CN114772627B - Dehydration purification method and application of solid electrolyte - Google Patents
Dehydration purification method and application of solid electrolyte Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 212
- 230000018044 dehydration Effects 0.000 title claims abstract description 80
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 80
- 238000000746 purification Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 105
- 238000010438 heat treatment Methods 0.000 claims abstract description 60
- 239000000654 additive Substances 0.000 claims abstract description 57
- 230000000996 additive effect Effects 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims description 41
- 239000012298 atmosphere Substances 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 17
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 38
- 239000013078 crystal Substances 0.000 abstract description 14
- 238000009835 boiling Methods 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 description 76
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000002001 electrolyte material Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/36—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 halogen being the only anion, e.g. NaYF4
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- C—CHEMISTRY; METALLURGY
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
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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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- 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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
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Abstract
The invention relates to the technical field of solid-state batteries, in particular to a dehydration purification method and application of a solid-state electrolyte. The dehydration and purification method provided by the invention comprises the following steps: contacting the solid electrolyte to be treated with a dehydration additive, and then heating to obtain the dehydrated and purified solid electrolyte; the dehydration additive satisfies at least the following conditions: the binding capacity of the dehydrated additive material with the solid electrolyte is superior to the binding capacity of water with the solid electrolyte; the decomposition temperature of the substance after the dehydration additive is combined with the solid electrolyte is lower than the collapse temperature of the crystal structure of the solid electrolyte; the boiling point of the dehydrated additive material is below the collapse temperature of the crystal structure of the solid electrolyte. Compared with other existing modes, the dehydration purification method provided by the invention has the advantages that the obtained electrolyte can be restored to the original conductivity level, and the battery can have higher capacity exertion and cycle retention rate.
Description
Technical Field
The invention relates to the technical field of solid-state batteries, in particular to a dehydration purification method and application of a solid-state electrolyte.
Background
The solid-state battery adopts the nonflammable solid electrolyte to replace the flammable organic liquid electrolyte, so that the safety of the battery system is greatly improved, meanwhile, the high-energy anode and the high-energy cathode can be better adapted, the weight of the system is reduced, and the synchronous improvement of the energy density is realized. Among various new battery systems, solid-state batteries are the next generation technology closest to industrialization, which has become a consensus of industry and scientific community.
Solid-state electrolytes are used in solid-state batteries instead of electrolyte components in conventional liquid-state batteries, but currently used inorganic solid-state electrolytes (including sulfide electrolytes, oxide electrolytes, halide electrolytes, etc.) generally have characteristics that are sensitive to water and that are extremely water-absorbent. Based on the above characteristics of the solid electrolyte, even if the solid electrolyte material can completely remove the moisture in the material by means of high-temperature sintering or the like during the preparation process, the solid electrolyte is inevitably contacted with trace moisture existing in the atmosphere or in the packaging container during long-term storage, and the solid electrolyte is extremely sensitive to the moisture and has strong water absorption capacity, the moisture existing outside gradually diffuses into the solid electrolyte with stronger water-capturing capacity, so that the solid electrolyte Li is a halide solid electrolyte 3 MX 6 (X can be one or more of F, cl and Br; M can be one or more of Sc, Y, zr, hf, ga, in, la, ce, pr, nd, pm, sm, eu, ga, la, dy, ho, er, tm, yb, lu) in solid electrolyte Li 3 MX 6 Upon contact with moisture in the atmosphere, a hydrate of the solid electrolyte, li, is formed 3 MX 6 ·nH 2 O(n≤8)。Li 3 MX 6 ·nH 2 O cannot withstand the voltage during the charge and discharge of the battery, and thus is decomposed during the charge and discharge of the battery, which is manifested as a decrease in battery capacity and a decrease in cycle life.
In addition, due to Li 3 MX 6 ·nH 2 The moisture in O exists as crystal water and cannot be easily removed by vacuum drying at low temperature. At present, li is generally calcined at high temperature 3 MX 6 ·nH 2 Removal of crystal water from O, li 3 MX 6 ·nH 2 O is present after heating as follows:
Li 3 MX 6 ·nH 2 O→3LiX+MOX+2HX↑+(n-1)H 2 O↑。
from the above formula, it can be seen that Li can be calcined at high temperature 3 MX 6 ·nH 2 Bound water in O is removed, but Li 3 MX 6 Due to H in the dehydration process 2 The effect of O can be cracked, and the generated LiX and MOX have no conductivity, so that the conductivity of the electrolyte after heat treatment is obviously reduced, the battery capacity is reduced, and the cycle performance is deteriorated.
Disclosure of Invention
The invention aims to overcome the defects that the existing method for dehydrating and purifying the solid electrolyte after water absorption by adopting a high-temperature calcination method causes cracking of the solid electrolyte in the dehydration process, and the generated LiX and MOX have no conductivity, so that the conductivity of the electrolyte after high-temperature calcination is obviously reduced, the battery capacity is reduced and the cycle performance is poor, and further provides a dehydration and purification method and application of the solid electrolyte.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for dehydration and purification of a solid electrolyte, comprising the steps of:
contacting the solid electrolyte to be treated with a dehydration additive, and then heating to obtain the dehydrated and purified solid electrolyte;
the dehydration additive satisfies at least the following conditions:
1) The binding capacity of the dehydrated additive material with the solid electrolyte is superior to the binding capacity of water with the solid electrolyte;
2) Decomposition temperature T of substance after dehydration additive and solid electrolyte are combined 1 Below the collapse temperature T of the crystal structure of the solid electrolyte 0 ；
3) Boiling point T of dehydration additive substance 2 Below the collapse temperature T of the crystal structure of the solid electrolyte 0 。
In order to avoid the generation of impurities caused by thermal cracking of the solid electrolyte during the water removal process, the solid electrolyte Li is halogenated 3 MX 6 For example, the invention is first described in Li 3 MX 6 ·nH 2 Introduction of solid electrolyte Li into O 3 MX 6 And H is 2 The third substance other than O, namely the dehydration additive, is a dehydration additive and Li 3 MX 6 ·nH 2 O is fully contacted with Li due to the dehydration additive 3 MX 6 The following reactions occur when the binding capacity of (a) is higher: li (Li) 3 MX 6 ·nH 2 O+nZ→Li 3 MX 6 ·nZ+nH 2 O, then adding the above Li 3 MX 6 nZ and nH 2 The mixture of O is heated at high temperature to remove impurities: li (Li) 3 MX 6 ·nZ+nH 2 O→Li 3 MX 6 +nZ↑+nH 2 O↑。
Preferably, the dehydration additive is in a gaseous or liquid state; preferably, the dehydration additive is selected from the group consisting of NH 4 F aqueous solution, NH 4 Aqueous Cl solution, NH 4 Br aqueous solution, NH 3 、F 2 、Cl 2 、Br 2 At least one of HCl aqueous solution and HBr aqueous solution. It will be appreciated that when the dehydration additive is in a liquid state, for example when the dehydration additive is NH 4 F aqueous solution, NH 4 Aqueous Cl solution, NH 4 When at least one of Br aqueous solution, HCl aqueous solution and HBr aqueous solution is used, the binding capacity of solute and solid electrolyte in the dehydration additive is better than that of water and solid electrolyte; decomposition temperature T of substance after solute and solid electrolyte are combined in dehydration additive 1 Below the collapse temperature T of the crystal structure of the solid electrolyte 0 The method comprises the steps of carrying out a first treatment on the surface of the Boiling point T of dehydration additive 2 Below the collapse temperature T of the crystal structure of the solid electrolyte 0 。
Preferably, when the dehydration additive is in a gaseous state, the contact of the solid electrolyte with the dehydration additive is performed under an atmosphere of the dehydration additive;
when the dehydration additive is in a liquid state, the contact of the solid electrolyte with the dehydration additive is performed under an inert atmosphere. The inert atmosphere in the present invention refers to a nitrogen atmosphere or an inert rare gas atmosphere.
Preferably, the contact time of the solid electrolyte to be treated and the dehydration additive is 1h-40h.
Preferably, the heating temperature T satisfies: t (T) 0 >T>T 1 And T is>T 2 T is not lower than waterT is the boiling point of (1) 1 >T 2 ；
Preferably, the heating temperature T is 410-540 ℃, and the heating time is 1-8 h.
Preferably, the method comprises the steps of,
when the dehydration additive is selected from NH 3 、F 2 、Cl 2 、Br 2 In at least one of the above, the dehydration purification method comprises the steps of:
placing the solid electrolyte to be treated in a dehydration additive gas atmosphere to enable the solid electrolyte to be fully contacted with the dehydration additive for 6-40h, then taking the solid electrolyte out of the dehydration additive gas atmosphere, heating the solid electrolyte to 410-500 ℃ in an inert atmosphere at a heating rate of 1-5 ℃/min, and preserving heat for 120-720min at a temperature of 410-500 ℃; finally, cooling the solid electrolyte material from 410-500 ℃ to room temperature at a cooling rate of 1-10 ℃/min to obtain the dehydrated and purified solid electrolyte;
when the dehydration additive is selected from NH 4 F aqueous solution, NH 4 Aqueous Cl solution, NH 4 When at least one of Br aqueous solution, HCl aqueous solution and HBr aqueous solution is adopted, the dehydration purification method comprises the following steps:
placing the solid electrolyte to be treated in a dehydration additive under inert atmosphere, stirring for 1-36h, heating the mixed solution to 90-120 ℃, keeping the temperature at the heating rate of 1-10 ℃/min, and keeping the temperature at 90-120 ℃ for 10-120min; then continuously heating from 90-120 ℃ to 300-400 ℃ at a heating rate of 1-10 ℃/min, and preserving heat for 5-60min at 300-400 ℃; then continuously heating from 300-400 ℃ to 410-500 ℃ at a heating rate of 1-5 ℃/min, and preserving heat for 120-720min at the temperature of 410-500 ℃; and finally, cooling the solid electrolyte material from the temperature of 410-500 ℃ to the room temperature at the cooling rate of 1-10 ℃/min to obtain the dehydrated and purified solid electrolyte.
The solid electrolyte to be treated is a solid electrolyte after water absorption; the invention does not specifically limit the water absorption of the solid electrolyte after water absorption, and the water absorption is optionally between 0 and 9 percent. In solid electrolyte Li 3 MX 6 For example, it is contacted with moisture in the atmosphereAfter that, a hydrate of the solid electrolyte, namely Li, is formed 3 MX 6 ·nH 2 O(n≤8)。
When the dehydration additive is selected from NH 4 F aqueous solution, NH 4 Aqueous Cl solution, NH 4 When at least one of Br aqueous solution, HCl aqueous solution and HBr aqueous solution is used, the mole ratio of solute in the dehydration additive to solid electrolyte to be treated is (1.2-3): 1, and the mass ratio of solute in the dehydration additive to water is (2-4): 10. It will be appreciated that the solutes herein correspond to NH in the respective aqueous solutions, respectively 4 F、NH 4 Cl、NH 4 Br、HCl、HBr。
Preferably, the method comprises the steps of,
the solid electrolyte includes a sulfide solid electrolyte, an oxide solid electrolyte, and a halide solid electrolyte; preferably, the solid electrolyte is a halide solid electrolyte, preferably having the chemical formula Li 3 MX 6 Wherein X is selected from one or more of F, cl and Br; m is selected from one or more of Sc, Y, zr, hf, ga, in, la, ce, pr, nd, pm, sm, eu, ga, la, dy, ho, er, tm, yb, lu.
The invention also provides a lithium secondary battery, which comprises a positive electrode layer, an electrolyte layer and a negative electrode layer, wherein at least one layer of the positive electrode layer, the electrolyte layer and the negative electrode layer contains the solid electrolyte obtained by the method.
The invention has the beneficial effects that:
1. the invention provides a dehydration and purification method of solid electrolyte, which comprises the steps of introducing solid electrolyte and H into the solid electrolyte to be treated 2 The binding capacity of the dehydration additive substances other than O and the solid electrolyte is better than that of water by controlling the binding capacity of the dehydration additive substances and the solid electrolyte; decomposition temperature T of substance after dehydration additive and solid electrolyte are combined 1 Below the collapse temperature T of the crystal structure of the solid electrolyte 0 The method comprises the steps of carrying out a first treatment on the surface of the The boiling point of the dehydration additive is lower than the crystal structure collapse temperature T of the solid electrolyte 0 And further contacting the solid electrolyte with the solution to be treated, and substituting crystal water in the solid electrolyteAfter the generation, the combination of the additive and the solid electrolyte is cracked by heating, so that the problems of reduced capacity and poor cycle performance of the electrolyte battery are avoided, and oxyhalide is generated by directly heating and decomposing the solid electrolyte after water absorption, so that the solid electrolyte can be restored to the original state after water absorption, the conductivity of the solid electrolyte material is reduced after dehydration, and the problems of reduced capacity and poor cycle performance of the electrolyte battery are solved.
Compared with the method for directly using the electrolyte after water absorption or using the traditional method for directly heating and dewatering the electrolyte after water absorption, the method for dewatering and purifying the solid electrolyte provided by the invention can restore the electrolyte treated by the method to the original conductivity level, and compared with other methods, the battery using the solid electrolyte provided by the invention can have higher capacity exertion and cycle retention rate.
2. The invention provides a dehydration purification method of solid electrolyte, further, the dehydration additive is selected from NH 4 F aqueous solution, NH 4 Aqueous Cl solution, NH 4 Br aqueous solution, NH 3 、F 2 、Cl 2 、Br 2 At least one of HCl aqueous solution and HBr aqueous solution. The invention adopts the specific dehydration additive to make the solid electrolyte fully contact with the solid electrolyte to be treated, replaces crystal water in the solid electrolyte, and then cracks the combination of the additive and the solid electrolyte by heating after replacing, thereby effectively avoiding the problems of reduced conductivity, reduced capacity and poor cycle performance of the electrolyte battery after the solid electrolyte material is dehydrated.
3. The dehydration and purification method of the solid electrolyte provided by the invention further comprises the following steps of: t (T) 0 >T>T 1 And T is>T 2 T is not lower than the boiling point of water, T 1 >T 2 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the heating temperature T is 410-540 ℃, and the heating time is 1-8 h. The invention can effectively ensure the pyrolysis of the combination of the additive and the solid electrolyte by controlling the specific heating temperature, does not damage the original solid electrolyte structure and produce impurities, further ensures that the conductivity of the electrolyte material is not obviously reduced after dehydration, and uses the electricityThe battery of the electrolyte material has no obvious effect of reducing the capacity and the cycle performance.
4. The method for dehydrating and purifying the solid electrolyte provided by the invention further comprises the step of heating by stage heating, and the combination of the additive and the solid electrolyte, the substituted crystal water, the attached additive and other components can be effectively ensured to be gradually removed by a specific stage heating mode, meanwhile, the original solid electrolyte structure is not damaged, no impurities are generated, the obvious reduction of the conductivity of the dehydrated electrolyte material is further ensured, and the capacity and the cycle performance of a battery using the electrolyte material are not obviously reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a cycle-specific capacity diagram of a solid-state battery prepared by the electrolyte material obtained in example 1 of the present invention.
Fig. 2 is an XRD pattern of the solid electrolyte before water absorption in example 1 of the present invention, the dehydrated and purified solid electrolyte obtained after the treatment of example 1, and the dehydrated and purified solid electrolyte obtained after the treatment of comparative example 2.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The present embodiment provides a solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 Method for dehydration purification of O, wherein solid electrolyte Li before water absorption 3 HoCl 6 The conductivity of the electrolyte is 1.36mS/cm, and the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 The method for obtaining O comprises the following steps: solid electrolyte Li which does not absorb water 3 HoCl 6 Exposed to an atmosphere having a relative humidity of 1.1% at 25℃for 3 hours to give Li 3 HoCl 6 Absorbing moisture in the air in the atmosphere, accelerating the water absorption process of the simulated electrolyte in the long-time storage process, and obtaining the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 O；
The obtained solid electrolyte after water absorption is dehydrated and purified, and the method comprises the following steps:
placing the solid electrolyte after water absorption in an ammonia gas (the concentration of ammonia gas is more than 99.9%) atmosphere in a closed environment, fully contacting the solid electrolyte with ammonia gas for 16h, then taking the solid electrolyte out of the ammonia gas atmosphere, heating the solid electrolyte to 420 ℃ under the protection of nitrogen gas, keeping the temperature at 420 ℃ for 240min at a heating rate of 3 ℃/min; and finally, cooling the solid electrolyte material from 420 ℃ to room temperature at a cooling rate of 5 ℃/min to obtain the dehydrated and purified solid electrolyte.
Example 2
The present embodiment provides a solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 Method for dehydration purification of O, wherein solid electrolyte Li before water absorption 3 HoCl 6 The conductivity of the electrolyte is 1.36mS/cm, and the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 The method for obtaining O comprises the following steps: solid electrolyte Li which does not absorb water 3 HoCl 6 Exposed to an atmosphere having a relative humidity of 1.1% at 25℃for 3 hours, so thatLi 3 HoCl 6 Absorbing moisture in the air in the atmosphere, accelerating the water absorption process of the simulated electrolyte in the long-time storage process, and obtaining the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 O；
The obtained solid electrolyte after water absorption is dehydrated and purified, and the method comprises the following steps:
placing the solid electrolyte after water absorption in NH under nitrogen atmosphere 4 Aqueous Cl solution (NH) 4 The molar ratio of Cl to solid electrolyte is 1.5:1, NH 4 NH in Cl aqueous solution 4 Cl and water in a mass ratio of 3.7:10), stirring for 16h by using a stirrer, heating the mixed solution to 100 ℃, keeping the temperature at 100 ℃ for 80min at a heating rate of 3 ℃/min; then continuously heating from 100 ℃ to 340 ℃, wherein the heating rate is 2 ℃/min, and preserving heat for 30min at 340 ℃; then continuously heating from 340 ℃ to 420 ℃, wherein the heating rate is 1 ℃/min, and preserving heat for 180min at the temperature of 420 ℃; and finally, cooling the solid electrolyte material from the temperature of 420 ℃ to the room temperature at the cooling rate of 5 ℃/min to obtain the dehydrated and purified solid electrolyte.
Example 3
The present embodiment provides a solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 Method for dehydration purification of O, wherein solid electrolyte Li before water absorption 3 HoCl 6 The conductivity of the electrolyte is 1.36mS/cm, and the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 The method for obtaining O comprises the following steps: solid electrolyte Li which does not absorb water 3 HoCl 6 Exposed to an atmosphere having a relative humidity of 1.1% at 25℃for 3 hours to give Li 3 HoCl 6 Absorbing moisture in the air in the atmosphere, accelerating the water absorption process of the simulated electrolyte in the long-time storage process, and obtaining the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 O；
The obtained solid electrolyte after water absorption is dehydrated and purified, and the method comprises the following steps:
placing the solid electrolyte after water absorption in an ammonia gas (the concentration of ammonia gas is more than 99.9%) atmosphere in a closed environment, fully contacting the solid electrolyte with ammonia gas for 6 hours, then taking the solid electrolyte out of the ammonia gas atmosphere, heating the solid electrolyte to 410 ℃ under the protection of nitrogen, heating the solid electrolyte at a speed of 1 ℃/min, and preserving heat for 120min at 410 ℃; and finally, cooling the solid electrolyte material from 410 ℃ to room temperature at a cooling rate of 1 ℃/min to obtain the dehydrated and purified solid electrolyte.
Example 4
The present embodiment provides a solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 Method for dehydration purification of O, wherein solid electrolyte Li before water absorption 3 HoCl 6 The conductivity of the electrolyte is 1.36mS/cm, and the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 The method for obtaining O comprises the following steps: solid electrolyte Li which does not absorb water 3 HoCl 6 Exposed to an atmosphere having a relative humidity of 1.1% at 25℃for 3 hours to give Li 3 HoCl 6 Absorbing moisture in the air in the atmosphere, accelerating the water absorption process of the simulated electrolyte in the long-time storage process, and obtaining the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 O；
The obtained solid electrolyte after water absorption is dehydrated and purified, and the method comprises the following steps:
placing the solid electrolyte after water absorption in an ammonia gas (the concentration of ammonia gas is more than 99.9%) atmosphere in a closed environment, fully contacting the solid electrolyte with ammonia gas for 40h, then taking the solid electrolyte out of the ammonia gas atmosphere, heating the solid electrolyte to 500 ℃ under the protection of nitrogen, heating the solid electrolyte at a speed of 5 ℃/min, and preserving heat for 720min at 500 ℃; and finally, cooling the solid electrolyte material from 500 ℃ to room temperature at a cooling rate of 10 ℃/min to obtain the dehydrated and purified solid electrolyte.
Example 5
The present embodiment provides a solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 Method for dehydration purification of O, wherein solid electrolyte Li before water absorption 3 HoCl 6 The conductivity of the electrolyte is 1.36mS/cm, and the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 The method for obtaining O comprises the following steps: solid electrolyte Li which does not absorb water 3 HoCl 6 Exposed to an atmosphere having a relative humidity of 1.1% at 25℃for 3 hours to give Li 3 HoCl 6 Absorbing moisture in the air in the atmosphere, accelerating the water absorption process of the simulated electrolyte in the long-time storage process, and obtaining the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 O；
The obtained solid electrolyte after water absorption is dehydrated and purified, and the method comprises the following steps:
placing the solid electrolyte after water absorption in NH under nitrogen atmosphere 4 Aqueous Cl solution (NH) 4 The mole ratio of Cl to solid electrolyte after water absorption is 1.2:1, NH 4 NH in Cl aqueous solution 4 Cl and water in a mass ratio of 2:10), stirring for 1h by using a stirrer, heating the mixed solution to 100 ℃, keeping the temperature at 100 ℃ for 120min at a heating rate of 10 ℃/min; then continuously heating from 100 ℃ to 300 ℃, keeping the temperature at 300 ℃ for 60min at a heating rate of 10 ℃/min; then continuously heating from 300 ℃ to 410 ℃, keeping the temperature at the temperature of 410 ℃ for 720min at the heating rate of 5 ℃/min; and finally, cooling the solid electrolyte material from the temperature of 410 ℃ to the room temperature at the cooling rate of 1 ℃/min to obtain the dehydrated and purified solid electrolyte.
Tested, solid electrolyte Li 3 HoCl 6 The collapse temperature T of the crystal structure of (2) 0 550 ℃, NH 4 Cl and solid electrolyte Li 3 HoCl 6 Decomposition temperature T of the bonded substance 1 400 ℃ and NH 4 Boiling point T of aqueous Cl solution 2 About 100 c.
Example 6
The present embodiment provides a solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 Method for dehydration purification of O, wherein solid electrolyte Li before water absorption 3 HoCl 6 The conductivity of the electrolyte is 1.36mS/cm, and the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 The method for obtaining O comprises the following steps: solid electrolyte Li which does not absorb water 3 HoCl 6 Exposed to an atmosphere having a relative humidity of 1.1% at 25℃for 3 hours to give Li 3 HoCl 6 Absorbing moisture in the air in the atmosphere, accelerating the water absorption process of the simulated electrolyte in the long-time storage process, and obtaining the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 O；
The obtained solid electrolyte after water absorption is dehydrated and purified, and the method comprises the following steps:
placing the solid electrolyte after water absorption in NH under nitrogen atmosphere 4 Aqueous Cl solution (NH) 4 The mol ratio of Cl to the solid electrolyte after water absorption is 3:1, NH 4 NH in Cl aqueous solution 4 Cl and water in a mass ratio of 4:10), stirring for 36h by using a stirrer, heating the mixed solution to 120 ℃, keeping the temperature at 120 ℃ for 10min at a heating rate of 1 ℃/min; then continuously heating from 120 ℃ to 380 ℃ at a heating rate of 1 ℃/min, and preserving heat for 5min at the temperature of 380 ℃; then continuously heating from 380 ℃ to 500 ℃, keeping the temperature at 500 ℃ for 120min, wherein the heating rate is 1 ℃/min; and finally, cooling the solid electrolyte material from the temperature of 500 ℃ to the room temperature at the cooling rate of 10 ℃/min to obtain the dehydrated and purified solid electrolyte.
Example 7
The present embodiment provides a solid electrolyte Li after water absorption 3 HoBr 6 ·nH 2 O dehydration purification method, which is different from example 2 in that NH is added 4 Substitution of aqueous Cl solution with NH 4 Br aqueous solution (NH) 4 The molar ratio of Br to solid electrolyte after water absorption is 1.5:1, NH 4 NH in Br aqueous solution 4 The mass ratio of Br to water was 3.7:10).
Example 8
The present embodiment provides a solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 O dehydration purification method, which is different from example 2 in that NH is added 4 The aqueous Cl solution was replaced with aqueous HCl (molar ratio of HCl to solid electrolyte after water absorption 1.5:1, mass ratio of HCl to water in aqueous HCl solution 3.7:10).
Example 9
The present embodiment provides a solid electrolyte Li after water absorption 3 HoBr 6 ·nH 2 O dehydration purification method, which is different from example 2 in that NH is added 4 The Cl aqueous solution is replaced by HBr aqueous solution (the mol ratio of HBr to solid electrolyte after water absorption is 1.5:1, and the mass ratio of HBr to water in the HBr aqueous solution is 3.7:10).
Comparative example 1
This comparative example provides a solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 O, wherein the solid electrolyte Li before water absorption 3 HoCl 6 The conductivity of the electrolyte is 1.36mS/cm, and the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 The method for obtaining O comprises the following steps: solid electrolyte Li which does not absorb water 3 HoCl 6 Exposed to an atmosphere having a relative humidity of 1.1% at 25℃for 3 hours to give Li 3 HoCl 6 Absorbing moisture in the air in the atmosphere, accelerating the water absorption process of the simulated electrolyte in the long-time storage process, and obtaining the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 O。
Comparative example 2
This comparative example provides a solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 Method for dehydration purification of O, wherein solid electrolyte Li before water absorption 3 HoCl 6 The conductivity of the electrolyte is 1.36mS/cm, and the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 The method for obtaining O comprises the following steps: solid electrolyte Li which does not absorb water 3 HoCl 6 Exposed to an atmosphere having a relative humidity of 1.1% at 25℃for 3 hours to give Li 3 HoCl 6 Absorbing moisture in the air in the atmosphere, accelerating the water absorption process of the simulated electrolyte in the long-time storage process, and obtaining the solid electrolyte Li after water absorption 3 HoCl 6 ·nH 2 O；
The obtained solid electrolyte after water absorption is dehydrated and purified, and the method comprises the following steps:
placing the solid electrolyte after water absorption in a nitrogen atmosphere in a closed environment, heating to 420 ℃, wherein the heating rate is 3 ℃/min, and preserving heat for 240min at the temperature of 420 ℃; and finally, cooling the solid electrolyte material from 240 ℃ to room temperature at a cooling rate of 5 ℃/min to obtain the dehydrated and purified solid electrolyte.
Test example 1
The solid electrolytes obtained in the above examples and comparative examples were tested for electrical conductivity and the test results are shown in table 1.
TABLE 1 conductivity of solid electrolytes
Test example 2
The solid electrolytes obtained in the above examples and comparative examples were prepared into solid batteries, respectively, and electrochemical performance tests were performed as follows: the solid electrolyte material obtained in the example or the comparative example was used as an electrolyte in a positive electrode, and LiNi 0.8 Co 0.1 Mn 0.1 O 2 As the positive electrode active material, the conductive carbon is Super P, wherein the mass ratio of the positive electrode active material to the solid electrolyte to the conductive carbon is 70:28:2; the solid electrolyte layer is obtained by tabletting the solid electrolyte material obtained In the above example or comparative example, the negative electrode is metal In, the solid battery is obtained after assembly, the solid battery is subjected to constant current discharge at 25 ℃ and 1C current, and the solid battery is cycled for 100 weeks, so that the 100 th week discharge specific capacity and the 100 th week discharge specific capacity retention rate are obtained. The test results are shown in Table 2.
Table 2 results of solid-state battery performance test
As can be seen from table 2, compared with the comparative example, the solid electrolyte material treated by the method of the present invention has significantly improved specific capacity and cycle retention rate of the assembled battery. As can be seen from fig. 2, the XRD spectrum of the solid electrolyte treated by the method of the present invention is substantially identical to the spectrum of the solid electrolyte before water absorption, and each diffraction peak corresponds to the XRD spectrum, which indicates that no impurity phase is generated in the solid electrolyte purified by the method of the present invention, and the solid electrolyte can maintain the state of the electrolyte before water absorption. In contrast, the electrolyte treated by the method of comparative example 2 produced, in addition to the diffraction peak of the electrolyte before water absorption, the remaining diffraction peak (marked by circles) corresponding to oxychlorides formed by decomposition of the hydrate of the electrolyte at high temperature.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (2)
1. A method for dehydration and purification of a solid electrolyte, comprising the steps of:
contacting the solid electrolyte to be treated with a dehydration additive, and then heating to obtain the dehydrated and purified solid electrolyte;
the dehydration additive is selected from NH 3 Or is selected from NH 4 F aqueous solution, NH 4 Aqueous Cl solution, NH 4 At least one of Br aqueous solution, HCl aqueous solution and HBr aqueous solution;
when the dehydration additive is selected from NH 3 In the process, the dehydration and purification method comprises the following steps:
placing the solid electrolyte to be treated in a dehydration additive gas atmosphere to enable the solid electrolyte to be fully contacted with the dehydration additive for 6-40h, then taking the solid electrolyte out of the dehydration additive gas atmosphere, heating the solid electrolyte to 410-500 ℃ in an inert atmosphere at a heating rate of 1-5 ℃/min, and preserving heat for 120-720min at a temperature of 410-500 ℃; finally, cooling the solid electrolyte material from 410-500 ℃ to room temperature at a cooling rate of 1-10 ℃/min to obtain the dehydrated and purified solid electrolyte;
when the dehydration additive is selected from NH 4 F aqueous solution, NH 4 Aqueous Cl solution, NH 4 When at least one of Br aqueous solution, HCl aqueous solution and HBr aqueous solution is adopted, the dehydration purification method comprises the following steps:
placing the solid electrolyte to be treated in a dehydration additive under inert atmosphere, stirring for 1-36h, heating the mixed solution to 90-120 ℃, keeping the temperature at the heating rate of 1-10 ℃/min, and keeping the temperature at 90-120 ℃ for 10-120min; then continuously heating from 90-120 ℃ to 300-400 ℃ at a heating rate of 1-10 ℃/min, and preserving heat for 5-60min at 300-400 ℃; then continuously heating from 300-400 ℃ to 410-500 ℃ at a heating rate of 1-5 ℃/min, and preserving heat for 120-720min at the temperature of 410-500 ℃; finally, cooling the solid electrolyte material from the temperature of 410-500 ℃ to the room temperature at the cooling rate of 1-10 ℃/min to obtain the dehydrated and purified solid electrolyte;
the solid electrolyte is a halide solid electrolyte;
the chemical general formula of the halide solid electrolyte is Li 3 MX 6 Wherein X is selected from one or more of F, cl and Br; m is selected from one or more of Sc, Y, zr, hf, ga, in, la, ce, pr, nd, pm, sm, eu, ga, la, dy, ho, er, tm, yb, lu.
2. The dehydration purification method according to claim 1, wherein the solid electrolyte to be treated is a water-absorbed solid electrolyte;
when the dehydration additive is selected from NH 4 F aqueous solution, NH 4 Aqueous Cl solution, NH 4 When at least one of Br aqueous solution, HCl aqueous solution and HBr aqueous solution is used, the mole ratio of solute in the dehydration additive to solid electrolyte to be treated is (1.2-3): 1, and the mass ratio of solute in the dehydration additive to water is (2-4): 10.
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