CN116640318A - Hierarchical pore ZIF-8, high-conductivity additive, solid electrolyte membrane and battery - Google Patents
Hierarchical pore ZIF-8, high-conductivity additive, solid electrolyte membrane and battery Download PDFInfo
- Publication number
- CN116640318A CN116640318A CN202310446486.0A CN202310446486A CN116640318A CN 116640318 A CN116640318 A CN 116640318A CN 202310446486 A CN202310446486 A CN 202310446486A CN 116640318 A CN116640318 A CN 116640318A
- Authority
- CN
- China
- Prior art keywords
- zif
- solution
- solid electrolyte
- zinc
- experimental group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 133
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 24
- 239000007784 solid electrolyte Substances 0.000 title claims description 73
- 239000012528 membrane Substances 0.000 title claims description 64
- 239000000654 additive Substances 0.000 title claims description 21
- 230000000996 additive effect Effects 0.000 title claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 159
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 104
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 48
- ZKZXQUJQRQQZMM-UHFFFAOYSA-N hydroxy nitrate zinc Chemical compound OO[N+](=O)[O-].[Zn] ZKZXQUJQRQQZMM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000011065 in-situ storage Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims description 36
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 32
- 229910052621 halloysite Inorganic materials 0.000 claims description 32
- 239000002071 nanotube Substances 0.000 claims description 32
- 239000002482 conductive additive Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 42
- 238000002360 preparation method Methods 0.000 abstract description 38
- 239000000463 material Substances 0.000 abstract description 31
- 238000013508 migration Methods 0.000 abstract description 17
- 230000005012 migration Effects 0.000 abstract description 17
- 238000003860 storage Methods 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 106
- 238000012360 testing method Methods 0.000 description 36
- 239000002994 raw material Substances 0.000 description 35
- 238000000034 method Methods 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 18
- 210000004027 cell Anatomy 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 230000001351 cycling effect Effects 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000001174 ascending effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- UUZZMWZGAZGXSF-UHFFFAOYSA-N peroxynitric acid Chemical compound OON(=O)=O UUZZMWZGAZGXSF-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The scheme provides a hierarchical pore ZIF-8, and the hierarchical pore ZIF-8 is prepared by the following steps: s1, mixing a sodium hydroxide solution and a zinc nitrate solution to obtain an in-situ reaction system, and reacting sodium hydroxide and zinc nitrate in the in-situ reaction system to synthesize a zinc hydroxyl nitrate intermediate; s2, adding a 2-methylimidazole solution into the in-situ reaction system, and in-situ growing the ZIF-8 on the zinc hydroxy nitrate intermediate, thereby preparing the hierarchical pore ZIF-8. Compared with the common ZIF-8, the hierarchical ZIF-8 prepared by the specific preparation method can provide more storage space for lithium ions, and can provide higher lithium ion conductivity and lithium ion migration number when being applied to electrical components, so that the electrical components applying the hierarchical ZIF-8 material have more excellent electrochemical performance.
Description
Technical Field
The invention relates to the technical field of lithium ion battery electrolyte, in particular to a hierarchical pore ZIF-8, a high-conductivity additive, a solid electrolyte membrane and a battery.
Background
As the demand for the consumer electronics market increases further, there is an increasing demand for efficient, safe electrochemical energy storage devices. Lithium ion batteries have received considerable attention from researchers as the most widely used electrochemical energy storage devices. However, the liquid organic electrolyte used in the current lithium ion battery has the safety problems of inflammability, easy leakage, toxicity, poor thermal stability and the like, and the separator is easy to be pierced by lithium dendrites to cause short circuit of the battery, so that the risks of fire explosion and the like are caused, and the development of the lithium ion battery is greatly limited. In contrast, all-solid-state batteries are considered to be the preferred direction of next-generation novel power batteries and energy storage batteries because of the adoption of solid electrolyte membranes, the advantages of high safety, high energy density and the like.
Currently, solid electrolyte membranes can be classified into two types, inorganic and organic polymers, depending on the raw materials they use. However, although the ionic conductivity of a single inorganic solid electrolyte membrane is high, the single inorganic solid electrolyte membrane has the problems of high brittleness, poor interface stability with an electrode and the like; although the single organic polymer solid electrolyte membrane has the advantages of good flexibility, easy processing, low cost and the like, the ionic conductivity of the single organic polymer solid electrolyte membrane is too low at normal temperature, and the requirement of the solid battery on the ionic conductivity of the electrolyte at room temperature cannot be met. Therefore, metal-organic frameworks (metal-organic frameworks, MOFs), which are mainly composed of metal ions and organic linkers, combine the rigidity of inorganic materials and preserve the flexibility of organic materials, are considered as one of the most promising next-generation battery technologies.
However, since the metal organic frame material itself has a limited pore structure, adsorption and storage of lithium ions are greatly limited, and thus the lithium ion conductivity is affected, so that the overall performance of the all-solid-state battery cannot be effectively increased. Accordingly, there is a need for an improved hierarchical pore ZIF-8 design that addresses the above-described problems.
Disclosure of Invention
The invention aims to provide a hierarchical pore ZIF-8, a high-conductivity additive, a solid electrolyte membrane and a battery, so as to improve the structure of the hierarchical pore ZIF-8, and the hierarchical pore ZIF-8 is applied to the solid electrolyte membrane and the battery, so that the ion conductivity and the lithium ion migration number of the solid electrolyte membrane can be improved, and the cycle stability and the charge-discharge efficiency of the battery are further improved.
According to one aspect of the present invention, there is provided a hierarchical ZIF-8, the hierarchical ZIF-8 being prepared by the steps of: s1, mixing a sodium hydroxide solution and a zinc nitrate solution to obtain an in-situ reaction system, and reacting sodium hydroxide and zinc nitrate in the in-situ reaction system to synthesize a zinc hydroxyl nitrate intermediate; s2, adding a 2-methylimidazole solution into the in-situ reaction system, and in-situ growing the ZIF-8 on the zinc hydroxy nitrate intermediate, thereby preparing the hierarchical pore ZIF-8.
The porous crystalline material coordinated self-assembled from zinc ions and 2-methylimidazole is called zeolitic imidazolate framework material (Zeolitic Imidazolate Framework-8, ZIF-8), and the conventional preparation method of ZIF-8 is to directly mix a zinc ion-containing solution with a 2-methylimidazole solution. The preparation method of the hierarchical pore ZIF-8 (H-ZIF-8 for short) comprises the steps of mixing a zinc ion-containing solution with a sodium hydroxide solution, and preparing a zinc hydroxy nitrate intermediate; and then adding a 2-methylimidazole solution into an in-situ reaction system containing zinc ions, and carrying out in-situ growth by taking a zinc hydroxy nitrate intermediate as a substrate to prepare the H-ZIF-8 provided by the invention. The ZIF-8 is grown in situ by utilizing the zinc hydroxy nitrate intermediate with a specific structure, so that the prepared ZIF-8 has a multi-level pore structure which comprises micropores, mesopores and macropores. Therefore, the prepared H-ZIF-8 has sufficient surface area and internal storage capacity, more storage space can be provided for lithium ions, and compared with the common ZIF-8, the H-ZIF-8 provided by the scheme is applied to an electrical component, so that the electrical component has higher lithium ion conduction capacity and lithium ion migration number, and a battery applying the H-ZIF-8 material has more excellent electrochemical performance.
Preferably, the feeding amounts of the sodium hydroxide solution and the zinc nitrate solution satisfy n (Zn 2+ )：n(OH - )＝1：0.6～1.2。
The zinc hydroxyl nitrate intermediate component synthesized by the in-situ reaction system comprises Zn by making the feeding amount of the sodium hydroxide solution and the zinc nitrate solution meet the above conditions 5 (OH) 8 (NO 3 ) 2 ·2H 2 O and Zn (OH) (NO 3 )·H 2 O. Compared with other zinc hydroxy nitrateInclude Zn 5 (OH) 8 (NO 3 ) 2 ·2H 2 O and Zn (OH) (NO 3 )·H 2 The intermediate of O has more active sites, can promote the generation of H-ZIF-8, and the prepared H-ZIF-8 material has micropores, mesopores and macropores, and also has a pore structure inside the material, so that the H-ZIF-8 material has enough storage space. Lithium ions can enter the inner space of the H-ZIF-8 through the multi-level pore structure, and lithium vacancies are left, so that the transportation of lithium ions in the material is realized. Therefore, the H-ZIF-8 provided by the scheme can be used for preparing the solid electrolyte membrane, and the lithium ion conduction capacity and the lithium ion migration number of a battery product applying the solid electrolyte membrane can be further improved. In addition, the zinc hydroxy nitrate intermediate prepared by the specific material proportion has regular shape and higher purity, especially contains less ZnO impurity, thereby improving the yield of the prepared H-ZIF-8 material and reducing the waste of raw materials.
Preferably, the concentration of the zinc nitrate solution is 0.2-1.0 mol/L, and the concentration of the sodium hydroxide solution is 0.1-0.3 mol/L.
The long-term experiments and researches of the inventor show that the concentration of the zinc nitrate solution and the sodium hydroxide solution can influence the pH value and the dissolution balance of an in-situ reaction system, so that the generation amount and the microscopic morphology of the zinc hydroxy nitrate intermediate are influenced, and the microscopic morphology of the H-ZIF-8 prepared by taking the zinc hydroxy nitrate intermediate as a nucleation growth site is further influenced. When the concentration of the zinc nitrate solution and the sodium hydroxide solution fall into the above range, the prepared product zinc hydroxy nitrate intermediate has uniform morphology and more growth sites, so that the H-ZIF-8 prepared under the reaction system can be applied to battery components, and the battery components have better lithium ion storage performance and higher lithium ion migration number.
Preferably, the feeding amount of the zinc nitrate solution and the 2-methylimidazole solution meets n (Zn) 2+ ): n (2-methylimidazole) =1: 30-35.
When the feeding amount of the zinc nitrate solution and the 2-methylimidazole solution meets the conditions, the zinc hydroxyl nitrate intermediate is used as a nucleation growth site, and zinc ions in an in-situ reaction system and the added 2-methylimidazole react on the zinc hydroxyl nitrate intermediate together, so that the prepared H-ZIF-8 has a multi-stage pore structure, the prepared H-ZIF-8 has good mechanical property and cannot be excessively fragile, the H-ZIF-8 material has good processing property, and components using the multi-stage pore ZIF-8 material have good quality stability.
Preferably, the concentration of the zinc nitrate solution is 0.2-1.0 mol/L, and the concentration of the 2-methylimidazole solution is 2-4 mol/L. The concentration of the 2-methylimidazole solution and the concentration of zinc ions in an in-situ reaction system also influence the generation and the microporous structure of the H-ZIF-8, and when the concentration of the zinc nitrate solution and the concentration of the 2-methylimidazole solution meet the conditions, the prepared H-ZIF-8 is favorable for rapid deintercalation of lithium ions in a battery product and can further improve the lithium ion conductivity and the lithium ion migration number of the battery product when the prepared H-ZIF-8 is applied to the battery product.
Preferably, the process for preparing the hierarchical pore ZIF-8 is carried out at 20-30 ℃; in S1, mixing a sodium hydroxide solution and a zinc nitrate solution, and reacting for 10-20 minutes to obtain a zinc hydroxyl nitrate intermediate; in S2, the reaction time of in-situ growth is 1.5-2.5 hours.
The preparation method has simple process and easy control of material structure, and the prepared zinc hydroxy nitrate is in a nano sheet structure by controlling reaction conditions, and the zinc hydroxy nitrate with the specific structure is used as a growth substrate of the H-ZIF-8, so that the microstructure of the H-ZIF-8 is further controlled.
According to a second aspect of the present invention, there is provided a highly conductive additive comprising the hierarchical pore ZIF-8 and halloysite nanotubes described above; according to the mass percentage, in the high-conductivity additive, the content of the hierarchical pore ZIF-8 is 65-75wt% and the content of the halloysite nanotube is 25-35wt%. In the high-conductivity additive, the multi-level pore structure of the H-ZIF-8 material and the hollow structure of the halloysite nanotube are matched with each other, so that more space is provided for storing lithium ions, the rapid movement of the lithium ions is promoted, the ion conductivity of a battery product applying the high-conductivity additive is effectively improved, and the electrochemical performance of the battery product is further improved. On the other hand, the chemical window of the battery is effectively widened and the cycle stability and the cycle life of the battery components are improved by utilizing the synergistic effect between the H-ZIF-8 material and the halloysite nanotube.
Preferably, the halloysite nanotubes have an average inner diameter of 15 to 60nm, an average outer diameter of 50 to 100nm, and an average tube length of 0.1 to 10um.
By using halloysite nanotubes with specific inner and outer diameters and tube lengths, not only can the hollow structure be utilized to provide more lithium ion storage space, but also the halloysite nanotubes have special tubular structures, the tube interior of the halloysite nanotubes is positively charged, the tube exterior of the halloysite nanotubes is negatively charged, and the positive charges in the tube can effectively fix the migration of anions in the electrolyte, so that the migration of lithium ions is promoted.
According to a third aspect of the present invention, there is provided a solid electrolyte membrane comprising the above-described high-conductivity additive, the high-conductivity additive being not less than 80% by mass in the solid electrolyte membrane.
The high-conductivity additive can improve the ion conductivity of the solid electrolyte membrane, so that the internal resistance of a battery applying the solid electrolyte membrane can be effectively reduced, the charge-discharge rate performance of the battery can be improved, the migration number of lithium ions of the solid electrolyte membrane can be improved, the concentration polarization in the charge-discharge process can be weakened, and the power of the battery can be further improved.
According to a fourth aspect of the present invention, there is provided a battery comprising the above solid electrolyte membrane, a positive electrode sheet, a negative electrode sheet, the solid electrolyte membrane being disposed between the positive electrode sheet and the negative electrode sheet.
The battery provided by the invention has the advantages of strong cycling stability, long cycling life and high charge and discharge efficiency.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
Experimental group 1-1
The experimental group is used for preparing a solid electrolyte membrane, and the adopted raw materials comprise a mixed solution of a high-conductivity additive containing H-ZIF-8 and halloysite nanotubes, isopropanol and polytetrafluoroethylene, wherein the content of the H-ZIF-8 in the high-conductivity additive is 70wt% and the content of the halloysite nanotubes is 30wt%; the average inner diameter of the halloysite nanotube is 40nm, the average outer diameter is 75nm, and the average tube length is 5um; the polytetrafluoroethylene content in the mixed solution was 15wt%.
The solid electrolyte membrane is prepared by the following steps:
uniformly mixing isopropanol and polytetrafluoroethylene mixed solution as solvent with the above high conductivity additive, grinding thoroughly until the solvent volatilizes, rolling the obtained mixture to obtain film sheet with thickness of 200 μm and punching diameter of 16mm, vacuum drying at 80deg.C for 24 hr, and soaking in 1mol/L LiPF under inert gas atmosphere 6 In the solution, it was activated for 24 hours to prepare a solid electrolyte membrane.
Wherein, the raw materials adopted in the H-ZIF-8 in the high-conductivity additive comprise zinc nitrate solution, sodium hydroxide solution and 2-methylimidazole solution. Specifically, the solvent of the zinc nitrate solution is deionized water, and the concentration of the zinc nitrate solution is 0.5mol/L; the solvent of the sodium hydroxide solution is deionized water, and the concentration of the sodium hydroxide solution is 0.2mol/L; the solvent of the 2-methylimidazole solution is deionized water, and the concentration of the 2-methylimidazole solution is 3mol/L.
The H-ZIF-8 is prepared by the following steps at 25 ℃:
s1, mixing a sodium hydroxide solution and a zinc nitrate solution to obtain an in-situ reaction system, and reacting sodium hydroxide and zinc nitrate in the in-situ reaction system for 15 minutes to synthesize a zinc hydroxy nitrate intermediate; wherein the feeding amount of the sodium hydroxide solution and the zinc nitrate solution is made to meet n (Zn) 2+ ): n (NaOH) =1:0.67; the zinc hydroxy nitrate intermediate comprises Zn 5 (OH) 8 (NO 3 ) 2 ·2H 2 O and Zn (OH) (NO 3 )·H 2 O。
S2, adding a 2-methylimidazole solution into an in-situ reaction system, in-situ growing ZIF-8 on a zinc hydroxy nitrate intermediate, wherein the in-situ growth reaction time is 2 hours, washing the obtained product with deionized water and absolute ethyl alcohol for 3 times in sequence, centrifuging the washed product, collecting precipitate, and vacuum drying at 80 ℃ to obtain the hierarchical pore ZIF-8. Wherein, the feeding amount of the zinc nitrate solution and the 2-methylimidazole solution meets n (Zn) 2+ ): n (2-methylimidazole) =1: 32.
experimental groups 1-2
The experimental group refers to the preparation method provided in the experimental group 1-1, and a solid electrolyte membrane is prepared. The experimental group differs from the experimental group 1-1 in that: in the process of preparing H-ZIF-8, the feeding amount of the sodium hydroxide solution and the zinc nitrate solution is adjusted to ensure that n (Zn 2+ ): n (NaOH) =1: 0.5. the rest of the raw materials and the preparation method are strictly consistent with the experimental group 1-1.
Experimental groups 1-3
The experimental group refers to the preparation method provided in the experimental group 1-1, and a solid electrolyte membrane is prepared. The experimental group differs from the experimental group 1-1 in that: in the process of preparing H-ZIF-8, the feeding amount of the sodium hydroxide solution and the zinc nitrate solution is adjusted to ensure that n (Zn 2+ ): n (NaOH) =1: 1. the rest of the raw materials and the preparation method are strictly consistent with the experimental group 1-1.
Experimental groups 1 to 4
The experimental group refers to the preparation method provided in the experimental group 1-1, and a solid electrolyte membrane is prepared. The experimental group differs from the experimental group 1-1 in that: in the process of preparing H-ZIF-8, the feeding amount of the sodium hydroxide solution and the zinc nitrate solution is adjusted to ensure that n (Zn 2+ ): n (NaOH) =1: 1.2. the rest of the raw materials and the preparation method are strictly consistent with the experimental group 1-1.
Experimental groups 1 to 5
The experimental group refers to the preparation method provided in the experimental group 1-1, and a solid electrolyte membrane is prepared. The experimental group and the experimental group1-1 is distinguished in that: in the process of preparing H-ZIF-8, the feeding amount of the sodium hydroxide solution and the zinc nitrate solution is adjusted to ensure that n (Zn 2+ ): n (NaOH) =1: 1.5. the rest of the raw materials and the preparation method are strictly consistent with the experimental group 1-1.
Example 2
Experimental group 2-1
The experimental group refers to the preparation method provided in the experimental group 1-1, and a solid electrolyte membrane is prepared. The experimental group differs from the experimental group 1-1 in that: in the process of preparing H-ZIF-8, the feeding amount of the zinc nitrate solution and the 2-methylimidazole solution is adjusted to meet n (Zn) 2+ ): n (2-methylimidazole) =1: 30. the rest of the raw materials and the preparation method are strictly consistent with the experimental group 1-1.
Experimental group 2-2
The experimental group refers to the preparation method provided in the experimental group 1-1, and a solid electrolyte membrane is prepared. The experimental group differs from the experimental group 1-1 in that: in the process of preparing H-ZIF-8, the feeding amount of the zinc nitrate solution and the 2-methylimidazole solution is adjusted to meet n (Zn) 2+ ): n (2-methylimidazole) =1: 35. the rest of the raw materials and the preparation method are strictly consistent with the experimental group 1-1.
Example 3
Experimental group 3-1
The experimental group refers to the preparation method provided in the experimental group 1-1, and a solid electrolyte membrane is prepared. The experimental group differs from the experimental group 1-1 in that: in the process of preparing H-ZIF-8, the concentration of the zinc nitrate solution is regulated to be 0.2mol/L, and the concentration of the sodium hydroxide solution is regulated to be 0.1mol/L. The rest of the raw materials and the preparation method are strictly consistent with the experimental group 1-1.
Experimental group 3-2
The experimental group refers to the preparation method provided in the experimental group 1-1, and a solid electrolyte membrane is prepared. The experimental group differs from the experimental group 1-1 in that: in the process of preparing H-ZIF-8, the concentration of the zinc nitrate solution is adjusted to be 1.0mol/L, and the concentration of the sodium hydroxide solution is adjusted to be 0.3mol/L. The rest of the raw materials and the preparation method are strictly consistent with the experimental group 1-1.
Experimental group 3-3
The experimental group refers to the preparation method provided in the experimental group 1-1, and a solid electrolyte membrane is prepared. The experimental group differs from the experimental group 1-1 in that: in the process of preparing H-ZIF-8, the concentration of the zinc nitrate solution is regulated to be 0.2mol/L, and the concentration of the 2-methylimidazole solution is regulated to be 2mol/L. The rest of the raw materials and the preparation method are strictly consistent with the experimental group 1-1.
Experimental groups 3 to 4
The experimental group refers to the preparation method provided in the experimental group 1-1, and a solid electrolyte membrane is prepared. The experimental group differs from the experimental group 1-1 in that: in the process of preparing H-ZIF-8, the concentration of the zinc nitrate solution is adjusted to be 1.0mol/L, and the concentration of the 2-methylimidazole solution is adjusted to be 4mol/L. The rest of the raw materials and the preparation method are strictly consistent with the experimental group 1-1.
Example 4
Experimental group 4-1
The experimental group refers to the preparation method provided in the experimental group 1-1, and a solid electrolyte membrane is prepared. The experimental group differs from the experimental group 1-1 in that: in the process of preparing the solid electrolyte membrane, the feeding amount of the H-ZIF-8 and the halloysite nanotubes is adjusted to ensure that the content of the H-ZIF-8 in the high-conductivity additive is 75 weight percent and the content of the halloysite nanotubes is 25 weight percent. The rest of the raw materials and the preparation method are strictly consistent with the experimental group 1-1.
Experimental group 4-2
The experimental group refers to the preparation method provided in the experimental group 1-1, and a solid electrolyte membrane is prepared. The experimental group differs from the experimental group 1-1 in that: in the process of preparing the solid electrolyte membrane, the feeding amount of the H-ZIF-8 and the halloysite nanotubes is adjusted to ensure that the content of the H-ZIF-8 in the high-conductivity additive is 65 weight percent and the content of the halloysite nanotubes is 35 weight percent. The rest of the raw materials and the preparation method are strictly consistent with the experimental group 1-1.
Experimental group 4-3
The experimental group refers to the preparation method provided in the experimental group 1-1, and a solid electrolyte membrane is prepared. The experimental group differs from the experimental group 1-1 in that: in the process of preparing the solid electrolyte membrane, the halloysite nanotubes adopted in the experimental group 1-1 are replaced by the H-ZIF-8 with the same quantity, which is equivalent to the fact that the solid electrolyte membrane prepared by the experimental group does not contain the halloysite nanotubes. The rest of the raw materials and the preparation method are strictly consistent with the experimental group 1-1.
Comparative example
Control group 1
The control group refers to the preparation method provided in experimental group 1-1 to prepare a solid electrolyte membrane. The experimental group was different from the experimental group 1-1 in that the preparation method for preparing ZIF-8 was different. The ZIF-8 is prepared by the following steps: uniformly mixing a 2-methylimidazole solution and a zinc nitrate solution, adding a sodium hydroxide solution, and continuously stirring at normal temperature and normal pressure for reaction for 1 hour; and (3) centrifugally separating, washing and drying the prepared mixture to obtain the ZIF-8. The other materials and the amounts thereof were strictly consistent with those of the experimental group 1-1.
Control group 2
The control group refers to the preparation method provided in experimental group 1-1 to prepare a solid electrolyte membrane. The control group differs from experimental group 1-1 in that: in the process of preparing the solid electrolyte membrane, the H-ZIF-8 selected in the experimental group 1-1 is replaced by an equal amount of ZIF-8 with the mark of MM2241158 produced by Shanghai regular script tree chemical technology Co. The rest of the raw materials and the preparation method are strictly consistent with the experimental group 1-1.
Control group 3
The control group refers to the preparation method provided in experimental group 1-1 to prepare a solid electrolyte membrane. The control group differs from experimental group 1-1 in that: in the process of preparing the solid electrolyte membrane, the equal amount of halloysite nanotubes are selected to replace the H-ZIF-8 adopted in the experimental group 1-1, which is equivalent to the fact that the solid electrolyte membrane prepared by the comparative group does not contain the H-ZIF-8. The rest of the raw materials and the preparation method are strictly consistent with the experimental group 1-1.
Test case
1. A reference subject: the solid electrolyte membranes provided in examples 1 to 4 and comparative examples.
2. Test items and methods:
(1) Ion conductivity: the test subjects were pressed into sheets with a thickness of 0.32mm and a diameter of 16mm, respectively, to prepare button cells. Stainless steel SS is used as a positive electrode plate and a negative electrode plate, a sheet prepared by a reference object is used as electrolyte, and the sheet is arranged between the positive electrode plate and the negative electrode plate, so that the symmetrical button cell (stainless steel SS|solid electrolyte|stainless steel SS) with the composition model of 2032 is prepared. The prepared symmetrical button cell (stainless steel ss|solid electrolyte|stainless steel SS) was evaluated at room temperature using an electrochemical alternating current impedance spectroscopy test (EIS) at a test frequency of 1Hz to 1MHz.
The ionic conductivity was calculated as: δ=l/(r×s), L is thickness, R is resistance, and S is contact area.
(2) Ion migration number: the test subjects were pressed into sheets with a thickness of 0.32mm and a diameter of 16mm, respectively, to prepare button cells. The lithium-containing material is used as a positive electrode plate and a negative electrode plate, a sheet prepared by a reference object is used as electrolyte, and the sheet is arranged between the positive electrode plate and the negative electrode plate to prepare the symmetric button cell (Li|solid electrolyte|Li) with the model number of 2032. And evaluating the prepared symmetrical button cell (Li|solid electrolyte|Li) by using a Bruce-Vincent-Evans method at room temperature, wherein the test polarization voltage is 10mV, and the cell impedance test frequency is 1 Hz-1 MHz.
The calculation formula of the migration number of lithium ions is as follows: t is t Li+ ＝(I S (ΔV–I 0 R 0 ))/(I(ΔV–I s R s ))。
I 0 And I S Respectively, a starting current and a stabilizing current, R 0 And R is S The interface resistance before and after polarization, deltaV is the polarization voltage.
(3) Chemical window: the test subjects were pressed into sheets with a thickness of 0.32mm and a diameter of 16mm, respectively, to prepare button cells. Stainless steel SS is used as a positive electrode plate and a negative electrode plate, a sheet prepared by a reference object is used as electrolyte, and the sheet is arranged between the positive electrode plate and the negative electrode plate, so that the symmetrical button cell (stainless steel SS|solid electrolyte|stainless steel SS) with the composition model of 2032 is prepared. The prepared symmetrical coin cell (stainless steel ss|solid electrolyte|stainless steel SS) was evaluated using Linear Sweep Voltammetry (LSV). The scanning speed is 10mV/s, and the voltage range is 0-9V. The measured decomposition voltage is recorded.
(4) Stability: the test subjects were pressed into sheets with a thickness of 0.32mm and a diameter of 16mm, respectively, to prepare button cells. The lithium-containing material is used as a positive electrode plate and a negative electrode plate, a sheet prepared by a reference object is used as electrolyte, and the sheet is arranged between the positive electrode plate and the negative electrode plate to prepare the symmetric button cell (Li|solid electrolyte|Li) with the model number of 2032. The prepared symmetrical button cell is subjected to stripping cycle test, and the current density is 0.1mA/cm 2 Constant current charge and discharge cycle was 1000 hours. The measured initial and average polarization voltages are recorded.
(5) Cycle performance: the test subjects were pressed into sheets with a thickness of 0.32mm and a diameter of 16mm, respectively, to prepare button cells. To contain LiFePO 4 The material of (2) is used as a positive electrode plate, a Li-containing material is used as a negative electrode plate, a slice correspondingly prepared by a reference object is used as electrolyte, and the slice is arranged between the positive electrode plate and the negative electrode plate to prepare the asymmetric button cell (Li|solid electrolyte|LiFePO) with the model of 2032 4 ). The asymmetric coin cell (Li|solid electrolyte|LiFePO) 4 ) Multiple charge and discharge runs were performed with a current density set at 0.1C (1c=170 mA/g) and the initial coulombic efficiency after infrared cycling was recorded.
3. Test results: the raw material formulation of the test subjects in this test example is shown in table 1; the test results are shown in tables 2 and 3.
TABLE 1 raw material formulation for each subject
TABLE 2 ion conductivity, ion migration number and chemical window of the individual subjects
| Group of | Ion conductivity (S/cm) | Ion migration number | Chemical window (V) |
| Experimental group 1-1 | 7.700×10 -3 | 0.840 | 4.08～7.48 |
| Experimental groups 1-2 | 7.204×10 -3 | 0.796 | 3.79～7.22 |
| Experimental groups 1-3 | 7.657×10 -3 | 0.829 | 4.01～7.45 |
| Experimental groups 1 to 4 | 7.677×10 -3 | 0.835 | 4.04～7.50 |
| Experimental groups 1 to 5 | 7.561×10 -3 | 0.805 | 3.85～7.27 |
| Experimental group 2-1 | 7.665×10 -3 | 0.833 | 4.05～7.42 |
| Experimental group 2-2 | 7.683×10 -3 | 0.836 | 4.07～7.45 |
| Experimental group 3-1 | 7.574×10 -3 | 0.831 | 4.01～7.41 |
| Experimental group 3-2 | 7.595×10 -3 | 0.834 | 4.03～7.45 |
| Experimental group 3-3 | 7.629×10 -3 | 0.833 | 4.04～7.43 |
| Experimental groups 3 to 4 | 7.588×10 -3 | 0.830 | 4.05～7.42 |
| Experimental group 4-1 | 7.636×10 -3 | 0.830 | 3.82～7.29 |
| Experimental group 4-2 | 7.605×10 -3 | 0.832 | 4.05～7.44 |
| Experimental group 4-3 | 1.01×10 -3 | 0.710 | 3.68～7.21 |
| Control group 1 | 1.03×10 -4 | 0.400 | 3.57～5.91 |
| Control group 2 | 1.01×10 -4 | 0.395 | 3.53～5.89 |
| Control group 3 | 9.26×10 -4 | 0.680 | 3.96～7.31 |
TABLE 3 stability and cycle performance of the individual subjects
Comparing the raw material formulations of examples 1-4 and comparative example in Table 1, it can be found that the H-ZIF-8 selected in examples 1-4 were prepared by in situ growth on zinc hydroxy nitrate intermediate. ZIF-8 selected in the control group 1 is prepared without the step of preparing zinc hydroxy nitrate intermediate; ZIF-8 selected in the control group 2 is a commercial product; the solid electrolyte membrane produced in control 3 did not contain H-ZIF-8.
Comparing the test results of examples 1 to 4 and comparative examples in tables 2 and 3, it was found that the solid electrolyte membranes provided in examples 1 to 4 were superior in performance to the solid electrolyte membranes provided in comparative examples. Examples 1 to 4 all prepared H-ZIF-8 by in-situ growth of zinc hydroxy nitrate intermediate, the prepared H-ZIF-8 has a multi-stage pore structure comprising micropores, mesopores and macropores, the prepared H-ZIF-8 has sufficient surface area and internal storage capacity, more storage space can be provided for lithium ions, and compared with the ZIF-8 prepared by the conventional preparation method provided in the comparative example, the H-ZIF-8 provided in examples 1 to 4 is applied to an electrical component, so that the electrical component has higher lithium ion conductivity and lithium ion migration number, and a battery using the H-ZIF-8 material has more excellent electrochemical performance. In examples 1-4, H-ZIF-8 was prepared by in-situ growth of zinc hydroxy nitrate, and the sodium hydroxide in the in-situ reaction system also increased the proton removal rate of the ligand 2-methylimidazole, thereby affecting the particle size and morphology of H-ZIF-8.
As can be seen from the raw material formulation shown in Table 1, the experimental group in example 1 is different in that n (Zn 2+ ): the ratio of n (NaOH) is different. N (Zn) in the raw materials of Experimental group 1-1 2+ ): n (NaOH) =1:0.67; n (Zn) in the raw materials of experiment groups 1-2 2+ ): n (NaOH) =1:0.5; n (Zn) in the raw materials of experimental groups 1 to 3 2+ ): n (NaOH) =1:1; n (Zn) in the raw materials of experiment groups 1 to 4 2+ ): n (NaOH) =1:1.2; n (Zn) in the raw materials of experiment groups 1 to 5 2+ )：n(NaOH)＝1:1.5。
Comparing the test results of example 1, it was found that as n (Zn 2+ ): the ratio of n (NaOH) is reduced, namely the feeding amount of NaOH is increased, and the electrochemical performance of the prepared H-ZIF-8 is also improved. And test data of test group 1-1 to test group 1-3 and test group 1-4 are compared with test groupThe test data for test group 1-2 and test group 1-5 are better, with test group 1-1 performing best. From this, it was demonstrated that n (Zn) was obtained by controlling the amounts of sodium hydroxide solution and zinc nitrate solution fed 2+ ): n (NaOH) =1: 0.6 to 1.2, the component contained in the prepared zinc hydroxy nitrate intermediate is Zn 5 (OH) 8 (NO 3 ) 2 ·2H 2 O and Zn (OH) (NO 3 )·H 2 O. The intermediate formed by the two zinc hydroxy nitrates has more active sites, can promote the generation of H-ZIF-8, and the prepared H-ZIF-8 material has a hierarchical pore structure, and also has a pore structure inside the material, so that the H-ZIF-8 material has enough storage space. Lithium ions can enter the inner space of the H-ZIF-8 through the multi-level pore structure, and lithium vacancies are left, so that the transportation of lithium ions in the material is realized. Therefore, the H-ZIF-8 is adopted to prepare the solid electrolyte membrane, so that the lithium ion conduction capacity and the lithium ion migration number of a battery product applying the solid electrolyte membrane can be further improved. In addition, the zinc hydroxy nitrate intermediate prepared by the feeding ratio has regular morphology and higher purity, especially contains less impurity ZnO, thereby improving the yield of the prepared H-ZIF-8 material and reducing the waste of raw materials.
As is clear from the raw material formulation shown in Table 1, the experimental groups in example 2 and experimental group 1-1 are different in that n (Zn 2+ ): the ratio of n (2-methylimidazole) is different. N (Zn) in the raw materials of Experimental group 1-1 2+ ): n (2-methylimidazole) =1:32; n (Zn) in the raw material of Experimental group 2-1 2+ ): n (2-methylimidazole) =1:30; n (Zn) in the raw material of Experimental group 2-2 2+ ): n (2-methylimidazole) =1:35.
Comparing the test results of example 2 and experimental group 1-1 in tables 2 and 3, it was found that as n (Zn 2+ ): the ratio of n (2-methylimidazole) is reduced, namely the feeding amount of the 2-methylimidazole is increased, and the electrochemical performance of the prepared H-ZIF-8 is also improved. In the experimental groups 1-1, 2-1 and 2-2, the feeding amounts of the zinc nitrate solution and the 2-methylimidazole solution can be made to be n (Zn 2+ ): n (2-methylimidazole) =1: 30-35, and the hydroxyl nitric acid prepared under the in-situ reaction systemThe zinc intermediate is used as a nucleation growth site, and zinc ions in an in-situ reaction system and added 2-methylimidazole are utilized to react on the zinc hydroxy nitrate intermediate, so that the prepared H-ZIF-8 has a multi-level pore structure, has good mechanical property and cannot be excessively brittle, and therefore, the H-ZIF-8 material has good processability, and an electrical component applying the multi-level pore ZIF-8 has good quality stability.
As is clear from the raw material formulation shown in Table 1, the experimental groups in example 3 and experimental group 1-1 are different in the concentration of the materials selected in the preparation of H-ZIF-8. Wherein, the concentration of the zinc nitrate solution selected in the experiment group 1-1 is 0.5mol/L, the concentration of the sodium hydroxide solution is 0.2mol/L, and the concentration of the 2-methylimidazole solution is 3mol/L; the concentration of the zinc nitrate solution selected in the experiment group 3-1 is 0.2mol/L, the concentration of the sodium hydroxide solution is 0.1mol/L, and the concentration of the 2-methylimidazole solution is 3mol/L; the concentration of the zinc nitrate solution selected in the experiment group 3-2 is 1.0mol/L, the concentration of the sodium hydroxide solution is 0.3mol/L, and the concentration of the 2-methylimidazole solution is 3mol/L. The concentration of the zinc nitrate solution selected in the experiment group 3-3 is 0.5mol/L, the concentration of the sodium hydroxide solution is 0.2mol/L, and the concentration of the 2-methylimidazole solution is 2mol/L; the concentration of the zinc nitrate solution selected in the experimental group 3-4 is 0.5mol/L, the concentration of the sodium hydroxide solution is 0.2mol/L, and the concentration of the 2-methylimidazole solution is 4mol/L.
Comparing the test results of example 3 and experimental group 1-1 in tables 2 and 3, it was found that the concentration of the zinc nitrate solution affected the microscopic morphology of the zinc hydroxy nitrate intermediate, and further affected the microscopic morphology of H-ZIF-8 using the zinc hydroxy nitrate intermediate as a nucleation growth site. Comparing the test results of the test groups 1-1, 3-1 and 3-2, and the electrochemical performance of the H-ZIF-8 shows a trend of descending after ascending along with the ascending of the concentration of the zinc nitrate solution and the sodium hydroxide solution. In the three experimental groups, the concentration of the zinc nitrate solution is 0.2-1.0 mol/L, and the concentration of the sodium hydroxide solution is 0.1-0.3 mol/L, so that the prepared product zinc hydroxy nitrate intermediate is uniform in appearance and has more growth sites, and when the H-ZIF-8 prepared under the reaction system is applied to a battery component, the battery component has better lithium ion storage performance and higher lithium ion migration number. Comparing the test results of the test groups 1-1, 3-3 and 3-4, and showing the trend of descending after the ascending of the electrochemical performance of the H-ZIF-8 along with the ascending of the concentration of the zinc nitrate solution and the concentration of the 2-methylimidazole solution. It is shown that the concentration of the 2-methylimidazole solution and the concentration of zinc ions in the in-situ reaction system also affect the generation of H-ZIF-8 and the micropore structure. In the three experimental groups, the concentration of the zinc nitrate solution is 0.2-1.0 mol/L, the concentration of the 2-methylimidazole solution is 2-4 mol/L, and when the prepared H-ZIF-8 is applied to battery products, the rapid deintercalation of lithium ions is facilitated, and the lithium ion conductivity and the lithium ion migration number of the battery products can be further improved. Wherein, in the experimental group 1-1, the concentration of the zinc nitrate solution is 0.5mol/L, the concentration of the sodium hydroxide solution is 0.2mol/L, the concentration of the 2-methylimidazole solution is 3mol/L, and the prepared H-ZIF-8 has the best performance.
As is clear from the raw material formulation shown in Table 1, the experimental groups in example 4, experimental groups 1-1, and control group 3 are different in that the mass ratio of H-ZIF-8 to halloysite nanotubes in the selected highly conductive additive is different when preparing the solid electrolyte membrane. Wherein, in the high-conductivity additive selected in the experimental group 1-1, the H-ZIF-8 accounts for 70wt percent and the halloysite nanotube accounts for 30wt percent; in the high-conductivity additive selected in the experiment group 4-1, the H-ZIF-8 accounts for 75wt percent, and the halloysite nanotube accounts for 25wt percent; in the high-conductivity additive selected in the experiment group 4-2, the H-ZIF-8 accounts for 65wt percent, and the halloysite nanotube accounts for 35wt percent; the solid electrolyte membrane prepared in the experimental group 4-3 does not contain halloysite nanotubes; the solid electrolyte membrane prepared in control group 3 did not contain H-ZIF-8.
Comparing the test results of the embodiment 4, the experiment group 1-1 and the comparison group 3, the test results of the experiment group 1-1, the experiment group 4-1 and the experiment group 4-2 are better than the test results of the experiment group 4-3 and the comparison group 3, so that the experiment group 1-1, the experiment group 4-1 and the experiment group 4-2 are mutually matched through the hierarchical pore structure of the H-ZIF-8 material and the hollow structure of the halloysite nanotube, more space is provided for storing lithium ions, the rapid movement of the lithium ions is promoted, the ion conductivity of the battery product using the H-ZIF-8 material and the halloysite nanotube is effectively improved, and the electrochemical performance of the battery product is further improved. On the other hand, the average polarization voltage of the experimental group 4-3 and the experimental group 1-1 can be found to be smaller than that of the experimental group 4-3, namely the solid electrolyte membrane prepared by the experimental group 1-1 has higher cycling stability, so that the H-ZIF-8 material and the halloysite nanotube have a synergistic effect, the chemical window of the battery can be effectively widened, and the cycling stability and the cycling life of the battery can be improved. And the inventor finds that the electrochemical performance of the prepared solid electrolyte membrane tends to be improved firstly and then reduced as the mass ratio of the H-ZIF-8 to the halloysite nanotubes is improved. In the high-conductivity additive selected in the experimental group 1-1, the H-ZIF-8 accounts for 70wt percent and the halloysite nanotube accounts for 30wt percent, so that the prepared solid electrolyte membrane has optimal electrochemical performance.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The hierarchical pore ZIF-8 is characterized in that the hierarchical pore ZIF-8 is prepared by the following steps:
s1, mixing a sodium hydroxide solution and a zinc nitrate solution to obtain an in-situ reaction system, wherein sodium hydroxide and zinc nitrate in the in-situ reaction system react to synthesize a zinc hydroxy nitrate intermediate;
s2, adding a 2-methylimidazole solution into the in-situ reaction system, and in-situ growing ZIF-8 on the zinc hydroxy nitrate intermediate, thereby preparing the hierarchical pore ZIF-8.
2. The hierarchical pore ZIF-8 according to claim 1, characterized in that the feeding amounts of the sodium hydroxide solution and the zinc nitrate solution satisfy n (Zn 2+ )：n(OH - )＝1：0.6～1.2。
3. The hierarchical porous ZIF-8 according to claim 2, wherein the concentration of the zinc nitrate solution is 0.2 to 1.0mol/L and the concentration of the sodium hydroxide solution is 0.1 to 0.3mol/L.
4. The hierarchical porous ZIF-8 according to claim 2, wherein the amount of zinc nitrate solution and 2-methylimidazole solution added satisfies n (Zn 2+ ): n (2-methylimidazole) =1: 30-35.
5. The hierarchical porous ZIF-8 as set forth in claim 4, wherein: the concentration of the zinc nitrate solution is 0.2-1.0 mol/L, and the concentration of the 2-methylimidazole solution is 2-4 mol/L.
6. The hierarchical porous ZIF-8 of any one of claims 1-5, wherein: the process for preparing the hierarchical pore ZIF-8 is carried out at 20-30 ℃; in the step S1, the sodium hydroxide solution and the zinc nitrate solution are mixed and then react for 10 to 20 minutes to obtain the zinc hydroxy nitrate intermediate; in S2, the reaction time of in-situ growth is 1.5-2.5 hours.
7. A highly conductive additive comprising the hierarchical porous ZIF-8 and halloysite nanotubes of any one of claims 1-6; in the high-conductivity additive, the content of the hierarchical pore ZIF-8 is 65-75wt% and the content of the halloysite nanotube is 25-35wt% according to mass percentage.
8. The highly conductive additive according to claim 7, wherein the halloysite nanotubes have an average inner diameter of 15 to 60nm, an average outer diameter of 50 to 100nm, and an average tube length of 0.1 to 10 μm.
9. A solid electrolyte membrane comprising the highly conductive additive according to any one of claims 7 or 8, the highly conductive additive being not less than 80% by mass in the solid electrolyte membrane.
10. A battery, characterized in that: a solid electrolyte membrane comprising the solid electrolyte membrane of claim 9, a positive electrode sheet, a negative electrode sheet, the solid electrolyte membrane disposed between the positive electrode sheet and the negative electrode sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310446486.0A CN116640318A (en) | 2023-04-24 | 2023-04-24 | Hierarchical pore ZIF-8, high-conductivity additive, solid electrolyte membrane and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310446486.0A CN116640318A (en) | 2023-04-24 | 2023-04-24 | Hierarchical pore ZIF-8, high-conductivity additive, solid electrolyte membrane and battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116640318A true CN116640318A (en) | 2023-08-25 |
Family
ID=87642496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310446486.0A Pending CN116640318A (en) | 2023-04-24 | 2023-04-24 | Hierarchical pore ZIF-8, high-conductivity additive, solid electrolyte membrane and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116640318A (en) |
-
2023
- 2023-04-24 CN CN202310446486.0A patent/CN116640318A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111244422B (en) | Organic ion doped vanadium oxide positive electrode material for water-based zinc ion battery and preparation method and application thereof | |
| EP4040556A1 (en) | Method of preparing and application of carbon-selenium composites | |
| CN108767276B (en) | Preparation method of nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for lithium-oxygen battery | |
| EP3174141B1 (en) | Process for producing a doped tungsten oxide material | |
| CN109768266B (en) | Three-dimensional nitrogen-doped carbon interlayer co-catalyzed by nitrogen and cobalt and preparation method thereof | |
| CN111646459A (en) | Preparation method and application of boron-doped graphene material | |
| WO2022237393A1 (en) | Preparation method for lithium iron phosphate | |
| CN108539263B (en) | Preparation method of solid electrolytes with sandwich structure | |
| CN114597341B (en) | Modified pre-lithiated silica material, preparation method and application thereof, and lithium ion battery | |
| CN111584929A (en) | Solid electrolyte, preparation method and lithium battery | |
| CN114530572A (en) | Composite modified negative electrode for aqueous metal battery | |
| CN112320792B (en) | Preparation method of negative electrode material for lithium ion battery and product thereof | |
| CN115693022B (en) | Zinc-iodine battery diaphragm based on covalent organic framework and preparation method and application thereof | |
| CN114069159B (en) | Diaphragm based on nitrogen-rich column layer structure MOF, and preparation method and application thereof | |
| CN114551982B (en) | Double-salt PEO-based polymer composite solid electrolyte and preparation method thereof | |
| CN116640318A (en) | Hierarchical pore ZIF-8, high-conductivity additive, solid electrolyte membrane and battery | |
| CN115188945A (en) | Coated positive electrode material and preparation method and application thereof | |
| CN111384368A (en) | Carbon-selenium composite material, preparation method thereof and application thereof in lithium-selenium battery | |
| CN114142033A (en) | Modified graphite negative electrode material for lithium ion battery | |
| CN113178561A (en) | Negative electrode material modified by reactive two-dimensional molecular brush SEI film, and preparation method and application thereof | |
| CN114520302B (en) | Aqueous metal battery and modified anode thereof | |
| CN117430824B (en) | Nitrogen-doped hollow MOF material and preparation method and application thereof | |
| CN117976839A (en) | Low-residual-alkali sodium ion positive electrode material and modification method thereof | |
| RU2423758C1 (en) | Composite mix for electrolyte of lithium current source | |
| CN118373422A (en) | Layered silicon material, surface oxygen content regulating and controlling method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |