CN116470132A - Metal-organic framework glass solid electrolyte and preparation method and application thereof - Google Patents
Metal-organic framework glass solid electrolyte and preparation method and application thereof Download PDFInfo
- Publication number
- CN116470132A CN116470132A CN202310542852.2A CN202310542852A CN116470132A CN 116470132 A CN116470132 A CN 116470132A CN 202310542852 A CN202310542852 A CN 202310542852A CN 116470132 A CN116470132 A CN 116470132A
- Authority
- CN
- China
- Prior art keywords
- glass
- mofs
- solid electrolyte
- metal
- solid
- 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
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 129
- 239000011521 glass Substances 0.000 title claims abstract description 88
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000012528 membrane Substances 0.000 claims description 66
- 229910052751 metal Inorganic materials 0.000 claims description 44
- 239000002184 metal Substances 0.000 claims description 44
- 239000011230 binding agent Substances 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- 150000002500 ions Chemical class 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 150000001768 cations Chemical class 0.000 claims description 13
- 238000005096 rolling process Methods 0.000 claims description 11
- 238000004146 energy storage Methods 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920006184 cellulose methylcellulose Polymers 0.000 claims description 2
- 239000011152 fibreglass Substances 0.000 claims description 2
- 229920006168 hydrated nitrile rubber Polymers 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 238000007578 melt-quenching technique Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 2
- 239000013155 zeolitic imidazolate framework-4 Substances 0.000 claims description 2
- 239000013156 zeolitic imidazolate framework-62 Substances 0.000 claims description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 2
- 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 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 33
- 239000002904 solvent Substances 0.000 description 26
- 238000005520 cutting process Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- WFLRGOXPLOZUMC-UHFFFAOYSA-N [Li].O=C=O Chemical compound [Li].O=C=O WFLRGOXPLOZUMC-UHFFFAOYSA-N 0.000 description 1
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013141 crystalline metal-organic framework Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to the technical field of glass materials and battery solid electrolytes, and discloses a metal-organic framework (MOFs) glass solid electrolyte, a preparation method and application thereof. The MOFs glass solid electrolyte has the characteristics of high room temperature ion conductivity, good air stability, electrochemical stability, mechanical strength, excellent dendrite inhibition capability, light weight and the like, and solves the problems of poor ion conductivity, poor compatibility with positive and negative electrodes, poor chemical and electrochemical stability, lack of flexibility, high cost and the like of the conventional solid electrolyte at room temperature.
Description
Technical Field
The invention relates to the technical field of glass materials and battery solid electrolytes, in particular to a metal-organic frame glass solid electrolyte, a preparation method and application thereof.
Background
Most of the current commercial power batteries, energy storage batteries and consumer batteries adopt organic electrolyte, so that risks of internal short circuit, ignition and explosion induced by leakage are faced, and life and property safety of users is seriously threatened. Therefore, developing a solid electrolyte with high ion conductivity and good compatibility with positive and negative electrodes, and developing a green, safe, and efficient solid battery are important approaches to solve the above problems.
Solid-state electrolytes are a core element for determining the performance of solid-state batteries, except for electrode materials, and currently reported solid-state battery electrolytes mainly include inorganic solid-state electrolytes (such as oxides and sulfides), polymer solid-state electrolytes and composite solid-state electrolytes.
Inorganic solid electrolytes, such as sulfides, although having high room temperature ionic conductivity (10 -4 ～10 -2 S cm -1 ) However, the air stability is poor, side reactions with lithium metal occur, the interface impedance is high, and the cracking is easy; the polymer solid electrolyte has better flexibility and interface compatibility, but lower ion conductivity at room temperature (10) -8 ～10 -6 S cm -1 ) The method comprises the steps of carrying out a first treatment on the surface of the The composite solid electrolyte, while integrating the advantages of both, has relatively low ionic conductivity at room temperature, typically about 10 -5 S cm -1 The ionic conductivity of the solid-state battery, which still cannot meet the normal performance of the solid-state battery, is larger than 10 -4 S cm -1 Is not limited.
Although great progress is made in improving room temperature ionic conductivity, improving interface compatibility and stability of solid electrolyte, the existing solid electrolyte still does not meet the production and use requirements of solid batteries, and the large-scale production of solid batteries is greatly restricted due to high raw material cost, strict preparation process requirements and the like.
Therefore, the development of a novel solid electrolyte material which integrates high ion conductivity, high chemical stability and low interface impedance, is low in cost and easy to process is a key for promoting the practical progress of the solid battery.
Disclosure of Invention
In order to solve the defects and shortcomings of the existing solid electrolyte technology, the primary aim of the invention is to provide MOFs glass solid electrolyte, which takes MOFs glass as a main matrix to form an MOFs glass electrolyte membrane or an MOFs glass electrolyte sheet with high room temperature ion conductivity, excellent performance and low cost.
The invention also aims at a preparation method of the MOFs glass solid electrolyte, which is characterized in that the MOFs glass solid electrolyte obtained by the preparation method has excellent ion conductivity, good compatibility and stability with the anode and the cathode of a battery and outstanding metal dendrite inhibition capability.
Another object of the present invention is to design and construct a solid-state battery with high safety and excellent performance. Wherein the cations transported in the MOFs glass are matched to the type of solid state battery of interest assembled. For example, the transported cations are lithium ions, i.e., solid state lithium batteries, etc. can be assembled.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the metal organic frame glass solid electrolyte is MOFs glass as the main material.
Preferably, the metal-organic framework glass includes, but is not limited to, phosphate-imidazole series (e.g., [ Zn (HPO) 4 )(H 2 PO 4 )](H 2 Im) 2 、[Zn 3 (H 2 PO 4 ) 6 (H 2 O) 3 ](HbIm)、[Zn 3 (H 2 PO 4 ) 6 (H 2 O) 3 ]H(2-MebIm)、[Zn 3 (H 2 PO 4 ) 6 (H 2 O) 3 ](BTA) and the like), a zeolitic imidazolate series (e.g., ZIF-4, ZIF-8, ZIF-62, ZIF-76 and the like), a titanyl cluster-hydroquinone series (e.g., ti) 16 O 16 (OEt) 32 、Ti 12 O 16 (O-iPr) 16 Etc.), thiocyanate (e.g. Cu 2 (SCN) 3 (C 4 bpy)) and bis-fluorosulfonyl imide-nitrile framework series (e.g., li [ N (SO) 2 F) 2 ](NCCH 2 CH 2 CN) 2 ) Metal-bis (acetamide) framework).
Preferably, the metal-organic framework glass is obtained by melting, quenching or ball milling, high pressure, X-ray irradiation.
Preferably, the binder includes, but is not limited to, an aqueous binder (PTFE, HNBR, SBR, CMC, PAN, LA, 133), an oily binder PVDF, or no binder is used.
Preferably, the binder content is: 0-10%, wherein the MOFs glass content in the MOFs glass solid electrolyte membrane is 50-97%, and the metal salt content in the solid electrolyte is as follows: 40-3%.
The preparation method of the metal-organic framework glass solid electrolyte further comprises the following steps:
s1: mixing MOFs glass, metal salt and binder uniformly according to a certain proportion;
s2: MOFs glass can be prepared into MOFs glass films or sheets by applying pressure, in which form it can be extruded and rolled, or by coating on a substrate to form a MOFs glass-based solid electrolyte film, or by melt-quenching into MOFs glass films or sheets.
Preferably, the MOFs glass film substrate includes, but is not limited to, polyethylene, polypropylene, polyacrylonitrile, cellulose films, and fiberglass films.
A solid state energy storage device having the MOFs glass solid state electrolyte described above, comprising a positive electrode, a negative electrode, and a solid state electrolyte between the positive electrode and the negative electrode, the solid state electrolyte being the MOFs glass solid state electrolyte of claim 1.
Preferably, the cations include, but are not limited to, any of Li ion, na ion, mg ion, ca ion, K ion, zn ion, proton, different types of cations corresponding to the respective solid-state batteries.
When the cation is Li ion, the solid-state lithium battery may be a solid-state lithium battery, and specifically, the solid-state lithium battery in the present application refers to a solid-state battery in which the carrier is lithium ion, for example, a solid-state lithium sulfur battery, a solid-state lithium-air battery, a solid-state lithium-oxygen battery, a solid-state lithium-carbon dioxide battery, a solid-state lithium ion battery, a solid-state lithium metal battery, or the like.
When the cation is Na ion, it may be a solid-state sodium battery.
When the cation is Mg ion, it may be a solid-state magnesium battery.
When the cations are Ca ions, they may be solid-state calcium batteries.
When the cation is K ion, it may be a solid-state potassium battery.
When the cations are Zn ions, they may be solid zinc batteries.
When the cation is proton, it may be a solid fuel cell.
In this application, the solid-state sodium battery, the solid-state magnesium battery, the solid-state calcium battery, the solid-state potassium battery, and the solid-state zinc battery are similar to the solid-state lithium battery, and are not described here again.
Compared with the prior art, the invention provides the metal-organic frame glass solid electrolyte, the preparation method and the application thereof, and has the following beneficial effects:
1. the MOFs glass solid electrolyte has the characteristics of high room temperature ion conductivity, good air stability, electrochemical stability, mechanical strength, excellent dendrite inhibition capability, light weight and the like, and solves the problems of poor ion conductivity, poor compatibility with positive and negative electrodes, poor chemical and electrochemical stability, lack of flexibility, high cost and the like of the conventional solid electrolyte at room temperature.
2. The energy storage battery using MOFs glass electrolyte as solid electrolyte in the invention has the advantages of long service life, high safety, high energy density and the like by virtue of the advantages of high ion conductivity, excellent dendrite inhibition capability, low cost, light weight and the like of MOFs glass, is obviously superior to other solid electrolyte systems, and opens up a new direction for the design and research and development of novel solid batteries.
3. The solid-state battery provided by the invention has the advantages of thinned structural layout, good flexibility, low raw material cost, low energy consumption in preparation, simple production process, strong practicability and wide application prospect in the field of solid-state energy storage.
Drawings
FIG. 1 is an ion impedance spectrum of MOFs glass solid-state electrolyte prepared in the first embodiment of the invention at room temperature;
FIG. 2 is a graph showing the voltage and time relationship of MOFs glass solid-state electrolyte prepared in example two of the present invention;
fig. 3 is a graph showing the long cycle performance of the MOFs glass solid-state battery prepared in example three of the present invention at a current density of 1C;
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Referring to fig. 1-3, a MOFs glass-based solid electrolyte is prepared:
s1: MOFs glass, a binder and metal salt are mixed according to the mass ratio of 75:10:15, mixing evenly, rolling to prepare a solid electrolyte membrane with the thickness of 70 mu m, and cutting the solid electrolyte membrane into a solid electrolyte membrane with the diameter of 19mm after vacuum drying;
s2: assembling the prepared solid electrolyte membrane into symmetrical cell according to the sequence of stainless steel electrode I and adding a little solvent on the solid electrolyte membrane, wherein FIG. 1 is ion impedance spectrum at room temperature with ion conductivity of 8.6X10 -5 S cm -1 ；
S3: and assembling the full cell according to the sequence of the positive electrode I and the solid electrolyte membrane I and the negative electrode I, adding a small amount of solvent on the solid electrolyte membrane, and standing for a period of time to test the electrochemical performance of the full cell.
Example two
Preparation of MOFs glass-based solid electrolyte:
s1: MOFs glass, a binder and metal salt are mixed according to the mass ratio of 70:20:10, mixing evenly, rolling to prepare a solid electrolyte membrane with the thickness of 100 mu m, vacuum drying and cutting into the required size;
s2: assembling the prepared solid electrolyte membrane into symmetrical cell according to the sequence of metal electrode I solid electrolyte membrane I metal electrode, adding a little solvent on the solid electrolyte membrane, and making voltage-time relationship curve of FIG. 2 at 0.1mA cm -2 The cycle performance diagram under the current density is that the battery is only 60.5mV after 400 hours of cycle, and the battery has good compatibility with a metal negative electrode;
s3: the full cell is assembled according to the sequence of the positive electrode I solid electrolyte membrane I negative electrode, a small amount of solvent is added on the solid electrolyte membrane, and the full cell is tested after a period of time of rest, and fig. 3 is a long-cycle performance diagram of the full cell under the current density of 1C, and the stable specific capacity of the full cell after 450 circles is 112mAh g -1 Exhibiting good electrochemical performance.
Example III
Preparation of MOFs glass-based solid electrolyte:
s1: MOFs glass, a binder and metal salt are mixed according to the mass ratio of 80:10:10, mixing evenly, rolling to prepare a solid electrolyte membrane with the thickness of 100 mu m, vacuum drying and cutting into the required size;
s2: the prepared solid electrolyte membrane is assembled into symmetrical cell according to the sequence of metal electrode I solid electrolyte membrane I metal electrode, and a little solvent is added on the solid electrolyte membrane, the ionic conductivity is 5.85×10 -4 S cm -1 ；
S3: and assembling the full cell according to the sequence of the positive electrode I and the solid electrolyte membrane I and the negative electrode I, adding a small amount of solvent on the solid electrolyte membrane, and standing for a period of time to test the electrochemical performance of the full cell.
Example IV
Preparation of MOFs glass-based solid electrolyte:
s1: MOFs glass, a binder and metal salt are mixed according to the mass ratio of 65:10:25, uniformly mixing, rolling to prepare a solid electrolyte membrane with the thickness of 90 mu m, vacuum drying and cutting into the required size;
s2: the prepared solid electrolyte membrane is electrically processed according to metalSymmetrical cell is assembled by sequentially arranging metal electrodes of solid electrolyte film, and adding a little solvent on the solid electrolyte film, wherein the ionic conductivity is 7.78X10% -5 S cm -1 ；
S3: and assembling the full cell according to the sequence of the positive electrode I and the solid electrolyte membrane I and the negative electrode I, adding a small amount of solvent on the solid electrolyte membrane, and standing for a period of time to test the electrochemical performance of the full cell.
Example five
Preparation of MOFs glass-based solid electrolyte:
s1: MOFs glass, a binder and metal salt are mixed according to the mass ratio of 75:5: mixing 20 materials, mixing uniformly, rolling to prepare a solid electrolyte membrane with the thickness of 60 mu m, vacuum drying and cutting into the required size;
s2: the prepared solid electrolyte membrane is assembled into symmetrical cell according to the sequence of metal electrode I solid electrolyte membrane I metal electrode, and a little solvent is added on the solid electrolyte membrane, the ionic conductivity is 1.77×10 -4 S cm -1 ；
S3: and assembling the full cell according to the sequence of the positive electrode I and the solid electrolyte membrane I and the negative electrode I, adding a small amount of solvent on the solid electrolyte membrane, and standing for a period of time to test the electrochemical performance of the full cell.
Example six
Preparation of MOFs glass-based solid electrolyte:
s1: MOFs glass, a binder and metal salt are mixed according to the mass ratio of 55:10:35, mixing evenly, rolling to prepare a solid electrolyte membrane with the thickness of 50 mu m, vacuum drying and cutting into the required size;
s2: the prepared solid electrolyte membrane is assembled into symmetrical cell according to the sequence of metal electrode I solid electrolyte membrane I metal electrode, and a little solvent is added on the solid electrolyte membrane, the ionic conductivity is 5.62 multiplied by 10 -4 S cm -1 ；
S3: and assembling the full cell according to the sequence of the positive electrode I and the solid electrolyte membrane I and the negative electrode I, adding a small amount of solvent on the solid electrolyte membrane, and standing for a period of time to test the electrochemical performance of the full cell.
Example seven
Preparation of MOFs glass-based solid electrolyte:
s1: MOFs glass, a binder and metal salt are mixed according to the mass ratio of 85:10:5, mixing materials, rolling to prepare a solid electrolyte membrane with the thickness of 50 mu m, vacuum drying and cutting into the required size;
s2: the prepared solid electrolyte membrane is assembled into symmetrical cell according to the sequence of metal electrode I solid electrolyte membrane I metal electrode, and a little solvent is added on the solid electrolyte membrane, the ionic conductivity is 7.67×10 -4 S cm -1 ；
S3: and assembling the full cell according to the sequence of the positive electrode I and the solid electrolyte membrane I and the negative electrode I, adding a small amount of solvent on the solid electrolyte membrane, and standing for a period of time to test the electrochemical performance of the full cell.
Example eight
Preparation of MOFs glass-based solid electrolyte:
s1: MOFs glass, a binder and metal salt are mixed according to the mass ratio of 75:10:15, mixing evenly, rolling to prepare a solid electrolyte membrane with the thickness of 50 mu m, vacuum drying and cutting into the required size;
s2: the prepared solid electrolyte membrane is assembled into symmetrical cell according to the sequence of metal electrode I solid electrolyte membrane I metal electrode, and a little solvent is added on the solid electrolyte membrane, the ionic conductivity is 5.28X10 -4 S cm -1 ；
S3: and assembling the full cell according to the sequence of the positive electrode I solid electrolyte membrane I negative electrode I, adding a small amount of solvent on the solid electrolyte membrane, and standing for 8 hours to test the electrochemical performance of the full cell.
Example nine
Preparation of MOFs glass-based solid electrolyte:
s1: MOFs glass, a binder and metal salt are mixed according to the mass ratio of 67:10:23, mixing, rolling to prepare a solid electrolyte membrane with the thickness of 50 mu m, vacuum drying and cutting into the required size;
s2: the prepared solid electrolyte membraneThe symmetrical cell is assembled by the sequence of metal electrode and solid electrolyte membrane, and a little solvent is added on the solid electrolyte membrane, the ionic conductivity is 12.8X10 -4 S cm -1 ；
S3: and assembling the full cell according to the sequence of the positive electrode I and the solid electrolyte membrane I and the negative electrode I, adding a small amount of solvent on the solid electrolyte membrane, and standing for a period of time to test the electrochemical performance of the full cell.
Examples ten
Preparation of MOFs glass-based solid electrolyte:
s1: MOFs glass, a binder and metal salt are mixed according to the mass ratio of 60:10:30, mixing evenly, rolling to prepare a solid electrolyte membrane with the thickness of 50 mu m, vacuum drying and cutting into the required size;
s2: the prepared solid electrolyte membrane is assembled into symmetrical cell according to the sequence of metal electrode I solid electrolyte membrane I metal electrode, and 6 μl solvent is added on the solid electrolyte membrane, the ionic conductivity is 14.7X10 -4 S cm -1 ；
S3: and assembling the full cell according to the sequence of the positive electrode I and the solid electrolyte membrane I and the negative electrode I, adding a small amount of solvent on the solid electrolyte membrane, and standing for a period of time to test the electrochemical performance of the full cell.
Example eleven
Preparation of MOFs glass-based solid electrolyte:
s1: MOFs glass, a binder and metal salt are mixed according to the mass ratio of 95:0:5, mixing evenly, extruding to prepare a solid electrolyte sheet with the thickness of 250 mu m;
s2: the prepared solid electrolyte sheet is assembled into symmetrical battery according to the sequence of metal electrodes I, and a little solvent is added on the solid electrolyte sheet, the ionic conductivity is 1.54 multiplied by 10 -4 S cm -1 ；
S3: and assembling the full battery according to the positive electrode I solid electrolyte sheet I negative electrode sequence, adding a small amount of solvent on the solid electrolyte sheet, and standing for a period of time to perform the electrochemical performance test of the full battery.
Example twelve
Preparation of MOFs glass-based solid electrolyte:
s1: MOFs glass, a binder and metal salt are mixed according to the mass ratio of 85:10:5, compounding, coating the substrate;
s2: the prepared solid electrolyte membrane is assembled into symmetrical battery according to the sequence of metal electrode I solid electrolyte membrane I metal electrode, and a little solvent is added on the solid electrolyte sheet, the ionic conductivity is 3.67 multiplied by 10 -4 S cm -1 ；
S3: and assembling the full battery according to the positive electrode I solid electrolyte sheet I negative electrode sequence, adding a small amount of solvent on the solid electrolyte sheet, and standing for one period to perform the electrochemical performance test of the full battery.
Example thirteen
Preparation of MOFs glass-based solid electrolyte:
s1: crystalline MOFs, a binder and metal salt are mixed according to the mass ratio of 95:0:5, mixing evenly, extruding to prepare a solid electrolyte sheet with the thickness of 250 mu m, and placing the solid electrolyte sheet into an inert gas furnace for melting-quenching treatment to obtain a vitrified solid electrolyte sheet;
s2: the prepared solid electrolyte sheet is assembled into symmetrical battery according to the sequence of metal electrodes I, and a little solvent is added on the solid electrolyte sheet, the ionic conductivity is 1.92 multiplied by 10 -4 S cm -1 ：
S3: and assembling the full battery according to the positive electrode I solid electrolyte sheet I negative electrode sequence, adding a small amount of solvent on the solid electrolyte sheet, and standing for a period of time to perform the electrochemical performance test of the full battery.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The metal-organic frame glass solid electrolyte comprises metal-organic frame glass, metal salt and a binder, and is characterized in that: and mixing and rolling the metal organic frame glass, metal salt and a binder to obtain the MOFs glass solid electrolyte membrane, wherein the MOFs glass solid electrolyte membrane can be a MOFs glass solid electrolyte sheet, and the MOFs glass contains mobilizable cations.
2. The metal-organic framework glass solid state electrolyte of claim 1, wherein: the metal-organic framework glass includes, but is not limited to, phosphate-imidazole series (e.g., [ Zn (HPO) 4 )(H 2 PO 4 )](H 2 Im) 2 、[Zn 3 (H 2 PO 4 ) 6 (H 2 O) 3 ](HbIm)、[Zn 3 (H 2 PO 4 ) 6 (H 2 O) 3 ]H(2-MebIm)、[Zn 3 (H 2 PO 4 ) 6 (H 2 O) 3 ](BTA) and the like), a zeolitic imidazolate series (e.g., ZIF-4, ZIF-8, ZIF-62, ZIF-76 and the like), a titanyl cluster-hydroquinone series (e.g., ti) 16 O 16 (OEt) 32 、Ti 12 O 16 (O-iPr) 16 Etc.), thiocyanate (e.g. Cu 2 (SCN) 3 (C 4 bpy)) and bis-fluorosulfonyl imide-nitrile framework series (e.g., li [ N (SO) 2 F) 2 ](NCCH 2 CH 2 CN) 2 ) Metal-bis (acetamide) framework).
3. The metal-organic framework glass solid state electrolyte of claim 1, wherein: the metal-organic framework glass is obtained by melting, quenching or ball milling, high-pressure and X-ray irradiation.
4. The metal-organic framework glass solid state electrolyte of claim 1, wherein: cations present in the MOFs glass include any one of Li ions, na ions, mg ions, ca ions, K ions, zn ions, and protons.
5. The metal-organic framework glass solid state electrolyte of claim 1, wherein: the binder includes, but is not limited to, an aqueous binder (PTFE, HNBR, SBR, CMC, PAN, LA 133), an oily binder PVDF, or no binder is used.
6. The metal-organic framework glass solid state electrolyte of claim 1, wherein: the content of the binder is as follows: 0-10%, wherein the MOFs glass content in the MOFs glass-based solid electrolyte membrane is 50-97%.
7. The preparation method of the metal organic frame glass solid electrolyte is characterized by comprising the following steps of: the preparation method also comprises the following steps:
s1: mixing MOFs glass, metal salt and binder uniformly according to a certain proportion;
s2: MOFs glass can be prepared into MOFs glass films or sheets by applying pressure, in which form the MOFs glass can be extruded and rolled, or by coating on a substrate to form a MOFs glass-based solid electrolyte membrane, or by melt-quenching into MOFs glass sheets.
8. The method for preparing a metal-organic framework glass solid electrolyte according to claim 7, wherein: the MOFs glass film substrates include, but are not limited to, polyethylene, polypropylene, polyacrylonitrile, cellulose films, and fiberglass films.
9. The solid state energy storage device adopting the electrolyte comprises a positive electrode, a negative electrode and a solid state electrolyte between the positive electrode and the negative electrode, and is characterized in that: the solid state electrolyte is the MOFs glass-based solid state electrolyte of claim 1.
10. A solid state energy storage device as claimed in claim 9, wherein: the content of metal salt in the solid electrolyte is as follows: 40-3%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310542852.2A CN116470132A (en) | 2023-05-15 | 2023-05-15 | Metal-organic framework glass solid electrolyte and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310542852.2A CN116470132A (en) | 2023-05-15 | 2023-05-15 | Metal-organic framework glass solid electrolyte and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116470132A true CN116470132A (en) | 2023-07-21 |
Family
ID=87184442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310542852.2A Pending CN116470132A (en) | 2023-05-15 | 2023-05-15 | Metal-organic framework glass solid electrolyte and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116470132A (en) |
-
2023
- 2023-05-15 CN CN202310542852.2A patent/CN116470132A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103746089B (en) | A kind of solid lithium battery with gradient-structure and preparation method thereof | |
| CN110071284B (en) | Method for protecting lithium metal electrode | |
| WO2020098427A1 (en) | Lithium ion battery negative electrode material and non-aqueous electrolyte battery | |
| CN107195962A (en) | A kind of composite solid electrolyte and preparation method thereof | |
| CN102969473A (en) | Organic/inorganic composite porous thin film and electrochemical energy storing device using same | |
| CN111435757B (en) | Composite polymer electrolyte, preparation method thereof and lithium battery | |
| CN114373982B (en) | Liquid ether organic electrolyte-based low-negative electrode secondary sodium battery and preparation method thereof | |
| CN111786013B (en) | Composite solid electrolyte and preparation method thereof | |
| CN111987348B (en) | Preparation method of NASICON type solid-state battery | |
| CN111725559A (en) | Solid electrolyte, method for preparing the same, and lithium secondary solid battery | |
| CN113258032B (en) | Negative electrode material, negative electrode slurry, battery cell, low-temperature-resistant battery and preparation method of battery | |
| CN110943258A (en) | PVDF-HFP composite lignocellulose gel polymer electrolyte membrane and preparation method thereof | |
| CN113270691A (en) | Pole piece/diaphragm integrated lithium ion battery and preparation method thereof | |
| CN112289995A (en) | Composite positive electrode slurry, positive electrode plate and solid-state battery | |
| CN109360947B (en) | Preparation method of porous carbon cathode material of quasi-solid-state lithium-sulfur battery | |
| CN115010941B (en) | Preparation method and application of ionic covalent organic framework nano-sheet protective layer through electrodeposition | |
| CN116470132A (en) | Metal-organic framework glass solid electrolyte and preparation method and application thereof | |
| CN116014128A (en) | Lithium battery negative electrode material and preparation method thereof | |
| CN1441507A (en) | Prepn of polyvinylidene difluoride film for secondary lithium ion battery | |
| CN112768756B (en) | Solid electrolyte material, and composite solid electrolyte and all-solid-state battery prepared from same | |
| CN116470133A (en) | Polymer/metal-organic framework glass solid electrolyte and preparation method and application thereof | |
| CN117430832B (en) | Multilayer potassium ion gel electrolyte and preparation method thereof | |
| CN114899349B (en) | Method for inhibiting growth of zinc dendrite by modifying zinc of negative electrode of zinc ion battery | |
| KR100515421B1 (en) | Method for manufacturing lithium secondary cell and lithium secondary cell obtained by its method | |
| KR102587795B1 (en) | Electrode for secondary battery and method for preparing the same |
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 |