CN115498364B - Modified composite diaphragm for battery and preparation method and application thereof - Google Patents
Modified composite diaphragm for battery and preparation method and application thereof Download PDFInfo
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- CN115498364B CN115498364B CN202211339800.7A CN202211339800A CN115498364B CN 115498364 B CN115498364 B CN 115498364B CN 202211339800 A CN202211339800 A CN 202211339800A CN 115498364 B CN115498364 B CN 115498364B
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- 239000002131 composite material Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000012528 membrane Substances 0.000 claims abstract description 102
- 229920000642 polymer Polymers 0.000 claims abstract description 79
- -1 phenolic amine Chemical class 0.000 claims abstract description 56
- 150000001450 anions Chemical class 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229920005597 polymer membrane Polymers 0.000 claims abstract description 27
- WAWVSIXKQGJDBE-UHFFFAOYSA-K trilithium thiophosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=S WAWVSIXKQGJDBE-UHFFFAOYSA-K 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 84
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000011259 mixed solution Substances 0.000 claims description 35
- 238000011065 in-situ storage Methods 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 239000011737 fluorine Substances 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 235000013824 polyphenols Nutrition 0.000 claims description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- 150000007524 organic acids Chemical class 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 229920000573 polyethylene Polymers 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 239000007983 Tris buffer Substances 0.000 claims description 11
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- FNYDIAAMUCQQDE-UHFFFAOYSA-N 4-methylbenzene-1,3-diol Chemical compound CC1=CC=C(O)C=C1O FNYDIAAMUCQQDE-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 150000007517 lewis acids Chemical class 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 4
- IYXUFOCLMOXQSL-UHFFFAOYSA-N (2,2-difluoroacetyl) 2,2-difluoroacetate Chemical compound FC(F)C(=O)OC(=O)C(F)F IYXUFOCLMOXQSL-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- CGDXUTMWWHKMOE-UHFFFAOYSA-N difluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)F CGDXUTMWWHKMOE-UHFFFAOYSA-N 0.000 claims description 3
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 3
- 229960001553 phloroglucinol Drugs 0.000 claims description 3
- 229940079877 pyrogallol Drugs 0.000 claims description 3
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 70
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 46
- 229920001021 polysulfide Polymers 0.000 abstract description 37
- 239000005077 polysulfide Substances 0.000 abstract description 37
- 150000008117 polysulfides Polymers 0.000 abstract description 37
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 27
- 239000003792 electrolyte Substances 0.000 abstract description 23
- 230000004048 modification Effects 0.000 abstract description 14
- 238000012986 modification Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract 2
- 238000001035 drying Methods 0.000 description 27
- 238000005406 washing Methods 0.000 description 26
- 239000000243 solution Substances 0.000 description 13
- 125000006575 electron-withdrawing group Chemical group 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 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 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
Abstract
The invention belongs to the technical field of battery diaphragms, and discloses a modified composite diaphragm for a battery, a preparation method and application thereof, wherein the modified composite diaphragm for the battery comprises a polymer diaphragm matrix and a functional modified layer loaded on the polymer diaphragm matrix; wherein the functional modification layer comprises a phenolic amine polymer network, and an anion capture site and a lithium thiophosphate functional compound loaded on the phenolic amine polymer network. According to the invention, the functional modification layer is loaded on the surface of the polymer membrane, the composition and the structure of the functional modification layer are regulated and controlled, the obtained composite membrane can enhance the affinity between the surface of the membrane and electrolyte, improve the ionic conductivity, promote the conversion and utilization of lithium polysulfide through chemical adsorption and catalysis, and inhibit the shuttle effect of lithium polysulfide. The modified composite diaphragm for the battery can be particularly applied to lithium metal batteries or lithium sulfur batteries.
Description
Technical Field
The invention belongs to the technical field of battery diaphragms, and particularly relates to a modified composite diaphragm for a battery, and a preparation method and application thereof.
Background
With the continuous development of electric automobiles and green energy sources, the requirements of people on mobile power supplies are also continuously increasing, and lithium metal batteries and lithium sulfur batteries are still the directions of researches of scientists. Separator is one of the important components of batteries, but polymer separators currently in commercial use still have some problems such as: surface inertia and poor affinity with electrolyte; lithium ion transmission is uneven, and lithium dendrites are easy to form; the pore size is large, and the shuttling of lithium polysulfide cannot be prevented in a lithium sulfur battery. In order to solve the problems, the method for loading the functional modification layer on the surface of the commercial polymer diaphragm is simple and convenient to operate and has obvious effect.
Chinese patent CN107546355B forms a very thin compact layer on the surface of a commercial lithium-sulfur battery separator by interfacial polymerization reaction to regulate and control the pore size of the separator, and at the same time, increases the surface hydrophilicity of the separator and makes the surface of the separator negatively charged, so that the shuttle effect of lithium polysulfide can be inhibited by physical barrier and electrostatic repulsion, and the cycle performance of the battery is improved. The Chinese patent application CN114512769A carries out hydrophilic modification on a commercial polyolefin membrane through tannic acid, then carries out amide interface polymerization reaction, forms an adjustable ultrathin limiting layer on the surface of the commercial polyolefin membrane, can inhibit shuttling of lithium polysulfide through physical separation and chemical adsorption dual limiting action, improves coulomb efficiency and cycle stability of a lithium-sulfur battery, and shows more excellent electrochemical performance.
However, many scholars consider that the inhibition of the shuttle effect of lithium polysulfide through the actions of physical separation, chemical adsorption or electrostatic repulsion is a method for treating the symptoms but not the root cause, and the catalytic material is added into the diaphragm or the electrode material to promote the conversion of lithium polysulfide into lithium minority sulfide, so that the shuttle of lithium polysulfide can be more effectively inhibited, the utilization rate of active substances is enhanced, and the battery performance is improved.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention aims to provide a modified composite membrane for a battery, a preparation method and application thereof, wherein the functional modification layer is loaded on the surface of a commercial polymer membrane, the composition and structure of the functional modification layer are regulated and controlled, the obtained composite membrane can enhance the affinity between the surface of the membrane and electrolyte, improve the ion conductivity, promote the conversion and utilization of lithium polysulfide through chemical adsorption and catalysis, and inhibit the shuttle effect of the lithium polysulfide. The modified composite diaphragm for the battery is applied to a lithium metal battery or a lithium sulfur battery, can improve the utilization rate of active substances of the battery, enhances the cycling stability of the battery, and achieves the aim of improving the performance of the battery.
In order to achieve the above object, according to one aspect of the present invention, there is provided a modified composite separator for a battery, characterized by comprising a polymer separator substrate, and a functional modification layer supported on the polymer separator substrate; wherein the functional modification layer comprises a phenolic amine polymer network, and an anion capture site and a lithium thiophosphate functional compound loaded on the phenolic amine polymer network.
As a further preferred aspect of the present invention, the phenolamine polymer network is formed by in situ polymerization of phenolamine on the surface of the polymeric separator substrate.
As a further preferred aspect of the present invention, in the functional modification layer, the lithium thiophosphate functional compound is supported by lewis acid base action in the functional modification layer.
As a further preferred aspect of the present invention, the polymer separator substrate includes any one of a polyethylene separator, a polypropylene separator, a polyethylene/polypropylene composite separator, a polyimide separator, and a polyvinylidene fluoride separator.
According to another aspect of the invention, the invention provides a preparation method of a modified composite membrane for a battery, which is characterized in that the preparation method comprises the steps of firstly forming a polymer network on the surface of a polymer membrane through in-situ polymerization of phenolic amine, then combining the polymer network with fluorine-containing organic acid/anhydride to form an anion capturing network, and then combining the anion capturing network with lithium thiophosphate through the action of Lewis acid alkali, so as to obtain the modified composite membrane for the battery;
wherein the fluorine-containing organic acid/anhydride is fluorine-containing organic acid and/or fluorine-containing organic anhydride.
As a further preferred aspect of the present invention, the preparation method specifically comprises the steps of:
(1) Placing the polymer membrane in an alkaline solution containing a polyhydric phenol compound and a polyhydric amine compound at the same time, and performing in-situ polymerization to obtain a polymer network modified polymer membrane;
(2) Dissolving fluorine-containing organic acid/anhydride and triethylamine in an organic solvent at the same time, and then placing the polymer membrane modified by the polymer network into the organic solvent for reaction to obtain the polymer membrane modified by the anion capturing network;
(3) And dissolving lithium thiophosphate in a mixed solution of triethylamine and methanol, and then placing the anion capturing network modified polymer membrane into the mixed solution for reaction to obtain the modified composite membrane for the battery.
As a further preferred aspect of the present invention, in the step (1), the polymer separator includes any one of a polyethylene separator, a polypropylene separator, a polyethylene/polypropylene composite separator, a polyimide separator, and a polyvinylidene fluoride separator;
the polyphenol compound comprises one or more of catechol, resorcinol, hydroquinone, 2-methyl resorcinol, 4-methyl resorcinol, pyrogallol, phloroglucinol and metaphloroglucinol;
the polyamine compound comprises one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine;
the alkaline solution is obtained by simultaneously adding a polyhydric phenol compound and a polyhydric amine compound into a tris aqueous solution; in the obtained alkaline solution, the concentration of the polyhydric phenol compound is 0.2-20 mmol/L, and the ratio of the concentration of the polyhydric phenol compound to the concentration of the polyhydric amine compound is 0.5-2;
the reaction time of the in-situ polymerization is 0.5-48 h, and the reaction temperature is 20-50 ℃.
As a further preferred aspect of the present invention, in the step (2), the fluorine-containing organic acid/acid anhydride is one or more of trifluoromethanesulfonic anhydride, trifluoromethanesulfonic acid, difluoromethanesulfonic acid, trifluoroacetic acid and difluoroacetic acid anhydride;
the organic solvent is one of dichloromethane and chloroform; the ratio of the amount of the fluorine-containing organic acid/acid anhydride substance to the amount of the polyamine substance is 1 to 18; the ratio of the amount of the substance of triethylamine to the amount of the substance of polyamine is 1 to 18;
the reaction time of the reaction is 0.5-48 h, and the reaction temperature is-30 ℃.
As a further preferred aspect of the present invention, in the step (3), the lithium thiophosphate is Li 3 PS 4 、Li 2 P 2 S 6 、Li 7 P 3 S 11 、Li 4 P 2 S 6 、Li 4 P 2 S 7 One or more of the following;
the volume ratio of the triethylamine to the methanol in the mixed solution of the triethylamine and the methanol is 1:4-1:1; the ratio of the amount of the lithium thiophosphate substance to the amount of the polyamine substance is 1 to 18;
the reaction time of the reaction is 0.5-48 h, and the reaction temperature is 20-50 ℃.
According to another aspect of the invention, there is provided the use of the modified composite separator for batteries as described above as a separator in lithium metal batteries or lithium sulfur batteries; preferably, the lithium metal battery is assembled according to the sequence of a positive electrode shell, a lithium iron phosphate pole piece, electrolyte, the modified composite diaphragm for the battery, a lithium piece, a steel sheet, an elastic piece and a negative electrode shell;
the lithium-sulfur battery is assembled according to the sequence of the positive electrode shell, the sulfur pole piece, the electrolyte, the modified composite diaphragm for the battery, the lithium piece, the steel sheet, the elastic sheet and the negative electrode shell.
By the above technical scheme, compared with the prior art, the invention can obtain the following
The beneficial effects are that:
(1) According to the modified composite membrane for the battery, the functional modification layer is loaded on the surface of the commercial polymer membrane, so that the lithium polysulfide can be captured through chemical adsorption, the lithium polysulfide is promoted to be converted into less lithium sulfide through catalysis, the shuttle effect of the lithium polysulfide is strongly and effectively restrained, and the utilization rate of active substances is improved. The modified composite membrane for the battery is prepared by forming a polymer network on the surface of the polymer membrane through in-situ polymerization of the phenolic amine, then combining the polymer network with fluorine-containing organic acid/anhydride to form an anion capturing network, and then combining the modified composite membrane for the battery with a lithium thiophosphate functional compound through the action of Lewis acid and alkali, and is easy to regulate and control the thickness of the functional modified layer, simple in preparation process and low in raw material cost, can react particularly at room temperature, and is easy to realize large-scale preparation.
The lithium thiophosphate functional compound not only can chemically adsorb lithium polysulfide by forming sulfur bonds, but also can be used as a redox medium to catalyze the conversion of lithium polysulfide into lithium less sulfide. However, the lithium thiophosphate functional compound is dissolved in the electrolyte, and thus it is difficult to apply it to a battery separator. The invention uses fluorine-containing organic acid/anhydride with stronger electronegativity to react with imine to form an anion capture network on the polymer membrane substrate in situ, and the lithium thiophosphate functional compound and the anion capture site can be connected through Lewis acid-base interaction.
(2) According to the modified composite diaphragm for the battery, disclosed by the invention, the modified composite diaphragm is loaded on a commercial polymer diaphragm in an in-situ polymerization mode, a compact polymer network functional modified layer is formed on the surface of the diaphragm, the polymer network can reduce the aperture of the polymer diaphragm, and a physical barrier layer is formed on lithium polysulfide; the functional modified layer contains a large amount of ions and polar groups, so that the affinity between the surface of the diaphragm and the electrolyte can be enhanced, the contact angle between the diaphragm and the electrolyte can be reduced, the ion conductivity can be improved, the uniform transmission of lithium ions can be promoted, and the growth of lithium dendrites can be inhibited; polar groups and anion capture sites capable of adsorbing lithium polysulfide; the lithium thiophosphate can form a sulfur bond with the lithium polysulfide, adsorb and promote the conversion of the lithium polysulfide into less lithium sulfide, and effectively inhibit the shuttle effect of the lithium polysulfide in the lithium sulfur battery; these functions act synergistically to effectively improve battery performance.
(3) The modified composite diaphragm for the battery can be particularly applied to a lithium metal battery or a lithium sulfur battery, has the functions of enhancing the circulation stability of the battery and improving the utilization rate of active substances of the battery, and can achieve the effect of improving the performance of the battery. The modified composite diaphragm for the battery is further used for constructing a lithium metal battery or a lithium sulfur battery, and the battery assembling method is similar to the conventional lithium metal battery (or lithium sulfur battery) battery assembling method in the prior art, and the lithium metal battery (or lithium sulfur battery) battery is assembled according to the sequence of a positive electrode shell, a lithium iron phosphate pole piece (or a sulfur pole piece), electrolyte, the modified composite diaphragm for the battery, a lithium piece, a steel sheet, an elastic sheet and a negative electrode shell.
Drawings
FIG. 1 is a scanning electron microscope image of a polyethylene separator (abbreviated as PE) and a modified composite separator (abbreviated as LPS-ARN/PE) of example 1, wherein (a) in FIG. 1 corresponds to PE and (b) in FIG. 1 corresponds to LPS-ARN/PE.
FIG. 2 is an ultraviolet-visible absorption curve of experiments in which PE and LPS-ARN/PE of example 1 were adsorbed to lithium polysulfide.
FIG. 3 is a graph showing the redox potential of PE and LPS-ARN/PE of example 1, respectively, in response to an electrolyte for lithium sulfur batteries with/without lithium polysulfide.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The lithium metal battery constructed in the following examples was assembled by sequentially assembling a positive electrode case, a lithium iron phosphate electrode sheet, an electrolyte for a lithium metal battery, a modified composite separator for a battery, a lithium sheet, a steel sheet, an elastic sheet, and a negative electrode case, wherein the electrolyte solute for a lithium metal battery was 1mol/L LiPF 6 The solvent is a mixed solution of ethylene carbonate and dimethyl carbonate in a volume ratio of 1:1, and the addition amount is 40 mu L; the lithium sulfur battery is formed by sequentially assembling a positive electrode shell, a sulfur pole piece, electrolyte for the lithium sulfur battery, a modified composite diaphragm for the battery, a lithium piece, a steel sheet, an elastic sheet and a negative electrode shell, wherein the solute of the electrolyte for the lithium sulfur battery is 1mol/L LiTFSI and 1wt% LiNO 3 The solvent is a mixed solution of 1, 3-dioxolane and ethylene glycol dimethyl ether in a volume ratio of 1:1, and the addition amount is 40 mu L.
Example 1
A modified composite diaphragm for a battery is a modified composite diaphragm formed by combining a polymer diaphragm and a functional modified layer. A preparation method of a modified composite membrane for a battery comprises the steps of forming a polymer network on the surface of the polymer membrane through in-situ polymerization of phenolic amine, then combining the polymer network with a strong electron-withdrawing group to form an anion capturing network, and finally combining the anion capturing network with an electron-rich lithium thiophosphate functional compound. The application of the modified composite diaphragm for the battery is that the modified composite diaphragm for the battery is applied to a lithium sulfur battery.
The preparation of the modified composite separator for the battery comprises the following steps:
(1) Dissolving 0.06mmol of catechol and 0.06mmol of pentaethylenehexamine in 30mL of tris solution, and uniformly mixing;
(2) Placing a polyethylene diaphragm with the diameter of 85mm in the mixed solution obtained in the step (1), standing at 25 ℃ for 24 hours, taking out, washing and drying to obtain a polymer network modified diaphragm;
(3) Dissolving 0.18mmol of trifluoromethanesulfonic anhydride and 0.18mmol of triethylamine in dichloromethane, placing the polymer network modified membrane obtained in the step (2) in the dichloromethane for reaction, standing at 25 ℃ for 24 hours, taking out the polymer network modified membrane, washing and drying the polymer network modified membrane to obtain an anion capturing network modified membrane;
(4) Will 0.18mmol Li 3 PS 4 Dissolving in a mixed solution of 6mL of triethylamine and 24mL of methanol, placing the anion capture network modified membrane obtained in the step (3) into the mixed solution for reaction, standing for 24 hours at 25 ℃, taking out the membrane, washing and drying the membrane to obtain the modified composite membrane for the battery;
(5) And (3) applying the modified composite diaphragm obtained in the step (4) to a lithium-sulfur battery.
A series of comparative tests were performed on the modified composite separator for battery (abbreviated as LPS-ARN/PE) and the polyethylene separator (abbreviated as PE) in example 1, and the results were as follows.
The surface of the diaphragm is observed by a scanning electron microscope, and the result is shown in the attached figure 1, so that the functional modified layer on the surface of LPS-ARN/PE can be uniformly covered on PE, the aperture of PE can be reduced, and the physical barrier to lithium polysulfide can be formed.
The contact angle between the electrolyte and the separator for the lithium-sulfur battery is tested by a video optical contact angle measuring instrument, wherein the LPS-ARN/PE is 37.5 degrees, and the PE is 41.8 degrees, which shows that the functional modified layer in the LPS-ARN/PE can enhance the affinity between the electrolyte and the surface of the separator.
Further dripping 40 mu L of electrolyte for lithium-sulfur battery into the diaphragm, placing between two steel sheets, sealing in the battery case, and testing the conductivity by an electrochemical workstation, wherein LPS-ARN/PE is 0.52mS cm -1 Is 0.17mS cm higher than PE -1 It was demonstrated that the functional modification layer in LPS-ARN/PE was able to increase ionic conductivity.
The LPS-ARN/PE and PE (diameter 16mm, three pieces each) were immersed in 5mL of lithium polysulfide tetrahydrofuran solution (5 mmol/L), and the initial lithium polysulfide solution (PE and LPS-ARN/PE were not added) was compared, and after standing for 48 hours, the ultraviolet-visible absorption curve obtained by measuring the supernatant was measured, and as a result, as shown in FIG. 2, the intensity of the absorption curve of the lithium polysulfide solution after immersing LPS-ARN/PE was significantly reduced, indicating that LPS-ARN/PE was able to absorb lithium polysulfide.
After 40 mu L of electrolyte (0.2 mol/L) for lithium sulfur battery containing lithium polysulfide and electrolyte for lithium sulfur battery without lithium polysulfide are respectively added into LPS-ARN/PE and PE, a carbon/diaphragm/carbon symmetrical battery is assembled, and an oxidation-reduction potential curve is tested, and as shown in a figure 3, the comparison shows that the LPS-ARN/PE has obvious oxidation-reduction current peak (0.76V) when being acted with the electrolyte containing lithium polysulfide, and no current is generated when being acted with the electrolyte without lithium polysulfide, so that the LPS-ARN/PE can cause the lithium polysulfide to undergo oxidation-reduction reaction; the redox current peak does not appear when PE acts on the electrolyte containing or not containing lithium polysulfide, and the redox reaction of the lithium polysulfide is proved to be generated when PE acts on the functional modified layer of the invention, which shows that LPS-ARN/PE can catalyze the conversion of the lithium polysulfide into less lithium sulfide, thereby inhibiting the shuttle effect of the lithium polysulfide and improving the utilization rate of active substances.
The battery is subjected to a cyclic charge and discharge test, and the initial discharge specific capacity of the battery containing LPS-ARN/PE is 830.4mAh g under the current density of 1C -1 PE-containing battery 671.8mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the After 500 cycles, the average cell capacity per cycle decay was 0.07% with LPS-ARN/PE.
The performance comparison shows that the modified composite membrane for the battery has the functions of enhancing the affinity between the surface of the membrane and electrolyte, improving the ionic conductivity, adsorbing and catalyzing the conversion of lithium polysulfide, and can improve the performance of the battery.
Example 2
A modified composite diaphragm for a battery is a modified composite diaphragm formed by combining a polymer diaphragm and a functional modified layer. A preparation method of a modified composite membrane for a battery comprises the steps of forming a polymer network on the surface of the polymer membrane through in-situ polymerization of phenolic amine, then combining the polymer network with a strong electron-withdrawing group to form an anion capturing network, and finally combining the anion capturing network with an electron-rich lithium thiophosphate functional compound. The modified composite diaphragm for the battery is applied to a lithium metal battery.
The preparation of the modified composite separator for the battery comprises the following steps:
(1) Dissolving 0.06mmol of catechol and 0.06mmol of pentaethylenehexamine in 30mL of tris solution, and uniformly mixing;
(2) Placing a polyethylene diaphragm with the diameter of 85mm in the mixed solution obtained in the step (1), standing at 25 ℃ for 24 hours, taking out, washing and drying to obtain a polymer network modified diaphragm;
(3) Dissolving 0.18mmol of trifluoromethanesulfonic anhydride and 0.18mmol of triethylamine in dichloromethane, placing the polymer network modified membrane obtained in the step (2) in the dichloromethane for reaction, standing at 25 ℃ for 24 hours, taking out the polymer network modified membrane, washing and drying the polymer network modified membrane to obtain an anion capturing network modified membrane;
(4) Will 0.18mmol Li 3 PS 4 Dissolving in a mixed solution of 6mL of triethylamine and 24mL of methanol, placing the anion capture network modified membrane obtained in the step (3) into the mixed solution for reaction, standing for 24 hours at 25 ℃, taking out the membrane, washing and drying the membrane to obtain the modified composite membrane for the battery;
(5) And (3) applying the modified composite diaphragm obtained in the step (4) to a lithium metal battery.
The battery is subjected to a cyclic charge and discharge test, and the initial discharge specific capacity of the battery containing LPS-ARN/PE is 141.2mAh g under the current density of 3C -1 PE-containing battery was 132.0mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the CirculationAfter 500 times, the average cell capacity per cycle decay was 0.121% with LPS-ARN/PE.
Example 3
A modified composite diaphragm for a battery is a modified composite diaphragm formed by combining a polymer diaphragm and a functional modified layer. A preparation method of a modified composite membrane for a battery comprises the steps of forming a polymer network on the surface of the polymer membrane through in-situ polymerization of phenolic amine, then combining the polymer network with a strong electron-withdrawing group to form an anion capturing network, and finally combining the anion capturing network with an electron-rich lithium thiophosphate functional compound. The modified composite diaphragm for the battery is applied to a lithium metal battery.
The preparation of the modified composite separator for the battery comprises the following steps:
(1) Dissolving 0.003mmol of resorcinol, 0.003mmol of hydroquinone and 0.006mmol of diethylenetriamine in 30mL of tris solution, and uniformly mixing;
(2) Placing a polypropylene diaphragm with the diameter of 85mm in the mixed solution obtained in the step (1), standing at 50 ℃ for 0.5h, taking out, washing and drying to obtain a polymer network modified diaphragm;
(3) Dissolving 0.006mmol of trifluoroacetic anhydride and 0.006mmol of triethylamine in chloroform, placing the polymer network modified membrane obtained in the step (2) in the chloroform for reaction, standing at 30 ℃ for 0.5h, taking out the membrane, washing and drying the membrane to obtain the anion capturing network modified membrane;
(4) Will 0.006mmol Li 3 PS 4 Dissolving in a mixed solution of 6mL of triethylamine and 24mL of methanol, placing the anion capture network modified membrane obtained in the step (3) in the mixed solution for reaction, standing for 0.5h at 50 ℃, taking out the membrane, washing and drying the membrane to obtain the modified composite membrane for the battery;
(5) And (3) applying the modified composite diaphragm obtained in the step (4) to a lithium metal battery.
Example 4
A modified composite diaphragm for a battery is a modified composite diaphragm formed by combining a polymer diaphragm and a functional modified layer. A preparation method of a modified composite membrane for a battery comprises the steps of forming a polymer network on the surface of the polymer membrane through in-situ polymerization of phenolic amine, then combining the polymer network with a strong electron-withdrawing group to form an anion capturing network, and finally combining the anion capturing network with an electron-rich lithium thiophosphate functional compound. The modified composite diaphragm for the battery is applied to a lithium metal battery.
The preparation of the modified composite separator for the battery comprises the following steps:
(1) Dissolving 0.6mmol of hydroquinone, 0.15mmol of triethylene tetramine and 0.15mmol of tetraethylene pentamine in 30mL of tris solution, and uniformly mixing;
(2) Placing a polyethylene/polypropylene composite membrane with the diameter of 85mm in the mixed solution obtained in the step (1), standing at 20 ℃ for 48 hours, taking out, washing and drying to obtain a polymer network modified membrane;
(3) Dissolving 1.2mmol of trifluoromethanesulfonic acid and 1.2mmol of triethylamine in dichloromethane, placing the polymer network modified membrane obtained in the step (2) in the dichloromethane for reaction, standing at-30 ℃ for 2 hours, taking out the membrane, washing and drying the membrane to obtain the anion capturing network modified membrane;
(4) 1.2mmol of Li 2 P 2 S 6 Dissolving in a mixed solution of 6mL of triethylamine and 24mL of methanol, placing the anion capture network modified membrane obtained in the step (3) into the mixed solution for reaction, standing for 48 hours at 20 ℃, taking out the membrane, washing and drying the membrane to obtain the modified composite membrane for the battery;
(5) And (3) applying the modified composite diaphragm obtained in the step (4) to a lithium metal battery.
Example 5
A modified composite diaphragm for a battery is a modified composite diaphragm formed by combining a polymer diaphragm and a functional modified layer. A preparation method of a modified composite membrane for a battery comprises the steps of forming a polymer network on the surface of the polymer membrane through in-situ polymerization of phenolic amine, then combining the polymer network with a strong electron-withdrawing group to form an anion capturing network, and finally combining the anion capturing network with an electron-rich lithium thiophosphate functional compound. The application of the modified composite diaphragm for the battery is that the modified composite diaphragm for the battery is applied to a lithium sulfur battery.
The preparation of the modified composite separator for the battery comprises the following steps:
(1) Dissolving 0.1mmol of 2-methylresorcinol and 0.2mmol of tetraethylenepentamine in 30mL of tris solution, and uniformly mixing;
(2) Placing a polyethylene diaphragm with the diameter of 85mm in the mixed solution obtained in the step (1), standing for 12 hours at 25 ℃, taking out, washing and drying to obtain a polymer network modified diaphragm;
(3) Dissolving 0.2mmol of trifluoromethanesulfonic acid, 0.2mmol of difluoromethanesulfonic acid and 0.4mmol of triethylamine in chloroform, placing the polymer network modified membrane obtained in the step (2) in the chloroform for reaction, standing at 0 ℃ for 3 hours, taking out the membrane, washing and drying the membrane to obtain the anion capturing network modified membrane;
(4) Will 0.2mmol Li 7 P 3 S 11 Dissolving in a mixed solution of 15mL of triethylamine and 15mL of methanol, placing the anion capture network modified membrane obtained in the step (3) in the mixed solution for reaction, standing for 4 hours at 25 ℃, taking out the membrane, washing and drying the membrane to obtain the modified composite membrane for the battery;
(5) And (3) applying the modified composite diaphragm obtained in the step (4) to a lithium-sulfur battery.
Example 6
A modified composite diaphragm for a battery is a modified composite diaphragm formed by combining a polymer diaphragm and a functional modified layer. A preparation method of a modified composite membrane for a battery comprises the steps of forming a polymer network on the surface of the polymer membrane through in-situ polymerization of phenolic amine, then combining the polymer network with a strong electron-withdrawing group to form an anion capturing network, and finally combining the anion capturing network with an electron-rich lithium thiophosphate functional compound. The modified composite diaphragm for the battery is applied to a lithium metal battery.
The preparation of the modified composite separator for the battery comprises the following steps:
(1) Dissolving 0.1mmol of 4-methylresorcinol and 0.1mmol of tetraethylenepentamine in 30mL of tris solution, and uniformly mixing;
(2) Placing a polyvinylidene fluoride diaphragm with the diameter of 85mm in the mixed solution obtained in the step (1), standing for 12 hours at 25 ℃, taking out, washing and drying to obtain a polymer network modified diaphragm;
(3) Dissolving 0.4mmol of trifluoroacetic acid and 0.4mmol of triethylamine in dichloromethane, placing the polymer network modified membrane obtained in the step (2) in the dichloromethane for reaction, standing at 0 ℃ for 3 hours, taking out the membrane, washing and drying the membrane to obtain the anion capturing network modified membrane;
(4) Will 0.2mmol Li 4 P 2 S 6 Dissolving in a mixed solution of 15mL of triethylamine and 15mL of methanol, placing the anion capture network modified membrane obtained in the step (3) in the mixed solution for reaction, standing for 4 hours at 25 ℃, taking out the membrane, washing and drying the membrane to obtain the modified composite membrane for the battery;
(5) And (3) applying the modified composite diaphragm obtained in the step (4) to a lithium metal battery.
Example 7
A modified composite diaphragm for a battery is a modified composite diaphragm formed by combining a polymer diaphragm and a functional modified layer. A preparation method of a modified composite membrane for a battery comprises the steps of forming a polymer network on the surface of the polymer membrane through in-situ polymerization of phenolic amine, then combining the polymer network with a strong electron-withdrawing group to form an anion capturing network, and finally combining the anion capturing network with an electron-rich lithium thiophosphate functional compound. The application of the modified composite diaphragm for the battery is that the modified composite diaphragm for the battery is applied to a lithium sulfur battery.
The preparation of the modified composite separator for the battery comprises the following steps:
(1) Dissolving 0.1mmol of pyrogallol and 0.15mmol of pentaethylenehexamine in 30mL of tris solution, and uniformly mixing;
(2) Placing a polyimide diaphragm with the diameter of 85mm in the mixed solution obtained in the step (1), standing at 25 ℃ for 12 hours, taking out, washing and drying to obtain a polymer network modified diaphragm;
(3) Dissolving 2.7mmol of difluoro acetic acid and 2.7mmol of triethylamine in dichloromethane, placing the polymer network modified membrane obtained in the step (2) in the dichloromethane for reaction, standing at 0 ℃ for 0.5h, taking out the membrane, washing and drying the membrane to obtain the anion capturing network modified membrane;
(4) Will 2.7mmol Li 4 P 2 S 7 Dissolving in a mixed solution of 15mL of triethylamine and 15mL of methanol, placing the anion capture network modified membrane obtained in the step (3) in the mixed solution for reaction, standing for 4 hours at 25 ℃, taking out the membrane, washing and drying the membrane to obtain the modified composite membrane for the battery;
(5) And (3) applying the modified composite diaphragm obtained in the step (4) to a lithium-sulfur battery.
Example 8
A modified composite diaphragm for a battery is a modified composite diaphragm formed by combining a polymer diaphragm and a functional modified layer. A preparation method of a modified composite membrane for a battery comprises the steps of forming a polymer network on the surface of the polymer membrane through in-situ polymerization of phenolic amine, then combining the polymer network with a strong electron-withdrawing group to form an anion capturing network, and finally combining the anion capturing network with an electron-rich lithium thiophosphate functional compound. The modified composite diaphragm for the battery is applied to a lithium metal battery.
The preparation of the modified composite separator for the battery comprises the following steps:
(1) 0.1mmol of phloroglucinol and 0.2mmol of pentaethylenehexamine are dissolved in 30mL of tris solution and evenly mixed;
(2) Placing a polyethylene diaphragm with the diameter of 85mm in the mixed solution obtained in the step (1), standing for 12 hours at 25 ℃, taking out, washing and drying to obtain a polymer network modified diaphragm;
(3) Dissolving 0.4mmol of difluoroacetic anhydride and 0.4mmol of triethylamine in dichloromethane, placing the polymer network modified membrane obtained in the step (2) in the dichloromethane for reaction, standing at 0 ℃ for 3 hours, taking out the membrane, washing and drying the membrane to obtain the anion capturing network modified membrane;
(4) Will 0.8mmol Li 4 P 2 S 6 And 0.1mmol Li 4 P 2 S 7 Dissolving in a mixed solution of 15mL of triethylamine and 15mL of methanol, placing the anion capture network modified membrane obtained in the step (3) in the mixed solution for reaction, standing for 4 hours at 25 ℃, taking out the membrane, washing and drying the membrane to obtain the modified composite membrane for the battery;
(5) And (3) applying the modified composite diaphragm obtained in the step (4) to a lithium metal battery.
Example 9
A modified composite diaphragm for a battery is a modified composite diaphragm formed by combining a polymer diaphragm and a functional modified layer. A preparation method of a modified composite membrane for a battery comprises the steps of forming a polymer network on the surface of the polymer membrane through in-situ polymerization of phenolic amine, then combining the polymer network with a strong electron-withdrawing group to form an anion capturing network, and finally combining the anion capturing network with an electron-rich lithium thiophosphate functional compound. The modified composite diaphragm for the battery is applied to a lithium metal battery.
The preparation of the modified composite separator for the battery comprises the following steps:
(1) Dissolving 0.1mmol of trimellitic phenol and 0.2mmol of tetraethylenepentamine in 30mL of tris solution, and uniformly mixing;
(2) Placing a polypropylene diaphragm with the diameter of 85mm in the mixed solution obtained in the step (1), standing at 25 ℃ for 12 hours, taking out, washing and drying to obtain a polymer network modified diaphragm;
(3) Dissolving 0.4mmol of trifluoromethanesulfonic anhydride and 0.4mmol of triethylamine in dichloromethane, placing the polymer network modified membrane obtained in the step (2) in the dichloromethane for reaction, standing at 20 ℃ for 48 hours, taking out the polymer network modified membrane, washing and drying the polymer network modified membrane to obtain the anion capturing network modified membrane;
(4) Will 0.2mmol Li 3 PS 4 Dissolving in a mixed solution of 15mL of triethylamine and 15mL of methanol, placing the anion capturing network modified membrane obtained in the step (3) in the mixed solution for reaction, standing for 4 hours at 25 ℃, taking out, and washingWashing and drying to obtain the modified composite diaphragm for the battery;
(5) And (3) applying the modified composite diaphragm obtained in the step (4) to a lithium metal battery.
The above embodiments are merely examples, and for example, in the step of forming a polymer network by in situ polymerization of a phenol amine, the concentration and/or reaction time and/or reaction temperature of a polyhydric phenol compound, a polyhydric amine compound, and the like, the thickness of the functional modified layer of the modified composite separator may be controlled, for example, the greater the concentration of phenol or amine, the thicker the modified layer tends to be; the thickness of the modified layer can be regulated and controlled by technicians according to the actual requirements during application so as to realize better edge performance and the like; the concentration of the polyhydric phenol compound is preferably controlled to be 0.2-20 mmol/L, the concentration of the polyhydric amine compound is controlled to be 0.5-2 times of the concentration of the polyhydric phenol compound, the reaction time is controlled to be 0.5-48 h, the reaction temperature is controlled to be 20-50 ℃, the thickness of the functional modified layer is easy to regulate and control, and the requirements on the performance of a diaphragm during the cyclic charge and discharge of a battery are met.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (4)
1. The preparation method is characterized in that firstly, a polymer network is formed on the surface of a polymer membrane through in-situ polymerization of phenolic amine, then the polymer network is combined with fluorine-containing organic acid/anhydride to form an anion capturing network, and then the anion capturing network is combined with lithium thiophosphate through the action of Lewis acid alkali, so that the modified composite membrane for the battery is obtained;
wherein the fluorine-containing organic acid/anhydride is fluorine-containing organic acid and/or fluorine-containing organic anhydride;
the preparation method specifically comprises the following steps:
(1) Placing the polymer membrane in an alkaline solution containing a polyhydric phenol compound and a polyhydric amine compound at the same time, and performing in-situ polymerization to obtain a polymer network modified polymer membrane;
(2) Dissolving fluorine-containing organic acid/anhydride and triethylamine in an organic solvent at the same time, and then placing the polymer membrane modified by the polymer network into the organic solvent for reaction to obtain the polymer membrane modified by the anion capturing network;
(3) And dissolving lithium thiophosphate in a mixed solution of triethylamine and methanol, and then placing the anion capturing network modified polymer membrane into the mixed solution for reaction to obtain the modified composite membrane for the battery.
2. The method of claim 1, wherein in the step (1), the polymer membrane comprises any one of a polyethylene membrane, a polypropylene membrane, a polyethylene/polypropylene composite membrane, a polyimide membrane, and a polyvinylidene fluoride membrane;
the polyphenol compound comprises one or more of catechol, resorcinol, hydroquinone, 2-methyl resorcinol, 4-methyl resorcinol, pyrogallol, phloroglucinol and metaphloroglucinol;
the polyamine compound comprises one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine;
the alkaline solution is obtained by simultaneously adding a polyhydric phenol compound and a polyhydric amine compound into a tris aqueous solution; in the obtained alkaline solution, the concentration of the polyhydric phenol compound is 0.2-20 mmol/L, and the ratio of the concentration of the polyhydric phenol compound to the concentration of the polyhydric amine compound is 0.5-2;
the reaction time of the in-situ polymerization is 0.5-48 h, and the reaction temperature is 20-50 ℃.
3. The method according to claim 1, wherein in the step (2), the fluorine-containing organic acid/acid anhydride is one or more of trifluoromethanesulfonic anhydride, trifluoromethanesulfonic acid, difluoromethanesulfonic acid, trifluoroacetic anhydride, difluoroacetic acid, and difluoroacetic anhydride;
the organic solvent is one of dichloromethane and chloroform; the ratio of the amount of the fluorine-containing organic acid/acid anhydride substance to the amount of the polyamine substance is 1 to 18; the ratio of the amount of the substance of triethylamine to the amount of the substance of polyamine is 1 to 18;
the reaction time of the reaction is 0.5-48 h, and the reaction temperature is-30 ℃.
4. The method of claim 1, wherein in step (3), the lithium thiophosphate is Li 3 PS 4 、Li 2 P 2 S 6 、Li 7 P 3 S 11 、Li 4 P 2 S 6 、Li 4 P 2 S 7 One or more of the following;
the volume ratio of the triethylamine to the methanol in the mixed solution of the triethylamine and the methanol is 1:4-1:1; the ratio of the amount of the lithium thiophosphate substance to the amount of the polyamine substance is 1 to 18;
the reaction time of the reaction is 0.5-48 h, and the reaction temperature is 20-50 ℃.
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| CN202211339800.7A Active CN115498364B (en) | 2022-10-28 | 2022-10-28 | Modified composite diaphragm for battery and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613780A (en) * | 2013-11-14 | 2014-03-05 | 中国科学院化学研究所 | Method for surface modification of hydrophobic polymer microporous membrane |
| CN109148796A (en) * | 2017-06-19 | 2019-01-04 | 通用汽车环球科技运作有限责任公司 | Acid for lithium ion electrochemical cells power-performance removes function diaphragm |
| CN114497721A (en) * | 2022-01-07 | 2022-05-13 | 哈尔滨工业大学 | Composite electrolyte film, preparation method thereof and application thereof in solid-state lithium battery |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613780A (en) * | 2013-11-14 | 2014-03-05 | 中国科学院化学研究所 | Method for surface modification of hydrophobic polymer microporous membrane |
| CN109148796A (en) * | 2017-06-19 | 2019-01-04 | 通用汽车环球科技运作有限责任公司 | Acid for lithium ion electrochemical cells power-performance removes function diaphragm |
| CN114497721A (en) * | 2022-01-07 | 2022-05-13 | 哈尔滨工业大学 | Composite electrolyte film, preparation method thereof and application thereof in solid-state lithium battery |
Non-Patent Citations (1)
| Title |
|---|
| Will Sulfide Electrolytes be Suitable Candidates for Constructing a Stable Solid/Liquid Electrolyte Interface?;Fan Bo 等;《ACS applied materials & interfaces》;第12卷(第47期);第52845-52856页 * |
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