochloric acid with the concentration of 12 mol/L;
in example 11: the acid is sulfuric acid with the concentration of 18.4 mol/L;
in example 12: the acid is a mixed acid of hydrochloric acid with the concentration of 12mol/L and sulfuric acid with the concentration of 18.4mol/L, wherein the mixing volume ratio of the hydrochloric acid to the sulfuric acid is 1: 1.
example 1
(1) In a nickel crucible, 0.3g of sodium hydroxide was weighed, the bottom of the crucible was covered with sodium hydroxide to form a sodium hydroxide layer, and 0.1002g of Li was weighed1.3Al0.3Ti1.7(PO4)3(LATP-1#) is placed on the sodium hydroxide layer, 0.2g of sodium hydroxide is weighed to cover the LATP-1#, the crucible is covered on an electric furnace and heated until the sodium hydroxide is molten, the LATP-1# is covered, and then nickel with a cover is coatedPlacing the crucible in a muffle furnace, preserving the temperature for 10min at 700 ℃ for carrying out a first contact reaction, and naturally cooling to obtain a first contact material;
(2) putting the first contact material into water at 60 ℃ to obtain 20mL of first contact material solution;
(3) adding 20mL of mixed acid into the first contact solution obtained in the step (2), covering a watch glass to prevent hydrochloric acid from volatilizing too fast, and heating for 20min at 100 ℃ to obtain a solid electrolyte solution;
(4) and (3) using water to fix and contain the solid electrolyte solution in a 200.0mL glass volumetric flask to obtain a solution to be detected.
Example 2
(1) In a nickel crucible, 0.3g of sodium hydroxide was weighed, the bottom of the crucible was covered with sodium hydroxide to form a sodium hydroxide layer, and 0.1002g of Li was weighed1.3Al0.3Ti1.7(PO4)3Placing (LATP-1#) on a sodium hydroxide layer, weighing 0.2g of sodium hydroxide to cover the LATP-1#, covering a crucible cover on an electric furnace, heating until the sodium hydroxide is molten, wrapping the LATP-1#, then placing a nickel crucible with a cover in a muffle furnace, preserving heat at 600 ℃ for 20min to perform a first contact reaction, and naturally cooling to obtain a first contact material;
(2) putting the first contact material into water at 80 ℃ to obtain 20mL of first contact material solution;
(3) adding 20mL of mixed acid into the first contact solution obtained in the step (2), covering a watch glass to prevent hydrochloric acid from volatilizing too fast, and heating for 40min at 80 ℃ to obtain a solid electrolyte solution;
(4) and (3) using water to fix and contain the solid electrolyte solution in a 200.0mL glass volumetric flask to obtain a solution to be detected.
Example 3
(1) Weighing 0.5g of sodium hydroxide in a nickel crucible, paving the sodium hydroxide at the bottom of the crucible to form a sodium hydroxide layer, weighing 0.1005g of LATP-1#, placing the LATP-1# on the sodium hydroxide layer, weighing 0.5g of sodium hydroxide to cover the LATP-1#, covering the crucible on an electric furnace, heating the crucible until the sodium hydroxide is molten, wrapping the LATP-1#, placing the nickel crucible with the cover in a muffle furnace, preserving the heat at 700 ℃ for 10min to perform a first contact reaction, and naturally cooling to obtain a first contact material;
(2) putting the first contact material into water at 60 ℃ to obtain 20mL of first contact material solution;
(3) adding 20mL of mixed acid into the first contact solution obtained in the step (2), covering a watch glass to prevent hydrochloric acid from volatilizing too fast, and heating for 25min at 100 ℃ to obtain a solid electrolyte solution;
(4) and (3) using water to fix and contain the solid electrolyte solution in a 200.0mL glass volumetric flask to obtain a solution to be detected.
Example 4
(1) Weighing 1g of sodium hydroxide in a nickel crucible, paving the sodium hydroxide at the bottom of the crucible to form a sodium hydroxide layer, weighing 0.1003g of LATP-1#, placing the LaTP-1#, weighing 0.5g of sodium hydroxide to cover the LaTP-1#, covering the crucible cover on an electric furnace, heating until the sodium hydroxide is molten, wrapping the LATP-1#, placing the nickel crucible with the cover in a muffle furnace, preserving the heat at 700 ℃ for 10min to perform a first contact reaction, and naturally cooling to obtain a first contact solution;
(2) putting the first contact material into water at 60 ℃ to obtain 20mL of first contact material solution;
(3) adding 20mL of mixed acid into the first contact solution obtained in the step (2), covering a watch glass to prevent hydrochloric acid from volatilizing too fast, and heating for 20min at 100 ℃ to obtain a solid electrolyte solution;
(4) and (3) using water to fix and contain the solid electrolyte solution in a 200.0mL glass volumetric flask to obtain a solution to be detected.
Example 5
(1) Weighing 2g of sodium hydroxide in a nickel crucible, paving the sodium hydroxide at the bottom of the crucible to form a sodium hydroxide layer, weighing 0.1005g of LATP-1#, placing the LATP-1#, weighing 1g of sodium hydroxide to cover the LATP-1#, covering the crucible with a cover on an electric furnace, heating until the sodium hydroxide is molten, wrapping the LATP-1#, placing the nickel crucible with the cover in a muffle furnace, preserving the heat at 700 ℃ for 10min to perform a first contact reaction, and naturally cooling to obtain a first contact material;
(2) putting the first contact material into water at 60 ℃ to obtain 20mL of first contact material solution;
(3) adding 20mL of mixed acid into the first contact solution obtained in the step (2), covering a watch glass to prevent hydrochloric acid from volatilizing too fast, and heating for 20min at 100 ℃ to obtain a solid electrolyte solution;
(4) and (3) using water to fix and contain the solid electrolyte solution in a 200.0mL glass volumetric flask to obtain a solution to be detected.
Example 6
(1) In a nickel crucible, 0.5g of sodium hydroxide was weighed, the bottom of the crucible was covered with sodium hydroxide to form a sodium hydroxide layer, and 0.1002g of Li was weighed1Ti2(PO4)3Placing (LATP-2#) on a sodium hydroxide layer, weighing 0.5g of sodium hydroxide to cover the LATP-2#, covering a crucible cover on an electric furnace, heating until the sodium hydroxide is molten, wrapping the LATP-2#, placing a nickel crucible with a cover in a muffle furnace, preserving heat at 700 ℃ for 10min to perform a first contact reaction, and naturally cooling to obtain a first contact material;
(2) putting the first contact material into water at 60 ℃ to obtain 20mL of first contact material solution;
(3) adding 20mL of mixed acid into the first contact solution obtained in the step (2), covering a watch glass to prevent hydrochloric acid from volatilizing too fast, and heating for 20min at 100 ℃ to obtain a solid electrolyte solution;
(4) and (3) using water to fix and contain the solid electrolyte solution in a 200.0mL glass volumetric flask to obtain a solution to be detected.
Example 7
(1) In a nickel crucible, 0.5g of sodium hydroxide was weighed, the bottom of the crucible was covered with sodium hydroxide to form a sodium hydroxide layer, and 0.1002g of Li was weighed1.1Al0.1Ti1.9(PO4)3Placing (LATP-3#) on a sodium hydroxide layer, weighing 0.5g of sodium hydroxide to cover the LATP-3#, covering a crucible cover on an electric furnace, heating until the sodium hydroxide is molten, wrapping the LATP-3#, placing a nickel crucible with a cover in a muffle furnace, preserving heat at 700 ℃ for 10min to perform a first contact reaction, and naturally cooling to obtain a first contact material;
(2) putting the first contact material into water at 60 ℃ to obtain 20mL of first contact material solution;
(3) adding 20mL of mixed acid into the first contact solution obtained in the step (2), covering a watch glass to prevent hydrochloric acid from volatilizing too fast, and heating for 20min at 100 ℃ to obtain a solid electrolyte solution;
(4) and (3) using water to fix and contain the solid electrolyte solution in a 200.0mL glass volumetric flask to obtain a solution to be detected.
Example 8
(1) In a nickel crucible, 0.5g of sodium hydroxide was weighed, the bottom of the crucible was covered with sodium hydroxide to form a sodium hydroxide layer, and 0.1002g of Li was weighed1.5Al0.5Ti1.5(PO4)3Placing (LATP-4#) on a sodium hydroxide layer, weighing 0.5g of sodium hydroxide to cover the LATP-4#, covering a crucible cover on an electric furnace, heating until the sodium hydroxide is molten, wrapping the LATP-4#, placing a nickel crucible with a cover in a muffle furnace, preserving heat at 700 ℃ for 10min to perform a first contact reaction, and naturally cooling to obtain a first contact material;
(2) putting the first contact material into water at 60 ℃ to obtain 20mL of first contact material solution;
(3) adding 20mL of mixed acid into the first contact solution obtained in the step (2), covering a watch glass to prevent hydrochloric acid from volatilizing too fast, and heating for 20min at 100 ℃ to obtain a solid electrolyte solution;
(4) and (3) using water to fix and contain the solid electrolyte solution in a 200.0mL glass volumetric flask to obtain a solution to be detected.
Example 9
(1) In a nickel crucible, 0.5g of sodium hydroxide was weighed, the bottom of the crucible was covered with sodium hydroxide to form a sodium hydroxide layer, and 0.1003g of Li was weighed1.3Ti2Si0.3P2.7O12Placing (LATP-5#) on a sodium hydroxide layer, weighing 0.5g of sodium hydroxide to cover the LATP-5#, covering a crucible cover on an electric furnace, heating until the sodium hydroxide is molten, wrapping the LATP-5#, placing a nickel crucible with a cover in a muffle furnace, preserving heat at 700 ℃ for 10min to perform a first contact reaction, and naturally cooling to obtain a first contact material;
(2) putting the first contact material into water at 60 ℃ to obtain 20mL of first contact material solution;
(3) adding 20mL of mixed acid into the first contact solution obtained in the step (2), covering a watch glass to prevent hydrochloric acid from volatilizing too fast, and heating for 20min at 100 ℃ to obtain a solid electrolyte solution;
(4) and (3) using water to fix and contain the solid electrolyte solution in a 200.0mL glass volumetric flask to obtain a solution to be detected.
Example 10
A test solution was prepared in a similar manner to example 1 except that 31mL of hydrochloric acid having a concentration of 12mol/L was used in place of the mixed acid in example 1, and the remainder was the same as in example 1, to obtain a test solution.
Example 11
A test solution was prepared in a similar manner to example 1 except that 10mL of sulfuric acid having a concentration of 18.4mol/L was used in place of the mixed acid in example 1, and the remainder was the same as in example 1, to obtain a test solution.
Example 12
A test solution was prepared in a similar manner to example 1 except that 15mL of a mixed acid (hydrochloric acid and sulfuric acid at a mixed volume ratio of 1:1) was used in place of the mixed acid in example 1, and the remainder was the same as in example 1, to obtain a test solution.
Test example
(a) Diluting the solution to be tested obtained in the above example by 10 times, and respectively obtaining the content c of the lithium element in the diluted solution according to a lithium standard working curve and an aluminum standard working curve by an ICP-AES test(Li)(. mu.g/mL) and the aluminum content c(Al)(mu g/mL), and further calculating to obtain the actually measured content of lithium and aluminum elements in the solid electrolyte, wherein the specific result is shown in Table 1;
(b) diluting the solution to be tested obtained in the above example by 10 times, adding 3.00mL of HCl and 10.00mL of DAPM solution into a 25.00mL colorimetric tube, adding 3.50mL of HCl and 10.00mL of DAPM solution, fixing the volume with water, standing for 20min, and testing absorbance A at 380m by using a TU-1810PC ultraviolet-visible spectrophotometer and a cuvette with a 1cm light path(Ti)Obtaining the content of the titanium element c in the colorimetric tube according to the standard working curve of the titanium(Ti)(μ g/mL) and further calculated to giveThe actual measurement content of the titanium element in the solid electrolyte is shown in the table 1;
diluting the solution to be tested obtained in the above example by 10 times, adding 1.50mL of the solution into a 25.00mL colorimetric tube, adding 1.00mL of ascorbic acid solution, mixing for 30s, adding 2.00mL of ammonium molybdate-antimony potassium tartrate solution, standing for 20min, and testing absorbance A at 706.6m by using a TU-1810PC ultraviolet-visible spectrophotometer and a cuvette with a 1cm light path(P)Obtaining the content of the phosphorus element in the colorimetric tube as c according to the phosphorus standard working curve(P)(mu g/mL) and then calculating to obtain the measured content of the phosphorus element in the solid electrolyte, and the specific results are shown in Table 1.
The actually measured content of Li, Al, Ti and P elements in the solid electrolyte is calculated by the following formula:
measured content of Li ═ c(Li)×10×200.0×10-6)/m×100％；
Measured content of Al ═ c(Al)×10×200.0×10-6)/m×100％；
Measured content of Ti ═ c(Ti)×25.00×10×200.0×10-6/3)/m×100％；
Measured content of P ═ c(P)×25.00×10×200.0×10-6/1.50)/m×100％；
Wherein m is the mass of the solid electrolyte.
TABLE 1
Table 1 (continuation watch)
It should be noted that the results of examples 2-12 in the above table are the average of the results obtained by testing three times, and the invention exemplarily provides the results of three times of test in example 1 to confirm that the method provided by the invention has good reproducibility.
In the context of the present invention, the theoretical content is a solid electrolyte having a defined molecular formula, for example LiaAlbTicPdOeThe theoretical contents of lithium, aluminum, titanium and phosphorus are calculated by the following formula:
theoretical content of Li ═ MLi×a/(MLi×a+MAl×b+MTi×c+MP×d+MO×e)×100％；
Theoretical content of Al ═ MAl×b/(MLi×a+MAl×b+MTi×c+MP×d+MO×e)×100％；
Theoretical content of Ti ═ MTi×c/(MLi×a+MAl×b+MTi×c+MP×d+MO×e)×100％；
Theoretical content of P ═ MP×d/(MLi×a+MAl×b+MTi×c+MP×d+MO×e)×100％；
Wherein M isLi、MAl、MTi、MP、MOThe molar masses of lithium, aluminum, titanium, phosphorus and oxygen, respectively, and when other doping elements are contained in the molecular formula, the calculation of the theoretical content is the same as the above, and is not repeated herein.
From the results, the solid electrolyte is subjected to alkali fusion-acid dissolution treatment by the method provided by the invention, so that the solution to be tested of the solid electrolyte for ICP and spectrophotometry can be obtained, the content of elements such as lithium, aluminum, titanium, phosphorus and the like in the solid electrolyte can be tested, and the method is simple and reliable and has good reproducibility.
Further, as can be seen from comparison of examples 1 to 9 with examples 10 to 12, the solid electrolyte solution obtained by the treatment of combining the alkali with the mixed acid of hydrochloric acid and sulfuric acid having a specific ratio and concentration has higher accuracy of the test results, particularly the test results of Ti element, when used for the test.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A method of treating a solid state electrolyte, the method comprising:
(1) carrying out first contact on a solid electrolyte and an alkaline substance to obtain a first contact material, wherein the temperature of the first contact is 500-1000 ℃;
(2) carrying out second contact on the first contact material and a solvent to obtain a first contact material solution;
(3) carrying out third contact on the first contact material solution and acid to obtain a solid electrolyte solution;
preferably, the solid electrolyte contains at least one element selected from lithium, aluminum, titanium and phosphorus.
2. The method of claim 1, wherein the method further comprises: in the step (1), before the first contact, the solid electrolyte and the alkaline substance are mixed at 350 ℃ and 300 ℃, and then the mixed material obtained by mixing is subjected to the first contact.
3. The method of claim 1 or 2, wherein the time of the first contacting is 5-30 min.
4. The method according to any one of claims 1 to 3, wherein the alkaline substance is used in a weight ratio of the alkaline substance to the solid electrolyte of 3 to 50: 1;
preferably, the weight ratio of the alkaline substance to the solid electrolyte is 5-30: 1.
5. the method according to any one of claims 1 to 4, wherein the alkaline substance is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium peroxide;
preferably, the alkaline substance is sodium hydroxide.
6. The method of any one of claims 1-4, wherein in step (3), the conditions of the third contacting comprise: the temperature is 60-100 deg.C, and the time is 5-60 min.
7. The method according to any one of claims 1 to 4, wherein, in the step (3), the acid is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid;
preferably, the acid is a mixed acid of hydrochloric acid and sulfuric acid.
8. The method according to any one of claims 1 to 4, wherein the acid is a mixed acid of hydrochloric acid having a concentration of 8 to 14mol/L and sulfuric acid having a concentration of 16 to 20 mol/L.
9. The method of claim 8, wherein, in the mixed acid, the volume ratio of the hydrochloric acid to the sulfuric acid is 3-10: 1.
10. a method of testing the elemental content of a solid electrolyte, the method comprising: sequentially dissolving the solid electrolyte and fixing the volume to obtain a solution to be detected;
and (b) testing the element content in the liquid to be tested by adopting the following mode (a) and/or mode (b):
(a) testing the content of lithium and/or aluminum in the liquid to be tested by using an inductively coupled plasma atomic emission spectrometry;
(b) testing the content of titanium and/or phosphorus in the solution to be tested by a spectrophotometry method;
wherein the dissolution treatment is carried out by the method according to any one of claims 1 to 9.
11. The method of claim 10, wherein the solid state electrolyte is lithium aluminum titanium phosphate (Li)1+xAlxTi2-x(P1- yMyO4)3Wherein x is more than or equal to 0 and less than 2, y is more than or equal to 0 and less than 1, and M is selected from Si, Ge and Sn.
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