CN116365021A - Composite solid electrolyte and preparation method and application thereof - Google Patents
Composite solid electrolyte and preparation method and application thereof Download PDFInfo
- Publication number
- CN116365021A CN116365021A CN202310567974.7A CN202310567974A CN116365021A CN 116365021 A CN116365021 A CN 116365021A CN 202310567974 A CN202310567974 A CN 202310567974A CN 116365021 A CN116365021 A CN 116365021A
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- composite solid
- lithium
- bdc
- cofe
- 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 59
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000000654 additive Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000013384 organic framework Substances 0.000 claims abstract description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 20
- 239000012621 metal-organic framework Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 239000013110 organic ligand Substances 0.000 claims description 8
- -1 polysiloxane Polymers 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 4
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QUMITRDILMWWBC-UHFFFAOYSA-N nitroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QUMITRDILMWWBC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 16
- 238000013508 migration Methods 0.000 abstract description 10
- 230000005012 migration Effects 0.000 abstract description 10
- 150000001450 anions Chemical class 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 8
- 239000011268 mixed slurry Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000005518 polymer electrolyte Substances 0.000 description 5
- 229910013684 LiClO 4 Inorganic materials 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000037427 ion transport Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Images
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
- 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)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a composite solid electrolyte, a preparation method and application thereof, wherein the composite solid electrolyte comprises a high molecular polymer, an additive and lithium salt, and the addition amount of the additive is 5-25% of the mass of the high molecular polymer; the additive is a catalyst having-NH 2 and/or-NO 2 Two-dimensional bimetallic-organic framework materials of groups; the invention utilizes the additive to effectively inhibit the migration of anions and improve Li + The ion migration number is based on various pore structures and surface functions of the additive, so that the ion transfer path of the solid electrolyte can be shortened, the number of active sites can be increased, and the ion conductivity of the solid electrolyte and the cycle performance of the battery can be effectively improved.
Description
Technical Field
The invention relates to the technical field of solid electrolytes, in particular to a composite solid electrolyte, a preparation method and application thereof.
Background
Among many energy storage technologies, lithium ion batteries play an important role due to the advantages of high energy density, long service life and the like. The metal lithium has extremely high theoretical capacity (3860 mAh/g) and the lowest electrode potential (3.04V relative to a standard hydrogen electrode), and is the best choice of the cathode material of the next-generation lithium ion battery. However, metallic lithium suffers from serious dendrite problems in conventional liquid electrolytes.
All-solid-state batteries can fully utilize metallic lithium, while their own assembly advantages can lead to higher energy densities. Generally, solid electrolytes can be classified into two types: an inorganic electrolyte and a polymer electrolyte. Inorganic electrolytes, although having high ionic conductivity, have serious interface problems that cause large impedance, thereby greatly limiting practical applications. The polymer electrolyte has the advantages of easy film formation, low cost and the like, and has good application potential in the future all-solid-state batteries. Polymer electrolytes have a great disadvantage: the ionic conductivity is low. The reason is mainly that: (1) the segment movement capability of the polymer is limited, such as the most common PEO polymer electrolyte is easy to crystallize, lithium ions are not suitable to migrate, and the interface is unstable; (2) the movement of lithium ions depends on coordination of polar atoms of the polymer, and has poor degree of freedom and poor mobility. The prior art generally improves ionic conductivity by copolymerization and crosslinking. However, these methods are mostly complex and cumbersome, limiting their application in practical production.
Modification of PEO polymer electrolytes by addition of MOFs is the direction of modification of much research in recent years. As disclosed in patent CN201910367824.5, a composite solid electrolyte material, a preparation method and application thereof are disclosed, and by introducing a metal-organic framework material with a special topological structure, and compounding the metal-organic framework material with an ion-conducting polymer matrix material and an alkali metal or alkaline earth metal salt, the electrolyte can be used at a high temperature, and has good ion transfer performance at a lower temperature. However, the solid electrolyte material still has the problem of low ionic conductivity at a lower temperature (25 ℃), which limits the application of the solid electrolyte material.
Disclosure of Invention
Based on the above-described problems existing in the prior art, the inventors have found that the migration of anions is dominant in the ion migration of the solid electrolyte, which increases the polarization of the battery. Based on this, the present invention provides a composite solid electrolyte, the solid electrolyte packageComprises a high molecular polymer, an additive and lithium salt, wherein the additive is used for effectively inhibiting the migration of anions and improving Li + The ion migration number is based on various pore structures and surface functions of the additive, so that the ion transfer path of the solid electrolyte can be shortened, the number of active sites can be increased, and the ion conductivity of the solid electrolyte and the cycle performance of the battery can be effectively improved.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the composite solid electrolyte comprises a high molecular polymer, an additive and lithium salt, wherein the additive is added in an amount of 5-25% of the mass of the high molecular polymer; the additive is a catalyst having-NH 2 and/or-NO 2 Two-dimensional bimetallic-organic framework materials of radicals.
In some embodiments, li in the lithium salt + And the molar ratio of the polar groups in the high molecular polymer is 1:10-30.
In some embodiments, the central metal ions of the bimetallic-organic framework material are Fe (III) and Co (III).
In some embodiments, the bimetallic organic framework is CoFe-BDC-NH 2 And/or CoFe-BDC-NO 2 。
In some embodiments, the CoFe-BDC-NH 2 Or CoFe-BDC-NO 2 The preparation of the composition comprises the following steps:
dissolving soluble ferric salt, soluble cobalt salt and an organic ligand in a first organic solvent, then adding deionized water, an alcohol solvent and triethylamine, and reacting for more than 24 hours to obtain the CoFe-BDC-NH 2 Or CoFe-BDC-NO 2 ；
Wherein the organic ligand is amino terephthalic acid or nitro terephthalic acid; the mole ratio of the soluble ferric salt, the soluble cobalt salt and the organic ligand is 1-2: 3:1.
in some embodiments, the first organic solvent is dimethylformamide.
In some embodiments, the alcoholic solvent is at least one of ethanol, methanol, propanol, isopropanol, butanol, isobutanol.
In some embodiments, the CoFe-BDC-NH 2 Or CoFe-BDC-NO 2 The preparation method of (2) also comprises the following steps:
after the reaction is completed, solid-liquid separation is carried out, the solid is washed by propanol and ethanol, and then vacuum drying is carried out, thus obtaining the final product.
In some embodiments, the high molecular polymer has a molecular weight of 10 5 ～5×10 6 g/mol。
In some embodiments, the high molecular polymer is at least one of polyethylene oxide, polymethyl methacrylate, polyacrylonitrile, polyvinylidene fluoride, and polysiloxane.
In some embodiments, the lithium salt is at least one of lithium perchlorate, lithium bis (trifluoromethanesulfonyl) imide, lithium trifluoromethanesulfonate, lithium bis (fluorosulfonyl) imide, lithium trifluoromethanesulfonate, lithium oxalyldifluoroborate.
The invention also provides a preparation method of the composite solid electrolyte of any embodiment, which comprises the following steps:
adding the high molecular polymer, the additive and the lithium salt into a second organic solvent, and uniformly mixing to obtain a mixed solution; and pouring the obtained mixed solution on a template, standing to volatilize the second organic solvent, and drying to obtain the composite solid electrolyte.
In some embodiments, the method of making comprises the steps of:
adding the high molecular polymer, the additive and the lithium salt into a second organic solvent, and uniformly stirring to obtain a mixed solution; and pouring the obtained mixed solution on a template, standing for 1-48h to volatilize the second organic solvent, and then drying at 50-120 ℃ to obtain the composite solid electrolyte.
In some embodiments, the second organic solvent is anhydrous acetonitrile.
The invention also provides application of the composite solid electrolyte in any embodiment in preparation of a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention will have-NH 2 or-NO 2 The two-dimensional bimetallic-organic frameworks (MOFs) of the groups are used as additives in solid electrolytes, on one hand, metal sites on the MOFs can interact with anions of lithium salts in the electrolytes to effectively inhibit the movement of the anions, and are Li + Provide a larger movement space, which is beneficial to Li + Is improved in Li + Ion mobility; at the same time, -NH on MOFs 2 or-NO 2 The adsorption of anions by the groups further inhibits the movement of anions, thereby further improving Li + Ion transport number of (a) is determined. On the other hand, based on the self-diversity of pore structures and surface functions of the bimetallic MOFs, li can be + Providing a fast ion transport path, shortening the ion transfer path, and adding-NH 2 or-NO 2 The groups promote MOFs to form more micropores and mesoporous structures in the formation process of the MOFs, increase the specific surface area of the MOFs, facilitate the contact with the high-molecular polymer, enhance the interaction with the high-molecular polymer and further improve the ion conductivity of the solid electrolyte; through detection, the composite solid electrolyte provided by the invention, li + The ion migration number can reach 0.64.
In addition, the addition of the two-dimensional sheet MOFs can effectively destroy the crystallization of the high-molecular polymer and further promote the migration of lithium ions.
In addition, based on the increase of the migration number of lithium ions, the interfacial ion transport stability can be enhanced, so that the energy density of the battery is improved, and the solid electrolyte is applied to the battery, so that the battery has a higher electrochemical window (more than 4.5V) and simultaneously has higher specific capacity and excellent cycle performance.
Drawings
FIG. 1 is an SEM image of a bimetallic-organic framework material prepared in example 1, wherein FIG. a is an SEM image of CoFe-BDC; panel b shows CoFe-BDC-NO 2 SEM images of (a); coFe-BDC-NH 2 SEM images of (a);
FIG. 2 is a TEM image and an elemental distribution scan of CoFe-BDC prepared in example 1;
FIG. 3 is a CoFe-BDC-NO prepared in example 1 2 A TEM image and an element distribution scan image of (a);
FIG. 4 is a CoFe-BDC-NH obtained in example 1 2 TEM images and elemental distribution scans of (a)
In fig. 5, a is an XRD pattern of the bimetal-organic framework material prepared in example 1; b is a raman spectrum of the bi-metal-organic framework material; c is an infrared spectrogram of the bimetal-organic framework material;
FIG. 6 is LiFePO prepared in example 4 4 Cycling performance test chart for Li cell at 0.3C current density;
FIG. 7 is LiFePO prepared in example 4 4 Capacity test chart of Li battery after 200 cycles at different current densities;
FIG. 8 is a graph of cyclic performance testing at 0.2C current density for NCM523/Li batteries prepared in example 4.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
Preparation of a bimetallic-organic framework material CoFe-BDC:
adding 1.5mmol of cobalt nitrate hexahydrate, 0.75mmol of ferric chloride hexahydrate and 1.5mmol of 1, 4-terephthalic acid into 50ml of dimethylformamide, and uniformly stirring and mixing; then adding 10ml of deionized water, 10ml of ethanol and 10ml of triethylamine, and stirring for reaction for 12 hours; after the reaction is completed, the mixed solution is centrifugally separated, solid and liquid are separated, the solid is washed by acetone and ethanol in sequence, and then the solid is placed in a vacuum drying oven for drying, so as to obtain CoFe-BDC.
Bimetallic-organic framework material CoFe-BDC-NH 2 Is prepared from the following steps: the same procedure as for the preparation of CoFe-BDC is distinguished by the fact that the organic ligand is 2-amino terephthalic acid.
Bimetallic organic framework material CoFe-BDC-NO 2 Is prepared from the following steps: the same procedure as for the preparation of CoFe-BDC is distinguished by the fact that the organic ligand is 2-nitroterephthalic acid.
SEM (scanning electron microscope) detection is carried out on the bimetal-organic framework prepared in the embodiment, and the detection result is shown in figure 1.
TEM detection and Atomic Force Microscope (AFM) detection are carried out on the bimetal-organic framework prepared in the embodiment, and the detection results are shown in figures 2-4;
XRD, raman spectrum and infrared detection are carried out on the bimetal-organic framework prepared in the embodiment, and the detection result is shown in figure 5.
As shown in FIG. 1, the bimetal-organic framework prepared by the method of the invention has a two-dimensional sheet structure.
And figures 2-5 fully illustrate the structure and elemental composition of the resulting bimetallic-organic framework.
Example 2
1. Preparation of CoFe-BDC-NO according to the procedure of example 1 2 ；
2. The preparation of the solid electrolyte comprises the following steps:
molecular weight is 3×10 6 g/mol PEO, liClO 4 According to EO and Li + The molar ratio of (2) is 20:1 in anhydrous acetonitrile, and then CoFe-BDC-NO 2 ，CoFe-BDC-NO 2 The addition amount of the catalyst is 10 weight percent of the mass of PEO, and the mixture is stirred uniformly at room temperature to obtain mixed slurry; pouring the mixed slurry on a polytetrafluoroethylene mould, standing, volatilizing at room temperature for more than 24 hours, then placing in a vacuum drying oven, and vacuum drying at 80 ℃ to obtain a composite solid electrolyte with the thickness of 100 mu m, named PEO/MOFs-NO 2 。
The composite solid electrolyte prepared in this exampleIon conductivity was measured at room temperature (25 ℃) according to the conventional methods in the art, and the test results were: ion conductivity of 5.0X10 -5 S/cm；Li + The ion transfer number was 0.5.
Example 3
1. Preparation of CoFe-BDC-NH according to the procedure of example 1 2 ；
2. The preparation of the solid electrolyte comprises the following steps:
molecular weight is 3×10 6 g/mol PEO, liClO 4 According to EO and Li + The molar ratio of (2) is 20:1 in anhydrous acetonitrile, then CoFe-BDC-NH 2 ，CoFe-BDC-NH 2 The addition amount of the catalyst is 10 weight percent of the mass of PEO, and the mixture is stirred uniformly at room temperature to obtain mixed slurry; pouring the mixed slurry on a polytetrafluoroethylene mould, standing, volatilizing at room temperature for more than 24 hours, then placing in a vacuum drying oven, and vacuum drying at 80 ℃ to obtain a composite solid electrolyte with the thickness of 100 mu m, named PEO/MOFs-NH 2 。
The ionic conductivity of the solid electrolyte prepared at normal temperature in this example was 6.5X10 -5 S/cm；Li + The ion transfer number was 0.64.
Comparative example 1
1. CoFe-BDC was prepared as in example 1;
2. the preparation of the composite solid electrolyte comprises the following steps:
molecular weight is 3×10 6 g/mol PEO, liClO 4 According to EO and Li + The molar ratio of (2) is 20:1, adding the mixture into anhydrous acetonitrile, then adding CoFe-BDC, wherein the addition amount of the CoFe-BDC is 10 weight percent of the PEO mass, and stirring the mixture uniformly at room temperature to obtain mixed slurry; pouring the mixed slurry on a polytetrafluoroethylene mould, standing, volatilizing at room temperature for more than 24 hours, then placing in a vacuum drying oven, and vacuum drying at 80 ℃ to obtain the composite solid electrolyte with the thickness of 100 mu m, which is named PEO/MOFs.
The ionic conductivity of the solid electrolyte prepared in this comparative example was 3.5X10 -5 S/cm；Li + The ion transfer number was 0.36.
Comparative example 2
Preparation of solid electrolyte:
molecular weight is 3×10 6 g/mol PEO, liClO 4 According to EO and Li + The molar ratio of (2) is 20:1 into anhydrous acetonitrile, and uniformly stirring at room temperature to obtain mixed slurry; pouring the mixed slurry on a polytetrafluoroethylene mould, standing, volatilizing at room temperature for more than 24 hours, then placing in a vacuum drying oven, and vacuum drying at 80 ℃ to obtain a composite solid electrolyte with the thickness of 100 mu m, named PEO/LiClO 4 。
The ionic conductivity of the solid electrolyte prepared in this comparative example was 7.1X10 -6 S/cm；Li + The ion migration number was 0.18.
Example 4
The solid electrolytes prepared in example 3 and comparative example 2 were subjected to electrochemical performance test, specifically as follows:
(1) The solid electrolyte was used to prepare full cells according to the conventional methods in the art, respectively, wherein the positive electrode active material was selected from commercial LiFePO 4 The negative electrode is a lithium sheet; after the battery assembly was completed, a charge-discharge cycle was performed, and the test results are shown in fig. 6. As shown in FIG. 6, PEO/MOFs-NH was tested after 200 cycles at a current density of 0.3C (1C=170 mA/h, 60 ℃) 2 A battery made of the solid electrolyte, the capacity of which is kept at 148mA/g; at a current density of 1C, the capacity was maintained at 132.29mA/g over 200 cycles; whereas PEO/LiClO 4 The capacity of the battery made of the solid electrolyte is only 57.8mA/g; at a current density of 1C, the capacity was 49.6mA/g. Furthermore, as shown in FIG. 6, PEO/LiClO 4 After 99 cycles of the solid electrolyte, the coulombic efficiency is almost disordered due to cell failure.
In addition, the cycling test was also performed at different current densities, and the capacity after 200 cycles is shown in fig. 7.
(2) The solid electrolytes were used to prepare full cells, respectively, according to conventional methods in the art, wherein the positive electrode active material was selected from the group consisting of commercial NCM523 (LiNi 0.5 Co 0.2 Mn 0.3 O 2 ) The negative electrode is a lithium sheet; after the battery assembly was completed, the battery was assembled at 0.2C (1c=170 mA/h, 60C) was subjected to charge-discharge cycles at a current density, and the test results are shown in fig. 8. As shown in FIG. 8, PEO/MOFs-NH was tested after 100 cycles at a current density of 0.2C 2 A battery made of the solid electrolyte, the capacity of which is kept at 138.1mA/g; whereas PEO/LiClO 4 The capacity of the battery made of the solid electrolyte is only 55.6mA/g.
Therefore, the solid electrolyte prepared by the invention has strong adaptability in different battery systems and shows excellent cycle performance.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The composite solid electrolyte is characterized by comprising a high molecular polymer, an additive and lithium salt, wherein the additive is added in an amount of 5-25% of the mass of the high molecular polymer; the additive is a catalyst having-NH 2 and/or-NO 2 Two-dimensional bimetallic-organic framework materials of radicals.
2. The composite solid electrolyte of claim 1 wherein the center metal ions of the bi-metal-organic framework material are Fe (III) and Co (III).
3. The composite solid electrolyte of claim 2 wherein the bimetallic organic frameworkIs CoFe-BDC-NH 2 And/or CoFe-BDC-NO 2 。
4. The composite solid electrolyte according to claim 3, wherein the CoFe-BDC-NH 2 Or CoFe-BDC-NO 2 The preparation of the composition comprises the following steps:
dissolving soluble ferric salt, soluble cobalt salt and an organic ligand in a first organic solvent, then adding deionized water, an alcohol solvent and triethylamine, and reacting for more than 24 hours to obtain the CoFe-BDC-NH 2 Or CoFe-BDC-NO 2 ；
Wherein the organic ligand is amino terephthalic acid or nitro terephthalic acid; the mole ratio of the soluble ferric salt, the soluble cobalt salt and the organic ligand is 1-2: 3:1.
5. the composite solid electrolyte according to claim 1, wherein the high molecular polymer has a molecular weight of 10 5 ～5×10 6 g/mol。
6. The composite solid electrolyte according to claim 1, wherein the high molecular polymer is at least one of polyethylene oxide, polymethyl methacrylate, polyacrylonitrile, polyvinylidene fluoride, and polysiloxane.
7. The composite solid electrolyte according to claim 1, wherein the lithium salt is at least one of lithium perchlorate, lithium bis (trifluoromethanesulfonyl) imide, lithium trifluoromethanesulfonate, lithium bis (fluorosulfonyl) imide, lithium trifluoromethanesulfonate, and lithium oxalyldifluoroborate.
8. The method for producing a composite solid electrolyte according to any one of claims 1 to 7, comprising the steps of:
adding the high molecular polymer, the additive and the lithium salt into a second organic solvent, and uniformly mixing to obtain a mixed solution; and pouring the obtained mixed solution on a template, standing to volatilize the second organic solvent, and drying to obtain the composite solid electrolyte.
9. The method for producing a composite solid electrolyte according to claim 8, comprising the steps of:
adding the high molecular polymer, the additive and the lithium salt into a second organic solvent, and uniformly stirring to obtain a mixed solution; and pouring the obtained mixed solution on a template, standing for 1-48h to volatilize the second organic solvent, and then drying at 50-120 ℃ to obtain the composite solid electrolyte.
10. Use of the composite solid electrolyte according to any one of claims 1 to 7 for the preparation of a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310567974.7A CN116365021A (en) | 2023-05-19 | 2023-05-19 | Composite solid electrolyte and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310567974.7A CN116365021A (en) | 2023-05-19 | 2023-05-19 | Composite solid electrolyte and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116365021A true CN116365021A (en) | 2023-06-30 |
Family
ID=86938108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310567974.7A Pending CN116365021A (en) | 2023-05-19 | 2023-05-19 | Composite solid electrolyte and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116365021A (en) |
-
2023
- 2023-05-19 CN CN202310567974.7A patent/CN116365021A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10892521B2 (en) | Solid polymer electrolyte based on modified cellulose and its use in lithium or sodium secondary batteries | |
| US10892489B2 (en) | Composite anode active material, and anode and lithium battery including composite anode active material | |
| KR20190072968A (en) | Negative electrode for metal battery, metal battery comprising the same, and method of preparing the negative electrode for metal battery | |
| CN113285118A (en) | Compound solid electrolyte based on MOF three-dimensional framework support and preparation method thereof | |
| CN111740156A (en) | Composite solid electrolyte membrane and preparation method thereof | |
| US20230402648A1 (en) | Solid-state electrolyte and preparation method thereof, and secondary battery | |
| CN105789531B (en) | Barrier membrane, preparation method and the secondary cell including it | |
| KR101841113B1 (en) | Cathode Active Material for Lithium Secondary Battery Which Ionized Metal Is Coated on Surface Thereof and Method for Preparation of the Same | |
| KR20170047661A (en) | Random copolymer, Electrolyte, Protected anode and Lithium battery comprising Random copolymer, and Preparation method of Random copolymer | |
| CN112421046B (en) | Preparation method of single-ion conductive polymer composite material for lithium metal secondary battery | |
| CN116826193A (en) | Electrolyte additive for aqueous zinc ion secondary battery and battery thereof | |
| CN111320753B (en) | Polymer, polymer electrolyte membrane, nonaqueous electrolyte solution, and lithium ion battery | |
| CN110729481A (en) | Lithium ion battery negative active material MnxFe1-xC2O4Synthetic method and application | |
| CN116365021A (en) | Composite solid electrolyte and preparation method and application thereof | |
| EP4078708B1 (en) | Quasi-solid zinc-iron redox battery | |
| CN114262447A (en) | Two-dimensional covalent organic framework material with cation framework, preparation method and application thereof, and lithium metal battery electrode | |
| CN112382786A (en) | Composition for forming solid polymer electrolyte, solid polymer electrolyte membrane, and lithium ion battery | |
| CN114430062B (en) | Composite electrolyte based on lithiated carbon point modification and preparation method and application thereof | |
| CN114050266B (en) | Selenium disulfide composite nitrogen-doped reduced graphene oxide positive electrode material, preparation method thereof, lithium-selenium disulfide battery and power-related equipment | |
| CN114455609B (en) | Preparation method and application of low-cost sodium ion battery positive electrode material with stable circulation | |
| CN117510924B (en) | Hollow zirconium-based metal organic framework crosslinked composite solid electrolyte, preparation method and application | |
| CN110229365B (en) | All-solid-state sodium ion battery electrolyte and preparation method thereof | |
| KR20020006134A (en) | Conducting Polymer/Manganese Oxide Composite Cathode Material for Lithium Secondary Batteries and Method for Making Same | |
| KR20240021102A (en) | Zwitterion covalent organic frameworks for solidstate secondary battery, electrolyte including same, and all-solid-state secondary battery including same | |
| Yang et al. | Highly Conductive Single-Ion Polymeric Electrolyte for Long-Cycle-Life Lithium Metal Batteries |
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 |