CN116979214A - Hydrogen-bonded organic framework material composite polymer diaphragm and preparation method and application thereof - Google Patents
Hydrogen-bonded organic framework material composite polymer diaphragm and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 75
- 229920000642 polymer Polymers 0.000 title claims abstract description 63
- 239000013384 organic framework Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 76
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 76
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 42
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 15
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 15
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 229920005597 polymer membrane Polymers 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 14
- 229920006254 polymer film Polymers 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyethylene carbonate Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002086 nanomaterial Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 4
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 238000007790 scraping Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000013110 organic ligand Substances 0.000 claims 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003063 flame retardant Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002127 nanobelt Substances 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000008878 coupling Effects 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
- A62C3/16—Fire prevention, containment or extinguishing specially adapted for particular objects or places in electrical installations, e.g. cableways
-
- 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a hydrogen bond organic framework material composite polymer membrane, a preparation method and application thereof, wherein the composite polymer membrane comprises the following components: a polymer matrix, and additives and lithium salts uniformly distributed in the polymer. The additive is a hydrogen bond organic framework material, and has the characteristics of ordered and porous structure, abundant hydrogen bond active sites and one/two-dimensional structure. The invention utilizes the high specific surface area and abundant hydrogen bond sites and good hydrogen bond reversibility of the hydrogen bond organic framework material, can realize the interaction with polymer molecules and lithium ions, provides an ion transmission channel in a coordinated and ordered way, can effectively improve the electrochemical performance of polymer electrolyte, simultaneously improves the mechanical performance of the diaphragm through the one-dimensional two-dimensional structure of the additive and the hydrogen bond formed between the additive and the polymer, and can decompose and absorb heat at high temperature and generate non-combustible substances to enhance the flame retardant performance of the polymer diaphragm.
Description
Technical Field
The invention belongs to the field of secondary lithium batteries, and particularly relates to a hydrogen bond organic framework material composite polymer diaphragm, a preparation method and application thereof.
Background
Lithium batteries, including lithium ion batteries and lithium metal batteries, are secondary battery types that have been used in the past while having great development prospects, and have the advantages of high specific capacity, high operability, and the like. However, the battery is easy to generate heat in the process of high-current quick charge and operation, and meanwhile, lithium dendrites can be formed in the long-term use of the battery, so that the danger of short circuit caused by the penetration of a diaphragm exists. Therefore, in use, when the heat in the battery is accumulated to a certain extent or when the battery is subjected to conditions such as impact damage by external force and the like to cause the electrode material to react with air to generate heat, the lithium battery is easy to have the risks of fire and even explosion caused by thermal runaway and serious consequences due to the high flammability of the liquid electrolyte and the common commercial pp diaphragm, and the phenomenon of fire and explosion of the battery has been reported, so that the further development and application of the lithium battery in the aspects of capacity, quick charge and the like are greatly restricted. Therefore, in order to avoid the high inflammable risks of liquid electrolyte and separator, polymer electrolyte separators have been widely paid attention to and studied for their advantages of good contact with electrodes, easy workability, certain lithium ion conductivity, high safety, etc. However, the polymer electrolyte membrane still suffers from the problems of low lithium ion conductivity, poor mechanical property, poor flame retardant property and the like of the polymer, so that the improvement of the electrochemical property, the mechanical property and the flame retardant property of the polymer electrolyte membrane becomes a key factor influencing the further development and the application of the lithium battery.
The polymer electrolyte commonly used at present cannot meet the current commercialization requirements due to the physical and chemical property limitation of the high molecular polymer, such as electrochemical property, mechanical property, flame retardant property and the like, and therefore needs to be improved. At present, the nano material is added and mixed with the polymer, and the hydrogen bond is generated between functional groups such as hydroxyl groups on the surfaces of the nano particles and the polymer, so that the lithium ion conductivity, the lithium ion transfer number and the mechanical property of the polymer are enhanced, and the method has the advantages of obvious effect, simplicity, easiness in operation, strong selectivity and the like. However, most nanomaterials are only functional groups with hydroxyl groups on the surface due to the action of Lewis acid and alkali, and the number and the mode of the generated functional groups are extremely limited, so that the effect of hydrogen bonding with polymers is extremely limited, and further, the improvement of the electrochemical performance and the mechanical performance of the polymer diaphragm is limited. Meanwhile, most of nano materials have certain thermal stability, but cannot play a role in heating and burning when the polymer components are out of control, so that the flame retardant property of the polymer diaphragm is affected. The hydrogen bond organic framework material is a highly ordered structure material which is assembled by organic or metal organic building units through intermolecular hydrogen bonding and has high specific surface area and adjustable porosity. Has great potential in the fields of molecular adsorption, fluorescent probes and the like, and gradually becomes one of research hotspots in the fields of chemistry and materials. The hydrogen bond organic frame material has very abundant hydrogen bond sites, has good repairability and reproducibility, can effectively act with a polymer and lithium ions, and can easily generate decomposition reaction at high temperature, absorb a large amount of heat and generate a large amount of flame-retardant gas. These properties can purposefully improve the electrochemical, mechanical and flame retardant properties of polymer electrolyte separators, but are still lacking in the field of polymer electrolyte separators. Therefore, developing a universal method for preparing the high-performance polymer electrolyte membrane compounded by the hydrogen bond organic frame material has important significance for the development and application of lithium batteries.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a hydrogen bond organic framework material composite polymer membrane, and a preparation method and application thereof. The invention selects one-dimensional/two-dimensional hydrogen bond organic frame material as additive, realizes the uniform distribution in polymer by utilizing the interaction between the hydrogen bond sites and polymer molecules, generates abundant bonding effect between the hydrogen bond organic frame material and polymer and lithium ions, and takes ordered porous structure as ion transmission channel, thus effectively improving the ion conduction performance of the polymer diaphragm, simultaneously effectively improving the mechanical performance of the polymer diaphragm by the one-dimensional/two-dimensional structure of the hydrogen bond organic frame material and the abundant hydrogen bonds generated between the hydrogen bond organic frame material and polymer molecules, and generating non-combustible substances while decomposing and absorbing a large amount of heat under high temperature condition. The obtained lithium battery has long cycling stability and high theoretical specific capacity; meanwhile, the process has the characteristics of simple and convenient operation and simple process, and is suitable for industrial production.
In order to realize the technical scheme, the invention adopts the following technical scheme:
a hydrogen bonded organic framework material composite polymer separator comprising: a polymer matrix, and additives and lithium salts uniformly distributed in the polymer. The additive is a one-dimensional nano belt or a two-dimensional nano sheet of a hydrogen bond organic framework material, and is a nano material with high specific surface area, multiple holes and adjustable highly ordered structure, which is formed by assembling organic or metal organic building units through intermolecular hydrogen bonding.
The mass ratio of the polymer matrix to the additive is 1: (0.01-1).
The thickness of the polymer electrolyte membrane is 30-300 microns.
The polymer electrolyte separator is obtained by the following two ways: the method comprises the following steps: and uniformly dissolving and dispersing the polymer matrix, the hydrogen bond organic framework material and the lithium salt in a solvent, transferring the mixed solution to a die, strickling, and volatilizing the solvent to obtain the polymer electrolyte membrane. The second method is as follows: and uniformly dissolving and dispersing the polymer matrix and the hydrogen bond organic framework material in a solvent, transferring the mixed solution to a die, scraping, volatilizing the solvent to obtain a polymer film, soaking the polymer film into the battery electrolyte, and taking out the polymer film after the polymer film completely adsorbs the electrolyte to obtain the polymer electrolyte membrane. The electrolyte solvent exists in the diaphragm obtained by the second method except the lithium salt, and the electrolyte solvent does not exist in the diaphragm obtained by the first method except the lithium salt. The separator of method two has higher lithium ion conductivity than that of method one, but the separator obtained by method one is less flammable.
The solvent is volatilized during the preparation of the electrolyte and is dried in a sealed container at a temperature lower than 80 ℃.
The uniform dissolution and dispersion in the solvent means that: the solution of the polymer matrix, lithium salt and additives was added with stirring and with the aid of ultrasound.
The hydrogen bond organic frame material is uniformly distributed in the polymer matrix and is in close contact with the polymer matrix, a large number of nitrogen and oxygen sites exist in the molecular structure and can form rich hydrogen bonds with the polymer matrix and lithium salt, so that the coupling of the polymer and the lithium salt is reduced, meanwhile, the highly ordered porous structure of the hydrogen bond organic frame material provides a lithium ion transmission channel, and the ion transmission of the composite diaphragm can be effectively improved. The one-dimensional/two-dimensional structure of the hydrogen-bonded organic framework material and the polymer matrix form a great number of rich hydrogen bonds, so that the diaphragm has enhanced mechanical properties. Meanwhile, the hydrogen bond organic framework material can decompose a large amount of heat absorption and generate nonflammable substances at the same time under the high temperature condition, so that the diaphragm is prevented from burning.
The hydrogen bond organic framework material is prepared by adopting the following method: the hydrogen bond organic framework material is prepared by dissolving 3, 5-diamino-1H-1, 2, 4-triazole and/or 4,4' - (9H-carbazole-1, 3,6, 8-tetrayl) tetrabenzaldehyde in N, N-dimethylacetamide, adding 1,4,5, 8-naphthalene tetracarboxylic dianhydride and/or tetraphenyl ethylene, stirring to form a clear solution, transferring the solution into a high-pressure reaction kettle, heating at 120-180 ℃ for reaction for 8-12 hours, naturally cooling to room temperature, centrifuging, washing and freeze-drying; wherein the molar ratio of 3, 5-diamino-1H-1, 2, 4-triazole and/or 4,4' - (9H-carbazole-1, 3,6, 8-tetrayl) tetrabenzaldehyde to 1,4,5, 8-naphthalene tetracarboxylic dianhydride and/or tetraphenyl ethylene is 1 (1-4).
The polymer matrix is selected from one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide, polymethyl methacrylate and polyethylene carbonate with lithium ion conducting capacity.
The lithium salt is one or more of lithium hexafluorophosphate, lithium difluorosulfonimide, lithium bistrifluoromethylsulfonimide, lithium tetrafluoroborate, lithium dioxaborate and lithium oxalyldifluoroborate.
The solvent is selected from one or more of water, alcohols, N-dimethylformamide and acetone.
The polymer electrolyte membrane of the invention can be applied to a secondary lithium battery.
The invention has the beneficial effects that:
(1) The hydrogen bond organic framework material adopted by the invention has very rich hydrogen bond sites, and simultaneously, the large specific surface area enables the hydrogen bond sites to generate rich physical and chemical actions with the polymer or lithium salt, thereby effectively enhancing the ion conduction performance of the diaphragm. Meanwhile, the hydrogen bond organic framework material has a highly ordered porous structure, can be used as a channel for transmitting lithium ions, and can be used for improving the ion conduction performance of the diaphragm.
(2) The organic frame material and the polymer adopted by the invention form a large number of hydrogen bonds, and the mechanical property of the polymer diaphragm can be enhanced by cooperating with the one-dimensional/two-dimensional structure as a framework. The hydrogen bond organic frame material can decompose and absorb a large amount of heat under the high temperature condition and simultaneously generate a large amount of nonflammable substances, so that the flame retardant property of the diaphragm is improved.
(3) The polymer electrolyte membrane can effectively inhibit the formation and growth of lithium dendrites, so that a lithium battery has longer cycle stability.
(4) The polymer electrolyte membrane can improve the specific capacity, the cycle life and the capacity retention rate of the battery.
(5) The preparation method can be operated by conventional heating and stirring equipment, and has the characteristics of simple and convenient operation and simple process.
(6) The cycle life of the semi-solid battery assembled by the diaphragm exceeds 1000 times, and the capacity of the lithium iron phosphate semi-solid full battery reaches 170mAh/g at 0.5C. Meanwhile, the process has the characteristics of simple and convenient operation and simple process, and is suitable for industrial production.
Drawings
FIG. 1 is a schematic diagram of the molecular structure of the preparation process of a hydrogen bonding organic framework material of example 1;
FIG. 2 is an SEM photograph of hydrogen bonded organic framework material of example 1;
FIG. 3 is a tensile test curve of a composite polymer electrolyte separator with HOFs added in example 1;
FIG. 4 is the cycling stability of the lithium symmetric battery of example 1 with and without the addition of a polymer electrolyte separator of hydrogen bonded organic framework material;
FIG. 5 is the cycling performance of the lithium/lithium iron phosphate full cell of the polymer electrolyte separator of example 1 with and without hydrogen bonding organic framework material;
fig. 6 is a lithium metal symmetric battery cycle stability of the polymer electrolyte separator in example 2.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
In the examples, the technical means used are conventional technical means in the art unless otherwise specified.
The electrochemical equipment is a Xinwei CT-4008T small current battery tester and an Shanghai Chenhua CHI electrochemical workstation, and the heating equipment is a heat-collecting water bath kettle and an oven.
Example 1 preparation of Polymer electrolyte separator
The method comprises the following steps:
(1) Preparation of hydrogen bond organic framework material
495.5 mg of 3, 5-diamino-1H-1, 2, 4-triazole (DAT) powder was completely dissolved in 50 ml of N, N-dimethylacetamide under an ice bath and nitrogen atmosphere, and 670 mg of 1,4,5, 8-naphthalene tetracarboxylic dianhydride (NTCDA) powder was then added and magnetically stirred for 1 hour to form a clear solution. Adding 125 ml of N, N-dimethylacetamide into the clear solution for dilution, transferring the diluted solution into a high-pressure reaction kettle, heating in an oven at 180 ℃ for 12 hours, naturally cooling to room temperature, centrifugally collecting a product, washing with N, N-dimethylformamide, methanol and distilled water for 5 times respectively, and finally freeze-drying to obtain hydrogen bond organic frame material (HOFs) powder, wherein the molecular structure of the powder is shown in figure 1. From the molecular structure, the HOFs material has rich nitrogen and oxygen sites and a hydrogen bond porous structure.
FIG. 2 is a scanning electron micrograph of HOFs powder prepared in this example. It can be seen from the figure that the prepared hydrogen bond organic framework material is a one-dimensional nanobelt.
(2) Polymer electrolyte separator preparation
1g of polyvinylidene fluoride-hexafluoropropylene was dissolved in 10mL of acetone at 40℃followed by 0.05g of polyethylene oxide and 50mg of HOFs material was slowly added multiple times and stirring was continued at 55℃for 2 hours. The resulting polymer solution was then poured onto a stainless steel plate and scraped off. The stainless steel was then dried in a sealed volume at room temperature for 6 hours and then vacuum dried for 12 hours. Cutting the polymer film to a proper size, soaking the polymer film in an electrolyte (1.0 mol/L of lithium bistrifluoromethylsulfonyl imide is dissolved in a mixed solution of 1, 3-dioxolane and ethylene glycol dimethyl ether with the volume ratio of 1:1, and contains 0.1mol/L of LiNO) 3 ) After 6 hours, a polymer membrane was obtained. The polymer separator without hydrogen bonding organic framework material was prepared as above, except that no hydrogen bonding organic framework material was added.
The film without HOFs material is semitransparent and milky white, and the polymer film with HOFs material is yellow and has uniform color distribution, because a certain bonding effect can be formed between the hydrogen bond organic frame material and the polymer monomer in the preparation process, so that the hydrogen bond organic frame material is uniformly distributed in the polymer electrolyte.
And (3) effect verification:
the polymer electrolyte separator was tested for lithium ion conductivity and flame retardant properties. The lithium ion conductivity of the polymer electrolyte after the addition of the additive is significantly improved to 5.6ms/cm (figure 4), which is far higher than 1.98 ms/cm of the polymer electrolyte membrane without the addition, because the chemical action of the extremely rich active sites of the hydrogen bond organic framework material and the polymer molecules and lithium salt can promote the lithium ion transmission, and the highly ordered porous structure of the hydrogen bond organic framework material can provide a transmission channel for lithium ions.
The results of the combustion test show that the hydrogen bond organic frame material polymer electrolyte obtained in the example 1 does not generate flame spontaneously in the process of firing, the polymer electrolyte stops burning when the fire source is removed, and the polymer electrolyte without HOFs material still continues to burn after the fire source is removed. This is because HOFs materials decompose and absorb a large amount of heat during the high temperature heating process while producing non-combustible materials, improving the flame retardant properties of the polymer separator.
The tensile strength of the polymer film was tested by a tensile test, and the tensile force of the polymer film added with the HOFs material exceeded 20MPs, whereas the tensile force of the polymer film without the HOFs material was only 2MPa. The one-dimensional hydrogen bond organic frame material is taken as a framework, so that the tensile strength of the polymer can be greatly improved.
And further assembling the lithium symmetrical battery to test the battery cycle stability. From the results, it can be seen that the battery performance of the polymer electrolyte separator to which the hydrogen bond organic frame material was added was significantly improved, and the battery was able to stably cycle for more than 2000 hours (1000 cycles). While the battery cycle life of the polymer separator without added hydrogen bonding organic frame material is only about 650 hours. This demonstrates that the stronger lithium ion conductivity and mechanical properties of the hydrogen bond organic framework material composite polymer membrane can inhibit the formation and growth of lithium dendrites, prolonging the cycle life. The capacity of the full battery assembled by the hydrogen bond organic framework material composite polymer electrolyte membrane at the current density of 0.5C can reach about 170mAh/g which is higher than 158mAh/g of an unadditized polymer membrane battery, and the capacity attenuation is reduced to 0.0926 percent/times which is smaller than 0.1407 percent/times of the unadditized polymer membrane battery.
Example 2 preparation of Polymer electrolyte separator
The hydrogen bonded organic framework material was prepared as in example 1.
The procedure for preparing the polymer electrolyte membrane was the same as in example 1, except that 0.5g of HOFs material was added.
And (3) effect verification:
the assembled lithium symmetric battery was tested for battery cycling stability. From the results, the performance of the polymer electrolyte added with the hydrogen bond organic frame material is obviously improved, and the battery can stably circulate for more than 1500 hours and has longer cycle life than the polymer diaphragm without the hydrogen bond organic frame material.
Example 3 preparation of Polymer electrolyte separator
(1) Preparation of hydrogen bond organic framework material: same as in example 1
(2) Preparation of a polymer electrolyte separator:
1g of polyvinylidene fluoride-hexafluoropropylene is dissolved in 10mL of acetone at 40 ℃, 0.05g of polyethylene oxide and 0.5g of LITFSI are added to be uniformly dissolved, 50mg of HOFs material is slowly added for multiple times, and stirring is continued for 2 hours at 55 ℃. The resulting polymer solution was then poured onto a stainless steel plate and scraped off. Then, the stainless steel was dried in a sealed volume at room temperature for 6 hours and then vacuum-dried for 12 hours to obtain a polymer membrane. The polymer separator without hydrogen bonding organic framework material was prepared as above, except that no hydrogen bonding organic framework material was added.
And (3) effect verification:
the polymer electrolyte separator was tested for lithium ion conductivity and cycle performance. The lithium ion conductivity of the polymer electrolyte after the addition of the additive is 0.878ms/cm, which is far higher than that of the polymer electrolyte membrane without the addition of the additive by 0.135ms/cm. At 0.1mA/cm 2 Under the condition of measurementIn the lithium-tested symmetrical battery, the cycle life of the assembled battery of the polymer electrolyte added with the hydrogen bond organic frame material reaches 1800 hours, and the cycle life of the assembled battery of the polymer electrolyte which is not added is only about 350 hours.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (9)
1. A hydrogen bonded organic framework material composite polymer membrane, characterized by: comprises a polymer matrix, additives and lithium salt, wherein the additives are uniformly distributed in the polymer, and the additives are hydrogen bond organic frame materials; wherein the mass ratio of the polymer matrix to the additive is 1: (0.01-1).
2. The composite polymer separator according to claim 1, wherein: the polymer matrix is one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide, polymethyl methacrylate and polyethylene carbonate with lithium ion conducting capacity.
3. The composite polymer separator according to claim 1, wherein: the lithium salt is one or more of lithium hexafluorophosphate, lithium difluorosulfonimide, lithium bistrifluoromethylsulfonimide, lithium tetrafluoroborate, lithium dioxaborate and lithium oxalyldifluoroborate.
4. The composite polymer separator according to claim 1, wherein: the hydrogen bond organic framework material is a highly ordered structure nano material which is assembled by organic or metal organic building units through intermolecular hydrogen bonding and has high specific surface area and adjustable multiple holes; the hydrogen bond organic framework material has a one-dimensional/two-dimensional structure and can generate rich mutual bonding effect with the polymer and the lithium salt.
5. The composite polymer separator according to claim 1, wherein: the hydrogen bond organic framework material is obtained by combining a plurality of organic ligands in a solvent.
6. The composite polymer separator according to claim 1, wherein: the hydrogen bond organic framework material is prepared by adopting the following method: dissolving 3, 5-diamino-1H-1, 2, 4-triazole or 4,4' - (9H-carbazole-1, 3,6, 8-tetrayl) tetrabenzaldehyde in N, N-dimethylacetamide, adding 1,4,5, 8-naphthalene tetracarboxylic dianhydride or tetraphenyl ethylene, stirring to form a clear solution, transferring the solution into a high-pressure reaction kettle, heating at 120-180 ℃ for reaction for 8-12 hours, naturally cooling to room temperature, centrifuging, washing, and freeze-drying to obtain the product; wherein the molar ratio of 3, 5-diamino-1H-1, 2, 4-triazole or 4,4' - (9H-carbazole-1, 3,6, 8-tetrayl) tetrabenzaldehyde to 1,4,5, 8-naphthalene tetracarboxylic dianhydride or tetraphenyl ethylene is 1 (1-4).
7. A method of making a composite polymeric separator according to any one of claims 1 to 6, wherein: uniformly dissolving and dispersing a polymer matrix, a hydrogen bond organic framework material and lithium salt in a solvent, transferring the mixed solution to a mould for strickling, and volatilizing the solvent to obtain a polymer electrolyte membrane; or uniformly dissolving and dispersing the polymer matrix and the hydrogen bond organic framework material in a solvent, transferring the mixed solution to a die, scraping, volatilizing the solvent to obtain a polymer film, soaking the polymer film into the lithium battery electrolyte, and taking out the polymer film after the polymer film completely adsorbs the electrolyte to obtain the polymer electrolyte diaphragm.
8. The method of manufacturing according to claim 7, wherein: the solvent is one or more of water, alcohols, N-dimethylformamide and acetone.
9. Use of the composite polymer separator of any one of claims 1-6 in a secondary lithium battery.
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