WO2023245949A1 - Metal-organic coordination polymer m2cax, preparation method therefor and use thereof - Google Patents
Metal-organic coordination polymer m2cax, preparation method therefor and use thereof Download PDFInfo
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- WO2023245949A1 WO2023245949A1 PCT/CN2022/128467 CN2022128467W WO2023245949A1 WO 2023245949 A1 WO2023245949 A1 WO 2023245949A1 CN 2022128467 W CN2022128467 W CN 2022128467W WO 2023245949 A1 WO2023245949 A1 WO 2023245949A1
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- metal
- coordination polymer
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- organic coordination
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 64
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 31
- 239000013110 organic ligand Substances 0.000 claims abstract description 23
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 14
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000010406 cathode material Substances 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- IPPWILKGXFOXHO-UHFFFAOYSA-N chloranilic acid Chemical compound OC1=C(Cl)C(=O)C(O)=C(Cl)C1=O IPPWILKGXFOXHO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- QFSYADJLNBHAKO-UHFFFAOYSA-N 2,5-dihydroxy-1,4-benzoquinone Chemical compound OC1=CC(=O)C(O)=CC1=O QFSYADJLNBHAKO-UHFFFAOYSA-N 0.000 claims description 4
- HSBQYDCVAYTMFR-UHFFFAOYSA-N 2,5-difluoro-3,6-dihydroxycyclohexa-2,5-diene-1,4-dione Chemical compound OC1=C(F)C(=O)C(O)=C(F)C1=O HSBQYDCVAYTMFR-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- DGQOCLATAPFASR-UHFFFAOYSA-N tetrahydroxy-1,4-benzoquinone Chemical compound OC1=C(O)C(=O)C(O)=C(O)C1=O DGQOCLATAPFASR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 239000012266 salt solution Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000007774 positive electrode material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 1
- 238000003760 magnetic stirring Methods 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910052727 yttrium Inorganic materials 0.000 description 8
- 239000011572 manganese Substances 0.000 description 7
- 239000005486 organic electrolyte Substances 0.000 description 7
- 239000007784 solid electrolyte Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 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 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- 238000012552 review Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 241000275031 Nica Species 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 2
- KTOXGWMDJYFBKK-UHFFFAOYSA-L manganese(2+);diacetate;dihydrate Chemical compound O.O.[Mn+2].CC([O-])=O.CC([O-])=O KTOXGWMDJYFBKK-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000379 polypropylene carbonate Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- GMZWPTALVQRAFV-UHFFFAOYSA-N 2,5-dibromo-3,6-dihydroxycyclohexa-2,5-diene-1,4-dione Chemical compound OC1=C(Br)C(=O)C(O)=C(Br)C1=O GMZWPTALVQRAFV-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000013082 iron-based metal-organic framework Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- -1 polypropylene carbonate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the invention belongs to the technical field of lithium-ion battery cathode materials in electrochemical energy storage, and specifically relates to metal-organic coordination polymer M 2 CA X and its preparation method and application.
- Lithium-ion batteries have been widely used in electric vehicles and various electronic products due to their good cycle stability and high energy density. It can be said that achieving the goals of "carbon neutrality" and "carbon peak” is inseparable from lithium-ion batteries.
- commercial lithium-ion battery cathode materials are mainly inorganic transition metals.
- commercial inorganic cathodes are severely restricted due to limited resources, unenvironmentally friendly processes, low theoretical capacity, and high cost.
- Organic matter has the advantages of abundant resources, high theoretical specific capacity, and adjustable molecular structure, and is considered to be a promising electrode material for lithium-ion batteries (Poizot, P.; Gaubicher, J.; Renault, S.; Dubois, L.; Liang, Y.; Yao, Y., Opportunities and Challenges for Organic Electrodes in Electrochemical Energy Storage. Chemical Reviews 2020, 120, 6490 ⁇ 6557.).
- the high solubility and inherent low conductivity of most low molecular weight organic molecules in liquid electrolytes restrict the development of their electrochemical properties. Polymerization is considered to be one of the most effective ways to address these challenges, but excessive polymerization often affects the electrochemical performance of lithium-ion batteries by reducing battery capacity.
- metal-organic coordination polymers can build a stable skeleton without sacrificing the density of redox-active species by introducing transition metal ions with high redox activity to bridge organic ligands. Due to its diverse and controllable structure, good pseudocapacitive performance and stable structure, it has shown great potential as an electrode material and has received widespread attention. However, its practical application still faces many challenges.
- the existing preparation methods of metal-organic coordination polymers mainly include hydrothermal and solvothermal methods (Reddy, R. C. K.; Lin, X.; Zeb, A.; Su, C. Y., Metal–Organic Frameworks and Their Derivatives as Cathodes for Lithium-Ion Battery Applications: A Review. Electrochemical Energy Reviews 2021, 5, 312-347.), these methods have problems such as low yield, long reaction time, large energy consumption, etc., and are difficult to be commercialized on a large scale.
- Metal-organic coordination polymer electrode materials face challenges in simultaneously realizing redox reactions involving transition metals and organic ligands (Ferey, G; Millange, F.; Morcrette, M.; Serre, C.; Doublet, M. L.; Greneche, J. M.; Tarascon, J. M., Mixed-Valence Li/Fe-Based Metal–Organic Frameworks with Both Reversible Redox and Sorption Properties.
- the purpose of the present invention is to propose metal-organic coordination polymers M 2 CA X and their preparation methods and applications.
- the preparation method is a universal The synthesis strategy of the metal-organic coordination polymer system, and the prepared metal-organic coordination polymer M 2 CA X is used as a cathode material in lithium-ion batteries.
- This preparation method can obtain a variety of metal-organic coordination polymers M 2 CA
- metal-organic coordination polymers can simultaneously realize the redox reactions of transition metals and organic ligands and have excellent electrochemical properties.
- the crystal structure of the metal - organic coordination polymer M 2 CA Improve the lithium storage specific capacity of electrode materials.
- a metal-organic coordination polymer its preparation method and its application as a positive electrode material for lithium ion batteries.
- the present invention provides a metal-organic coordination polymer M 2 CA X.
- the general structural formula of the metal-organic coordination polymer M 2 CA X is as follows:
- Y is one of H, hydroxyl (OH), Cl, Br, and F; M is one of Fe, Mn, Ni, and Cu; X is 2-3; n represents the number of repeating units.
- the room temperature two-step aqueous solution preparation method provided by the invention is: at room temperature, first use a simple acid-base neutralization reaction to obtain an aqueous solution of the organic ligand salt (Z 2 CA), and then prepare the organic ligand salt (Z 2 CA)
- the aqueous solution and the salt solution of the transition metal ion (MX + ) undergo a coordination reaction (the organic ligand CA 2 ⁇ coordinates with the transition metal ion M
- step (2) Co-precipitate the aqueous solution of the organic ligand salt Z 2 CA obtained in step (1) with a certain proportion of different types of transition metal ion (MX + ) salt solutions under magnetic stirring at a certain temperature and a certain speed for a certain period of time. , the reaction product is centrifuged and washed with water, filtered, and finally vacuum dried at a certain temperature for a certain period of time to obtain the metal-organic coordination polymer M 2 CA X .
- MX + transition metal ion
- the base ZOH is one of KOH and NaOH, corresponding to Z being K and Na respectively;
- RT represents room temperature, and room temperature is 25-35 ⁇ C;
- H 2 O represents the reaction conditions of aqueous solution.
- the organic ligand acid H 2 CA can be 2, 5-dihydroxy-p-benzoquinone, tetrahydroxy-p-benzoquinone, 2, 5-dichloro-3, 6-dihydroxy-p-benzoquinone, 2, 5-dibromo- One of 3, 6-dihydroxy-p-benzoquinone and 2, 5-difluoro-3, 6-dihydroxy-p-benzoquinone, respectively corresponding to Y being one of H, hydroxyl (OH), Cl, Br, and F kind.
- the base (ZOH) in step (1) can be one of potassium hydroxide (KOH) and sodium hydroxide (NaOH).
- the molar ratio of the organic ligand acid (H 2 CA) and base (ZOH) described in step (1) is 1:(2-3).
- transition metal ion ( MX+ ) described in step (2) may be one of Fe 3+ , Mn 3+ , Ni 2+ and Cu 2+ .
- step (2) the molar ratio of the organic ligand salt Z 2 CA to different kinds of transition metal ions ( MX+ ) is (1-4):2.
- concentration range of the different types of transition metal ion (MX + ) salt solutions and the aqueous solution of the organic ligand salt Z 2 CA described in step (2) is 0.1-2 mol/L.
- the different kinds of transition metal ions (M X+ ) in step (2) are one of Fe 3+ , Mn 3+ , Ni 2+ and Cu 2+ .
- step (2) the temperature of the co-precipitation reaction is room temperature 25-35 ⁇ C, the co-precipitation reaction time is 2-10 h, and the magnetic stirring speed is 300-400 r/min; the centrifugal speed is 6000-8000 r/min; the drying conditions are 120-150 ⁇ C vacuum drying 6-12 h.
- the invention also provides an economical and environmentally friendly metal-organic coordination polymer M 2 CA
- the present invention has the following beneficial effects:
- the room temperature two-step aqueous solution method adopted in the present invention is to react organic ligand salts obtained through the neutralization reaction of various organic ligand acids and bases with different types of transition metal ion ( MX+ ) salts at room temperature. Co-precipitation reaction is carried out under the conditions to prepare metal-organic coordination polymer M 2 CA X.
- M 2 CA X does not contain solvent molecules.
- This preparation method is not only simple, easy, green and environmentally friendly, but also can synthesize a variety of metal-organic coordination polymer materials at low cost, low energy consumption and high yield, providing a basis for large-scale commercial synthesis of metal-organic coordination polymer materials. A new approach.
- the metal-organic coordination polymer M 2 CA It can provide electrochemical active sites with metal ions at the same time, can provide a channel for the rapid transmission of lithium ions, and has excellent electrochemical performance.
- Figure 1 is a scanning electron microscope (SEM) image of the metal-organic coordination polymer CuCA prepared in Example 1 of the present invention at different scales.
- Figure 2 is a transmission electron microscope (TEM) image of the metal-organic coordination polymer CuCA prepared in Example 1 of the present invention.
- Figure 3 shows the metal-organic coordination polymer CuCA prepared in Example 1 of the present invention as a lithium-ion battery cathode material matched with metallic lithium anode, organic electrolyte and Celgard 2400 commercial separator at a current density of 100 mA g ⁇ 1 Electrochemical cycle performance plot.
- Figure 4 shows the electrochemical cycle of the metal-organic coordination polymer CuCA prepared in Example 1 of the present invention as a lithium-ion battery cathode material matched with a metal lithium anode and a polymer-based solid electrolyte at a current density of 100 mA g ⁇ 1 Performance graph.
- Figure 1 is a scanning electron microscope (SEM) image of the metal-organic coordination polymer CuCA prepared in Example 1 at different scales. It can be seen from Figure 1 that CuCA has a uniform nanosheet structure with a side length of 500 nm, with a thickness of 30 nm.
- Figure 2 is a transmission electron microscope (TEM) image of the metal-organic coordination polymer CuCA prepared in Example 1. It can be seen from Figure 2 that the nanosheet structure of the obtained CuCA is uniform and complete.
- SEM scanning electron microscope
- the metal-organic coordination polymer CuCA prepared in Example 1 is used as a cathode material in a lithium-ion battery with an organic electrolyte system.
- the steps are as follows:
- a metal Li piece is used as the negative electrode piece, 1 M LiTFSI in DME/DOL (1:1 Vol%) (where LiTFSI is lithium bistrifluoromethanesulfonimide, DME is ethylene glycol dimethyl ether, and DOL is 1,3-dioxolane) as the organic electrolyte, Celgard 2400 commercial separator is used as the battery separator, and the obtained positive electrode sheet is assembled into a lithium-ion battery with an organic electrolyte system in a glove box filled with inert gas.
- LiTFSI lithium bistrifluoromethanesulfonimide
- DME ethylene glycol dimethyl ether
- DOL 1,3-dioxolane
- Figure 3 shows the electrochemistry of the metal-organic coordination polymer CuCA prepared in Example 1 as a lithium-ion battery cathode material, matched with metallic lithium anode, organic electrolyte and Celgard 2400 commercial separator at a current density of 100 mA g ⁇ 1 Cycle performance graph.
- the assembled lithium-ion battery has a discharge specific capacity of 239.9 mAh g ⁇ 1 in the first cycle, and still has a specific capacity of 124.1 mAh g ⁇ 1 after 20 cycles.
- the Coulombic efficiency is 93.4%, showing excellent cycle stability. , indicating that the metal-organic coordination polymer CuCA has excellent lithium storage performance when used as a cathode material for lithium-ion batteries in organic electrolyte systems.
- 0.6 g of metal-organic coordination polymer CuCA, 0.3 g of conductive carbon, and 0.1 g of sodium carboxymethyl cellulose (CMC-Na) binder were ground in 2 mL of water solvent at a mass ratio of 6:3:1 for 30 min, adjust it into a uniform positive electrode conductive slurry, evenly coat it on the current collector aluminum foil, dry it under vacuum at 100 ⁇ C for 10 hours, and cut it into small discs with a diameter of 10 mm, which is the obtained metal-organic compound.
- a metal Li sheet is used as the negative electrode sheet, and the polymer-based solid electrolyte (PPC-PEO-LiTFSI-Al 2 O 3 solid electrolyte, where PPC is polypropylene carbonate, PEO is polyethylene oxide, and LiTFSI is bistrifluoromethane Lithium sulfonimide is assembled with the obtained positive electrode sheet in a glove box filled with inert gas to form a lithium-ion battery with a polymer-based solid electrolyte system.
- PPC-PEO-LiTFSI-Al 2 O 3 solid electrolyte where PPC is polypropylene carbonate, PEO is polyethylene oxide, and LiTFSI is bistrifluoromethane Lithium sulfonimide is assembled with the obtained positive electrode sheet in a glove box filled with inert gas to form a lithium-ion battery with a polymer-based solid electrolyte system.
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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Abstract
Disclosed are a metal-organic coordination polymer M2CAX, a preparation method therefor and use thereof. According to the present invention, a room-temperature two-step aqueous solution method is used for performing coordination on an organic ligand salt (CA2−) solution synthesized through an acid-base neutralization reaction and a salt solution comprising transition metal ions (MX+) to obtain various metal-organic coordination polymers M2CAX (M=Cu, Fe, Mn, Ni) capable of being used as a positive electrode material of a lithium ion battery. More importantly, the raw materials for preparing the metal-organic coordination polymer M2CAX have wide sources, low price, simple preparation method, low energy consumption, and universality. The lithium ion battery assembled by means of the metal-organic coordination polymer M2CAX as the positive electrode material has excellent electrochemical performance.
Description
本发明属于电化学储能中锂离子电池正极材料技术领域，具体涉及金属-有机配位聚合物M
2CA
X及其制备方法与应用。
The invention belongs to the technical field of lithium-ion battery cathode materials in electrochemical energy storage, and specifically relates to metal-organic coordination polymer M 2 CA X and its preparation method and application.
化石燃料的生产与使用造成的碳排放导致的环境污染是当今世界日益关注的关键问题。开发利用风能、太阳能等新能源是解决这一问题的有效途径。而新能源的有效利用对高性能的储能系统提出了更高的要求。锂离子电池以其良好的循环稳定性和高能量密度，在电动汽车和各类电子产品中都得到了广泛的应用。可以说要实现“碳中和”和“碳达峰”的目标离不开锂离子电池。目前商用锂离子电池正极材料主要以无机过渡金属为主，但由于资源有限、工艺不环保、理论容量低和成本高等原因，使得商业化的无机正极受到严重制约。Environmental pollution caused by carbon emissions caused by the production and use of fossil fuels is a key issue of increasing concern in today's world. The development and utilization of new energy sources such as wind energy and solar energy is an effective way to solve this problem. The effective utilization of new energy puts forward higher requirements for high-performance energy storage systems. Lithium-ion batteries have been widely used in electric vehicles and various electronic products due to their good cycle stability and high energy density. It can be said that achieving the goals of "carbon neutrality" and "carbon peak" is inseparable from lithium-ion batteries. Currently, commercial lithium-ion battery cathode materials are mainly inorganic transition metals. However, commercial inorganic cathodes are severely restricted due to limited resources, unenvironmentally friendly processes, low theoretical capacity, and high cost.
有机物具有资源丰富、理论比容量高、分子结构可调等优点，被认为是一种很有前途的锂离子电池电极材料（Poizot, P.;
Gaubicher, J.; Renault, S.; Dubois, L.; Liang, Y.; Yao, Y., Opportunities and
Challenges for Organic Electrodes in Electrochemical Energy Storage. Chemical
Reviews 2020, 120, 6490−6557.）。但大多数低分子量的有机分子在液体电解质中的高溶解度和固有的低电导率制约了其电化学性能的发展。聚合反应被认为是解决这些挑战最有效的方法之一，但聚合度过高通常会降低电池容量从而影响锂离子电池的电化学性能。Organic matter has the advantages of abundant resources, high theoretical specific capacity, and adjustable molecular structure, and is considered to be a promising electrode material for lithium-ion batteries (Poizot, P.;
Gaubicher, J.; Renault, S.; Dubois, L.; Liang, Y.; Yao, Y., Opportunities and
Challenges for Organic Electrodes in Electrochemical Energy Storage. Chemical
Reviews 2020, 120, 6490−6557.). However, the high solubility and inherent low conductivity of most low molecular weight organic molecules in liquid electrolytes restrict the development of their electrochemical properties. Polymerization is considered to be one of the most effective ways to address these challenges, but excessive polymerization often affects the electrochemical performance of lithium-ion batteries by reducing battery capacity.
与之相比，金属-有机配位聚合物通过引入氧化还原活性高的过渡金属离子桥联有机配体，可以在不牺牲氧化还原活性物质密度的情况下构建稳定的骨架。由于其结构多样可控、具有良好的赝电容性能和稳定的结构，作为电极材料显示出巨大的潜力，因而受到广泛关注，但其实际应用仍然面临许多挑战。In contrast, metal-organic coordination polymers can build a stable skeleton without sacrificing the density of redox-active species by introducing transition metal ions with high redox activity to bridge organic ligands. Due to its diverse and controllable structure, good pseudocapacitive performance and stable structure, it has shown great potential as an electrode material and has received widespread attention. However, its practical application still faces many challenges.
作为正极材料：As cathode material:
（1）现有的金属-有机配位聚合物的制备方法主要包含水热法和溶剂热的方法（Reddy, R. C. K.; Lin, X.; Zeb, A.; Su,
C. Y., Metal–Organic Frameworks and Their Derivatives
as Cathodes for Lithium-Ion Battery Applications: A Review. Electrochemical
Energy Reviews 2021, 5, 312-347.），这些方法存在产率低，反应时间较长、能耗较大等问题，难以得到大规模商业化应用。(1) The existing preparation methods of metal-organic coordination polymers mainly include hydrothermal and solvothermal methods (Reddy, R. C. K.; Lin, X.; Zeb, A.; Su,
C. Y., Metal–Organic Frameworks and Their Derivatives
as Cathodes for Lithium-Ion Battery Applications: A Review. Electrochemical
Energy Reviews 2021, 5, 312-347.), these methods have problems such as low yield, long reaction time, large energy consumption, etc., and are difficult to be commercialized on a large scale.
（2）金属-有机配位聚合物电极材料同时实现包括过渡金属和有机配体的氧化还原反应面临着挑战（Ferey, G;
Millange, F.; Morcrette, M.; Serre, C.; Doublet, M. L.; Greneche, J. M.;
Tarascon, J. M., Mixed-Valence Li/Fe-Based Metal–Organic
Frameworks with Both Reversible Redox and Sorption Properties. Angewandte
Chemie International Edition 2007, 46, 3259 –3263； Wu, Z.; Adekoya, D.; Huang, X.; Kiefel, M. J.; Xie, J.;
Xu, W.; Zhang, Q.; Zhu, D.; Zhang, S., Highly Conductive Two-Dimensional
Metal-Organic Frameworks for Resilient Lithium Storage with Superb Rate
Capability. ACS Nano 2020, 14, 12016-12026.），背后的储锂机理还需要进一步研究。综上所述，进一步优化金属-有机配位聚合物的制备策略与形态结构，深入理解其锂离子存储机理，有望构建容量高、稳定性好的新型金属-有机配位聚合物体系作为锂离子电池的高性能正极材料。(2) Metal-organic coordination polymer electrode materials face challenges in simultaneously realizing redox reactions involving transition metals and organic ligands (Ferey, G;
Millange, F.; Morcrette, M.; Serre, C.; Doublet, M. L.; Greneche, J. M.;
Tarascon, J. M., Mixed-Valence Li/Fe-Based Metal–Organic
Frameworks with Both Reversible Redox and Sorption Properties. Angewandte
Chemie International Edition 2007, 46, 3259 –3263; Wu, Z.; Adekoya, D.; Huang, X.; Kiefel, M. J.; Xie, J.;
Xu, W.; Zhang, Q.; Zhu, D.; Zhang, S., Highly Conductive Two-Dimensional
Metal-Organic Frameworks for Resilient Lithium Storage with Superb Rate
Capability. ACS Nano 2020, 14, 12016-12026.), the lithium storage mechanism behind it requires further research. In summary, further optimizing the preparation strategy and morphological structure of metal-organic coordination polymers, and in-depth understanding of their lithium ion storage mechanisms are expected to construct new metal-organic coordination polymer systems with high capacity and good stability as lithium ion batteries. High performance cathode material for batteries.
针对金属-有机配位聚合物作为锂离子电池正极材料存在的上述问题，本发明的目的在于提出金属-有机配位聚合物M
2CA
X及其制备方法与应用，该制备方法是一种通用的金属-有机配位聚合物体系的合成策略，所制备得到的金属-有机配位聚合物M
2CA
X作为正极材料在锂离子电池中应用。该制备方法通过简单的室温两步水溶液的方法，能够经济环保的得到多种金属-有机配位聚合物M
2CA
X (M=Cu、Fe、Mn、Ni)，且用此种制备方法得到的金属-有机配位聚合物作为锂离子电池正极材料时能够同时实现过渡金属和有机配体的氧化还原反应，并具有优异的电化学性能。
In view of the above-mentioned problems of metal-organic coordination polymers as cathode materials for lithium ion batteries, the purpose of the present invention is to propose metal-organic coordination polymers M 2 CA X and their preparation methods and applications. The preparation method is a universal The synthesis strategy of the metal-organic coordination polymer system, and the prepared metal-organic coordination polymer M 2 CA X is used as a cathode material in lithium-ion batteries. This preparation method can obtain a variety of metal-organic coordination polymers M 2 CA When used as cathode materials for lithium-ion batteries, metal-organic coordination polymers can simultaneously realize the redox reactions of transition metals and organic ligands and have excellent electrochemical properties.
本发明首次公开所述的金属-有机配位聚合物M
2CA
X的晶体结构内部不含溶剂分子，将金属-有机配位聚合物M
2CA
X作为电极材料，去除非活性的溶剂分子可以提高电极材料的储锂比容量。
The crystal structure of the metal - organic coordination polymer M 2 CA Improve the lithium storage specific capacity of electrode materials.
本发明采用的技术方案如下：The technical solutions adopted by the present invention are as follows:
一种金属-有机配位聚合物及其制备方法及其作为锂离子电池正极材料的应用。A metal-organic coordination polymer, its preparation method and its application as a positive electrode material for lithium ion batteries.
本发明提供金属-有机配位聚合物M
2CA
X，所述金属-有机配位聚合物M
2CA
X的结构通式如下：
The present invention provides a metal-organic coordination polymer M 2 CA X. The general structural formula of the metal-organic coordination polymer M 2 CA X is as follows:
其中，Y为H、羟基（OH）、Cl、Br、F中的一种；M为Fe、Mn、Ni、Cu中的一种；X为2-3；n表示重复单元数。Among them, Y is one of H, hydroxyl (OH), Cl, Br, and F; M is one of Fe, Mn, Ni, and Cu; X is 2-3; n represents the number of repeating units.
本发明提供的室温两步水溶液制备方法为：在室温条件下，首先采用简单的酸碱中和反应得到有机配体盐（Z
2CA）的水溶液，然后将有机配体盐（Z
2CA）的水溶液与过渡金属离子（M
X+）的盐溶液进行配位反应（有机配体CA
2
−与过渡金属离子M
X+配位），制备得到金属-有机配位聚合物M
2CA
X。
The room temperature two-step aqueous solution preparation method provided by the invention is: at room temperature, first use a simple acid-base neutralization reaction to obtain an aqueous solution of the organic ligand salt (Z 2 CA), and then prepare the organic ligand salt (Z 2 CA) The aqueous solution and the salt solution of the transition metal ion (MX + ) undergo a coordination reaction (the organic ligand CA 2 − coordinates with the transition metal ion M
进一步地，利用室温两步水溶液法得到的可用于锂离子电池正极材料的金属-有机配位聚合物M
2CA
X的制备方法包括如下步骤：
Further, the preparation method of the metal-organic coordination polymer M 2 CA
（1）按一定比例将有机配体酸（H
2CA）和碱（ZOH）加入水中，通过酸碱中和反应合成得到有机配体盐（Z
2CA）的水溶液；
(1) Add the organic ligand acid (H 2 CA) and alkali (ZOH) to water in a certain proportion, and synthesize an aqueous solution of the organic ligand salt (Z 2 CA) through an acid-base neutralization reaction;
（2）将步骤（1）得到的有机配体盐Z
2CA的水溶液与一定比例的不同种类过渡金属离子（M
X+）盐溶液在一定温度和一定转速的磁力搅拌下进行共沉淀反应一定时间，反应后的产物用水离心洗涤后过滤，最终在一定温度下真空干燥一定时间后得到金属-有机配位聚合物M
2CA
X。
(2) Co-precipitate the aqueous solution of the organic ligand salt Z 2 CA obtained in step (1) with a certain proportion of different types of transition metal ion (MX + ) salt solutions under magnetic stirring at a certain temperature and a certain speed for a certain period of time. , the reaction product is centrifuged and washed with water, filtered, and finally vacuum dried at a certain temperature for a certain period of time to obtain the metal-organic coordination polymer M 2 CA X .
进一步地，利用室温两步水溶液制备得到的可用于锂离子电池正极材料的金属-有机配位聚合物M
2CA
X的反应过程如下：
Furthermore, the reaction process of the metal-organic coordination polymer M 2 CA
其中，碱ZOH为KOH、NaOH中的一种，分别对应Z为K和Na；R.T.表示室温，室温为25-35 ˚C；H
2O表示在水溶液的反应条件下。
Among them, the base ZOH is one of KOH and NaOH, corresponding to Z being K and Na respectively; RT represents room temperature, and room temperature is 25-35 ˚C; H 2 O represents the reaction conditions of aqueous solution.
进一步地，步骤（1）所述有机配体酸H
2CA的结构通式如下：
Further, the general structural formula of the organic ligand acid H 2 CA in step (1) is as follows:
其中，有机配体酸H
2CA可为2, 5-二羟基对苯醌、四羟基苯醌、2, 5-二氯-3,
6-二羟基对苯醌、2, 5-二溴-3,
6-二羟基对苯醌、2, 5-二氟-3,
6-二羟基对苯醌中的一种，分别对应Y为H、羟基（OH）、Cl、Br、F中的一种。
Among them, the organic ligand acid H 2 CA can be 2, 5-dihydroxy-p-benzoquinone, tetrahydroxy-p-benzoquinone, 2, 5-dichloro-3, 6-dihydroxy-p-benzoquinone, 2, 5-dibromo- One of 3, 6-dihydroxy-p-benzoquinone and 2, 5-difluoro-3, 6-dihydroxy-p-benzoquinone, respectively corresponding to Y being one of H, hydroxyl (OH), Cl, Br, and F kind.
进一步地，步骤（1）中所述碱（ZOH）可为氢氧化钾（KOH）和氢氧化钠（NaOH）中的一种。Further, the base (ZOH) in step (1) can be one of potassium hydroxide (KOH) and sodium hydroxide (NaOH).
进一步地，步骤（1）中所述有机配体酸（H
2CA）和碱（ZOH）的摩尔比为1:(2-3)。
Further, the molar ratio of the organic ligand acid (H 2 CA) and base (ZOH) described in step (1) is 1:(2-3).
进一步地，步骤（2）中所述过渡金属离子（M
X+）可为Fe
3+、Mn
3+、Ni
2+和Cu
2+中的一种。
Further, the transition metal ion ( MX+ ) described in step (2) may be one of Fe 3+ , Mn 3+ , Ni 2+ and Cu 2+ .
进一步地，步骤（2）中有机配体盐Z
2CA与不同种类过渡金属离子（M
X+）的摩尔比为(1-4):2。
Further, in step (2), the molar ratio of the organic ligand salt Z 2 CA to different kinds of transition metal ions ( MX+ ) is (1-4):2.
进一步地，步骤（2）中有机配体盐Z
2CA与不同种类过渡金属离子（M
X+）的摩尔比为(1-3):2。
Further, in step (2), the molar ratio of the organic ligand salt Z 2 CA to different kinds of transition metal ions ( MX+ ) is (1-3):2.
进一步地，步骤（2）中所述不同种类过渡金属离子（M
X+）盐溶液和有机配体盐Z
2CA的水溶液的浓度范围为0.1-2
mol/L。
Further, the concentration range of the different types of transition metal ion (MX + ) salt solutions and the aqueous solution of the organic ligand salt Z 2 CA described in step (2) is 0.1-2 mol/L.
进一步地，步骤（2）中不同种类过渡金属离子（M
X+）为Fe
3+、Mn
3+、Ni
2+和Cu
2+中的一种。
Further, the different kinds of transition metal ions (M X+ ) in step (2) are one of Fe 3+ , Mn 3+ , Ni 2+ and Cu 2+ .
进一步地，步骤（2）中，所述共沉淀反应的温度为室温25-35
˚C，共沉淀反应的时间为2-10 h，所述磁力搅拌的转速为300-400
r/min；所述离心的转速为6000-8000 r/min；所述干燥的条件为120-150 ˚C真空干燥6-12
h。Further, in step (2), the temperature of the co-precipitation reaction is room temperature 25-35
˚C, the co-precipitation reaction time is 2-10 h, and the magnetic stirring speed is 300-400
r/min; the centrifugal speed is 6000-8000 r/min; the drying conditions are 120-150 ˚C vacuum drying 6-12
h.
本发明还提供一种经济环保的室温两步水溶液法制备得到的金属-有机配位聚合物M
2CA
X
(M=Cu、Fe、Mn、Ni)用作锂离子电池的正极材料。
The invention also provides an economical and environmentally friendly metal-organic coordination polymer M 2 CA
与现有技术相比，本发明有如下有益的效果：Compared with the prior art, the present invention has the following beneficial effects:
（1）本发明采用的室温两步水溶液法，是通过种类丰富的多种有机配体酸与碱进行中和反应得到的有机配体盐与不同种类过渡金属离子（M
X+）盐在室温条件下进行共沉淀反应，制备金属-有机配位聚合物M
2CA
X，得到的M
2CA
X不含溶剂分子。该制备方法不仅简单易行、绿色环保，且能低成本、低能耗、高产率的合成多种金属-有机配位聚合物材料，为大规模商业化合成金属-有机配位聚合物材料提供了一种新的途径。
(1) The room temperature two-step aqueous solution method adopted in the present invention is to react organic ligand salts obtained through the neutralization reaction of various organic ligand acids and bases with different types of transition metal ion ( MX+ ) salts at room temperature. Co-precipitation reaction is carried out under the conditions to prepare metal-organic coordination polymer M 2 CA X. The obtained M 2 CA X does not contain solvent molecules. This preparation method is not only simple, easy, green and environmentally friendly, but also can synthesize a variety of metal-organic coordination polymer materials at low cost, low energy consumption and high yield, providing a basis for large-scale commercial synthesis of metal-organic coordination polymer materials. A new approach.
（2）本发明制备得到的金属-有机配位聚合物M
2CA
X作为锂离子电池正极材料，结构稳定，可缓解脱嵌锂离子中产生的剧烈体积膨胀；更重要的是，有机配体与金属离子可同时提供电化学活性位点，可为锂离子的快速传输提供通道，具有优异的电化学性能。
(2) The metal-organic coordination polymer M 2 CA It can provide electrochemical active sites with metal ions at the same time, can provide a channel for the rapid transmission of lithium ions, and has excellent electrochemical performance.
图1为本发明实施例1制备得到的金属-有机配位聚合物CuCA不同尺度下的扫描电子显微镜（SEM）图像。Figure 1 is a scanning electron microscope (SEM) image of the metal-organic coordination polymer CuCA prepared in Example 1 of the present invention at different scales.
图2为本发明实施例1制备得到的金属-有机配位聚合物CuCA的透射电子显微镜（TEM）图像。Figure 2 is a transmission electron microscope (TEM) image of the metal-organic coordination polymer CuCA prepared in Example 1 of the present invention.
图3为本发明实施例1制备得到的金属-有机配位聚合物CuCA作为锂离子电池正极材料匹配金属锂负极、有机电解液和Celgard 2400商用隔膜，在100 mA g
−
1的电流密度下的电化学循环性能图。
Figure 3 shows the metal-organic coordination polymer CuCA prepared in Example 1 of the present invention as a lithium-ion battery cathode material matched with metallic lithium anode, organic electrolyte and Celgard 2400 commercial separator at a current density of 100 mA g − 1 Electrochemical cycle performance plot.
图4为本发明实施例1制备得到的金属-有机配位聚合物CuCA作为锂离子电池正极材料匹配金属锂负极和聚合物基固态电解质，在100 mA g
−
1的电流密度下的电化学循环性能图。
Figure 4 shows the electrochemical cycle of the metal-organic coordination polymer CuCA prepared in Example 1 of the present invention as a lithium-ion battery cathode material matched with a metal lithium anode and a polymer-based solid electrolyte at a current density of 100 mA g − 1 Performance graph.
为更好地理解本发明，下面结合具体的实施例对本发明作进一步的详细解释与说明，但本发明的实施方式与种类不受限于此。In order to better understand the present invention, the present invention will be further explained and described in detail below with reference to specific examples, but the implementation manner and types of the present invention are not limited thereto.
实施例Example
11
（1）首先，将1 mol的2, 5-二氯-3,
6-二羟基对苯醌（H
2CA，Y=Cl）和2 moL的氢氧化钾（KOH）加入到1000 mL水中，在25 ˚C下经过酸碱中和反应生成1 mol/L的有机钾盐的水溶液（K
2CA水溶液，Y=Cl，Z=K）；
(1) First, add 1 mol of 2,5-dichloro-3,6-dihydroxy-p-benzoquinone (H 2 CA, Y=Cl) and 2 mol of potassium hydroxide (KOH) into 1000 mL of water. After acid-base neutralization reaction at 25 ˚C, a 1 mol/L organic potassium salt aqueous solution (K 2 CA aqueous solution, Y=Cl, Z=K) is produced;
（2）然后将步骤（1）得到的1 mol/L的K
2CA水溶液（100 mL）与1 mol/L的硝酸铜三水合物（Cu(NO
3)
2·3H
2O）水溶液（100 mL）在300 r/min转速的磁力搅拌中，25 ˚C下按照1:1的摩尔比进行共沉淀反应2 h。反应后的产物用去离子水在6000 r/min的转速下离心洗涤3次后过滤，然后150
˚C真空干燥10 h后，得到金属-有机配位聚合物CuCA（Y=Cl）。
(2) Then mix the 1 mol/L K 2 CA aqueous solution (100 mL) obtained in step (1) with the 1 mol/L copper nitrate trihydrate (Cu(NO 3 ) 2 ·3H 2 O) aqueous solution (100 mL) with magnetic stirring at 300 r/min and 25 ˚C in a molar ratio of 1:1 for 2 h. The reaction product was centrifuged and washed three times with deionized water at 6000 r/min, filtered, and then vacuum dried at 150 ˚C for 10 h to obtain the metal-organic coordination polymer CuCA (Y=Cl).
图1为实施例1制备得到的金属-有机配位聚合物CuCA不同尺度下的扫描电子显微镜（SEM）图像，从图1中可以看出，CuCA为均匀的纳米片状结构，边长为500 nm，厚度为30 nm。图2为实施例1制备得到的金属-有机配位聚合物CuCA的透射电子显微镜（TEM）图像，从图2可以看出得到的CuCA的纳米片状结构均匀完整。Figure 1 is a scanning electron microscope (SEM) image of the metal-organic coordination polymer CuCA prepared in Example 1 at different scales. It can be seen from Figure 1 that CuCA has a uniform nanosheet structure with a side length of 500 nm, with a thickness of 30 nm. Figure 2 is a transmission electron microscope (TEM) image of the metal-organic coordination polymer CuCA prepared in Example 1. It can be seen from Figure 2 that the nanosheet structure of the obtained CuCA is uniform and complete.
实施例Example
22
（1）首先，将1 mol的2, 5-二氯-3,
6-二羟基对苯醌（H
2CA，Y=Cl）和2.5 mol的氢氧化钾（KOH）加入到1000 mL水中，在25 ˚C下经过酸碱中和反应生成1 mol/L的有机钾盐的水溶液（K
2CA水溶液，Y=Cl，Z=K）；
(1) First, add 1 mol of 2,5-dichloro-3,6-dihydroxy-p-benzoquinone (H 2 CA, Y=Cl) and 2.5 mol of potassium hydroxide (KOH) into 1000 mL of water. After acid-base neutralization reaction at 25 ˚C, a 1 mol/L organic potassium salt aqueous solution (K 2 CA aqueous solution, Y=Cl, Z=K) is produced;
（2）然后将步骤（1）得到的1 mol/L的K
2CA水溶液（150 mL）与1 mol/L的硝酸铁九水合物（Fe(NO
3)
3·9H
2O）水溶液（100 mL）在350 r/min转速的磁力搅拌中，25 ˚C下按照3:2的摩尔比进行共沉淀反应6 h。反应后的产物用去离子水在7000 r/min的转速下离心洗涤3次后过滤，然后120
˚C真空干燥12 h后，得到金属-有机配位聚合物Fe
2CA
3（Y=Cl）。
(2) Then mix the 1 mol/L K 2 CA aqueous solution (150 mL) obtained in step (1) with the 1 mol/L iron nitrate nonahydrate (Fe(NO 3 ) 3 ·9H 2 O) aqueous solution (100 mL) with magnetic stirring at 350 r/min and 25 ˚C at a molar ratio of 3:2 for 6 h. The reaction product was centrifuged and washed three times with deionized water at 7000 r/min, filtered, and then vacuum dried at 120 ˚C for 12 hours to obtain metal-organic coordination polymer Fe 2 CA 3 (Y=Cl) .
实施例Example
33
（1）首先，将1 mol的2, 5-二氯-3,
6-二羟基对苯醌（H
2CA，Y=Cl）和3 mol的氢氧化钠（NaOH）加入到1000 mL水中，在30 ˚C下经过酸碱中和反应生成1 mol/L的有机钠盐的水溶液（Na
2CA水溶液，Y=Cl，Z=Na）；
(1) First, add 1 mol of 2,5-dichloro-3,6-dihydroxy-p-benzoquinone (H 2 CA, Y=Cl) and 3 mol of sodium hydroxide (NaOH) into 1000 mL of water. After acid-base neutralization reaction at 30 ˚C, a 1 mol/L organic sodium salt aqueous solution (Na 2 CA aqueous solution, Y=Cl, Z=Na) is produced;
（2）然后将步骤（1）得到的1 mol/L的Na
2CA水溶液（150 mL）与1 mol/L的醋酸锰二水合物（Mn(CH
3COO)
3·2H
2O）水溶液（100 mL）在400 r/min转速的磁力搅拌中，30 ˚C下按照3:2的摩尔比进行共沉淀反应10 h。反应后的产物用去离子水在8000 r/min的转速下离心洗涤3次后过滤，然后130
˚C真空干燥10 h后，得到金属-有机配位聚合物Mn
2CA
3（Y=Cl）。
(2) Then mix the 1 mol/L Na 2 CA aqueous solution (150 mL) obtained in step (1) with the 1 mol/L manganese acetate dihydrate (Mn(CH 3 COO) 3 ·2H 2 O) aqueous solution ( 100 mL) was subjected to a co-precipitation reaction at a molar ratio of 3:2 at 30 ˚C for 10 h with magnetic stirring at 400 r/min. The reaction product was centrifuged and washed three times with deionized water at 8000 r/min, filtered, and then vacuum dried at 130 ˚C for 10 h to obtain the metal-organic coordination polymer Mn 2 CA 3 (Y=Cl). .
实施例Example
44
（1）首先，将1 mol的2, 5-二氯-3,
6-二羟基对苯醌（H
2CA，Y=Cl）和2 mol的氢氧化钠（NaOH）加入到1000 mL水中，在35 ˚C下经过酸碱中和反应生成1 mol/L的有机钠盐的水溶液（Na
2CA水溶液，Y=Cl，Z=Na）；
(1) First, add 1 mol of 2,5-dichloro-3,6-dihydroxy-p-benzoquinone (H 2 CA, Y=Cl) and 2 mol of sodium hydroxide (NaOH) into 1000 mL of water. After acid-base neutralization reaction at 35 ˚C, a 1 mol/L organic sodium salt aqueous solution (Na 2 CA aqueous solution, Y=Cl, Z=Na) is produced;
（2）然后将步骤（1）得到的1 mol/L的Na
2CA水溶液（100 mL）与1 mol/L的硝酸镍六水合物（Ni(NO
3)
2·6H
2O）水溶液（100 mL）在300 r/min转速的磁力搅拌中，35 ˚C下按照1:1的摩尔比进行共沉淀反应2 h。反应后的产物用去离子水在7000 r/min的转速下离心洗涤3次后过滤，然后140
˚C真空干燥8 h后，得到金属-有机配位聚合物NiCA（Y=Cl）。
(2) Then mix the 1 mol/L Na 2 CA aqueous solution (100 mL) obtained in step (1) with the 1 mol/L nickel nitrate hexahydrate (Ni(NO 3 ) 2 ·6H 2 O) aqueous solution (100 mL) with magnetic stirring at 300 r/min and 35 ˚C at a molar ratio of 1:1 for 2 h. The reaction product was centrifuged and washed three times with deionized water at 7000 r/min, filtered, and then vacuum dried at 140 ˚C for 8 h to obtain metal-organic coordination polymer NiCA (Y=Cl).
实施例Example
55
（1）首先，将0.1 mol的2, 5-二羟基对苯醌（H
2CA，Y=H）和0.2 mol的氢氧化钾（KOH）加入到1000 mL水中，在25 ˚C下经过酸碱中和反应生成0.1 mol/L的有机钾盐的水溶液（K
2CA水溶液，Y=H，Z=K）；
(1) First, add 0.1 mol of 2,5-dihydroxy-p-benzoquinone (H 2 CA, Y=H) and 0.2 mol of potassium hydroxide (KOH) to 1000 mL of water, and pass through acid at 25 ˚C Alkaline neutralization reaction generates 0.1 mol/L organic potassium salt aqueous solution (K 2 CA aqueous solution, Y=H, Z=K);
（2）然后将步骤（1）得到的0.1 mol/L的K
2CA水溶液（100 mL）与0.1 mol/L的硝酸铜三水合物（Cu(NO
3)
2·3H
2O）水溶液（200 mL）在300 r/min转速的磁力搅拌中，25 ˚C下按照1:2的摩尔比进行共沉淀反应4 h。反应后的产物用去离子水在6000 r/min的转速下离心洗涤3次后过滤，然后150
˚C真空干燥6 h后，得到金属-有机配位聚合物CuCA（Y=H）。
(2) Then mix the 0.1 mol/L K 2 CA aqueous solution (100 mL) obtained in step (1) with the 0.1 mol/L copper nitrate trihydrate (Cu(NO 3 ) 2 ·3H 2 O) aqueous solution (200 mL) with magnetic stirring at 300 r/min and 25 ˚C in a molar ratio of 1:2 for 4 h. The reaction product was centrifuged and washed three times with deionized water at 6000 r/min, filtered, and then vacuum dried at 150 ˚C for 6 h to obtain the metal-organic coordination polymer CuCA (Y=H).
实施例Example
66
（1）首先，将1 mol的四羟基苯醌（H
2CA，Y=羟基（OH））和2 mol的氢氧化钾（KOH）加入到500 mL水中，在25˚C下经过酸碱中和反应生成2 mol/L的有机钾盐的水溶液（K
2CA水溶液，Y=羟基（OH），Z=K）；
(1) First, add 1 mol of tetrahydroxybenzoquinone (H 2 CA, Y = hydroxyl (OH)) and 2 mol of potassium hydroxide (KOH) to 500 mL of water, and pass through acid-base solution at 25˚C And the reaction produces a 2 mol/L organic potassium salt aqueous solution (K 2 CA aqueous solution, Y = hydroxyl (OH), Z = K);
（2）然后将步骤（1）得到的2 mol/L的K
2CA水溶液（150 mL）与2 mol/L的硝酸铁九水合物（Fe(NO
3)
3·9H
2O）水溶液（100 mL）在350 r/min转速的磁力搅拌中，25 ˚C下按照3:2的摩尔比进行共沉淀反应9 h。反应后的产物用去离子水在7000 r/min的转速下离心洗涤3次后过滤，然后150
˚C真空干燥9 h后，得到金属-有机配位聚合物Fe
2CA
3（Y=羟基（OH））。
(2) Then mix the 2 mol/L K 2 CA aqueous solution (150 mL) obtained in step (1) with the 2 mol/L iron nitrate nonahydrate (Fe(NO 3 ) 3 ·9H 2 O) aqueous solution (100 mL) with magnetic stirring at 350 r/min and a co-precipitation reaction at a molar ratio of 3:2 at 25 ˚C for 9 h. The reaction product was centrifuged and washed 3 times with deionized water at 7000 r/min, filtered, and then vacuum dried at 150 ˚C for 9 hours to obtain metal-organic coordination polymer Fe 2 CA 3 (Y=hydroxyl ( OH)).
实施例Example
77
（1）首先，将0.5 mol的2, 5-二溴-3, 6-二羟基对苯醌（H
2CA，Y=Br）和1 mol的氢氧化钠（NaOH）加入到1000 mL水中，在25 ˚C下经过酸碱中和反应生成0.5 mol/L的有机钠盐的水溶液（Na
2CA水溶液，Y=Br，Z=Na）；
(1) First, add 0.5 mol of 2,5-dibromo-3,6-dihydroxy-p-benzoquinone (H 2 CA, Y=Br) and 1 mol of sodium hydroxide (NaOH) into 1000 mL of water. After acid-base neutralization reaction at 25 ˚C, a 0.5 mol/L organic sodium salt aqueous solution (Na 2 CA aqueous solution, Y=Br, Z=Na) is produced;
（2）然后将步骤（1）得到的0.5 mol/L的Na
2CA水溶液（200 mL）与0.5 mol/L的醋酸锰二水合物（Mn(CH
3COO)
3·2H
2O）水溶液（100 mL）在400 r/min转速的磁力搅拌中，25 ˚C下按照2:1的摩尔比进行共沉淀反应9 h。反应后的产物用去离子水在8000 r/min的转速下离心洗涤3次后过滤，然后135
˚C真空干燥12 h后，得到金属-有机配位聚合物Mn
2CA
3（Y=Br）。
(2) Then mix the 0.5 mol/L Na 2 CA aqueous solution (200 mL) obtained in step (1) with the 0.5 mol/L manganese acetate dihydrate (Mn(CH 3 COO) 3 ·2H 2 O) aqueous solution ( 100 mL) was subjected to a co-precipitation reaction at a molar ratio of 2:1 at 25 ˚C for 9 h with magnetic stirring at 400 r/min. The reaction product was centrifuged and washed 3 times with deionized water at 8000 r/min, filtered, and then vacuum dried at 135 ˚C for 12 hours to obtain the metal-organic coordination polymer Mn 2 CA 3 (Y=Br) .
实施例Example
88
（1）首先，将0.5 mol的2, 5-二氟-3, 6-二羟基对苯醌（H
2CA，Y=F）和1 mol的氢氧化钠（NaOH）加入到1000 mL水中，在25 ˚C下经过酸碱中和反应生成0.5 mol/L的有机钠盐的水溶液（Na
2CA水溶液，Y=F，Z=Na）；
(1) First, add 0.5 mol of 2,5-difluoro-3,6-dihydroxy-p-benzoquinone (H 2 CA, Y=F) and 1 mol of sodium hydroxide (NaOH) into 1000 mL of water. After acid-base neutralization reaction at 25 ˚C, a 0.5 mol/L organic sodium salt aqueous solution (Na 2 CA aqueous solution, Y=F, Z=Na) is produced;
（2）然后将步骤（1）得到的0.5 mol/L的Na
2CA水溶液（100 mL）与0.5 mol/L的硝酸镍六水合物（Ni(NO
3)
2·6H
2O）水溶液（100 mL）在300 r/min转速的磁力搅拌中，25 ˚C下按照1:1的摩尔比进行共沉淀反应3 h。反应后的产物用去离子水在6000 r/min的转速下离心洗涤3次后过滤，然后120
˚C真空干燥10 h后，得到金属-有机配位聚合物NiCA（Y=F）。
(2) Then mix the 0.5 mol/L Na 2 CA aqueous solution (100 mL) obtained in step (1) with the 0.5 mol/L nickel nitrate hexahydrate (Ni(NO 3 ) 2 ·6H 2 O) aqueous solution (100 mL) with magnetic stirring at 300 r/min and 25 ˚C in a molar ratio of 1:1 for 3 h. The reaction product was centrifuged and washed three times with deionized water at 6000 r/min, filtered, and then vacuum dried at 120 ˚C for 10 h to obtain metal-organic coordination polymer NiCA (Y=F).
应用例Application examples
11
将实施例1制备得到的金属-有机配位聚合物CuCA作为正极材料应用于有机电解液体系的锂离子电池，步骤如下：The metal-organic coordination polymer CuCA prepared in Example 1 is used as a cathode material in a lithium-ion battery with an organic electrolyte system. The steps are as follows:
将0.6 g金属-有机配位聚合物CuCA、0.3 g导电碳、0.1 g聚偏二氟乙烯（PVDF）粘结剂按照6:3:1的质量比在2 mL N-甲基吡咯烷酮（NMP）溶剂中研磨30 min，调成均匀的正极导电浆料，均匀涂覆在集流体铝箔上，100 ˚C温度下真空干燥10 h后，裁成直径为10 mm的小圆片，即为得到的金属-有机配位聚合物CuCA锂离子电池正极极片。Mix 0.6 g metal-organic coordination polymer CuCA, 0.3 g conductive carbon, and 0.1 g polyvinylidene fluoride (PVDF) binder in a mass ratio of 6:3:1 in 2 mL N-methylpyrrolidone (NMP). Grind it in a solvent for 30 minutes to prepare a uniform positive electrode conductive slurry, apply it evenly on the current collector aluminum foil, dry it under vacuum at 100 ˚C for 10 hours, and then cut it into small discs with a diameter of 10 mm, which is the obtained Metal-organic coordination polymer CuCA lithium ion battery cathode plate.
采用金属Li片作为负极极片，1 M LiTFSI in
DME/DOL (1:1 Vol%)（其中LiTFSI为双三氟甲烷磺酰亚胺锂，DME为乙二醇二甲醚，DOL为1,3-二氧戊环）作为有机电解液，Celgard 2400商用隔膜作为电池隔膜，与得到的正极极片在充满惰性气体的手套箱中组装成有机电解液体系的锂离子电池。A metal Li piece is used as the negative electrode piece, 1 M LiTFSI in
DME/DOL (1:1 Vol%) (where LiTFSI is lithium bistrifluoromethanesulfonimide, DME is ethylene glycol dimethyl ether, and DOL is 1,3-dioxolane) as the organic electrolyte, Celgard 2400 commercial separator is used as the battery separator, and the obtained positive electrode sheet is assembled into a lithium-ion battery with an organic electrolyte system in a glove box filled with inert gas.
图3为实施例1制备得到的金属-有机配位聚合物CuCA作为锂离子电池正极材料匹配金属锂负极、有机电解液和Celgard 2400商用隔膜，在100 mA g
−1的电流密度下的电化学循环性能图。其中，组装的锂离子电池在第1圈的放电比容量为239.9 mAh g
−1，循环20圈后仍有124.1
mAh g
−1的比容量，库伦效率为93.4％，表现出优异的循环稳定性，说明金属-有机配位聚合物CuCA作为锂离子电池正极材料应用于有机电解液体系的储锂性能优异。
Figure 3 shows the electrochemistry of the metal-organic coordination polymer CuCA prepared in Example 1 as a lithium-ion battery cathode material, matched with metallic lithium anode, organic electrolyte and Celgard 2400 commercial separator at a current density of 100 mA g −1 Cycle performance graph. Among them, the assembled lithium-ion battery has a discharge specific capacity of 239.9 mAh g −1 in the first cycle, and still has a specific capacity of 124.1 mAh g −1 after 20 cycles. The Coulombic efficiency is 93.4%, showing excellent cycle stability. , indicating that the metal-organic coordination polymer CuCA has excellent lithium storage performance when used as a cathode material for lithium-ion batteries in organic electrolyte systems.
应用例Application examples
22
将实施例1制备得到的金属-有机配位聚合物CuCA作为正极材料应用于聚合物基固态电解质体系的锂离子电池，步骤如下：The metal-organic coordination polymer CuCA prepared in Example 1 is used as a cathode material in a lithium-ion battery with a polymer-based solid electrolyte system. The steps are as follows:
将0.6 g金属-有机配位聚合物CuCA、0.3 g导电碳、0.1 g羧甲基纤维素钠（CMC-Na）粘结剂按照6:3:1的质量比在2 mL水溶剂中研磨30 min，调成均匀的正极导电浆料，均匀涂覆在集流体铝箔上，100 ˚C温度下真空干燥10 h后，裁成直径为10 mm的小圆片，即为得到的金属-有机配位聚合物CuCA锂离子电池正极极片。0.6 g of metal-organic coordination polymer CuCA, 0.3 g of conductive carbon, and 0.1 g of sodium carboxymethyl cellulose (CMC-Na) binder were ground in 2 mL of water solvent at a mass ratio of 6:3:1 for 30 min, adjust it into a uniform positive electrode conductive slurry, evenly coat it on the current collector aluminum foil, dry it under vacuum at 100 ˚C for 10 hours, and cut it into small discs with a diameter of 10 mm, which is the obtained metal-organic compound. Bit polymer CuCA lithium ion battery cathode plate.
采用金属Li片作为负极极片，聚合物基固态电解质（PPC-PEO-LiTFSI-Al
2O
3固态电解质，其中PPC为聚碳酸丙烯酯，PEO为聚环氧乙烷，LiTFSI为双三氟甲烷磺酰亚胺锂，与得到的正极极片在充满惰性气体的手套箱中组装成聚合物基固态电解质体系的锂离子电池。
A metal Li sheet is used as the negative electrode sheet, and the polymer-based solid electrolyte (PPC-PEO-LiTFSI-Al 2 O 3 solid electrolyte, where PPC is polypropylene carbonate, PEO is polyethylene oxide, and LiTFSI is bistrifluoromethane Lithium sulfonimide is assembled with the obtained positive electrode sheet in a glove box filled with inert gas to form a lithium-ion battery with a polymer-based solid electrolyte system.
图4为实施例1制备得到的金属-有机配位聚合物CuCA作为锂离子电池正极材料匹配金属锂负极和聚合物基固态电解质，在100 mA g
−1的电流密度下的电化学循环性能图。其中，组装的锂离子电池在第1圈的放电比容量为233.0 mAh g
−1，循环20圈后仍有182.9 mAh g
−1的比容量，库伦效率为98.9％，较有机电解液体系的循环性能更加稳定，说明金属-有机配位聚合物CuCA作为锂离子电池正极材料同样适合应用于聚合物基固态电解质体系。
Figure 4 is a diagram of the electrochemical cycle performance of the metal-organic coordination polymer CuCA prepared in Example 1 as a lithium-ion battery cathode material matched with a metal lithium anode and a polymer-based solid electrolyte at a current density of 100 mA g −1 . Among them, the assembled lithium-ion battery has a specific discharge capacity of 233.0 mAh g −1 in the first cycle. After 20 cycles, it still has a specific capacity of 182.9 mAh g −1 and a Coulombic efficiency of 98.9%, which is higher than that of the organic electrolyte system. The performance is more stable, indicating that the metal-organic coordination polymer CuCA is also suitable for use in polymer-based solid electrolyte systems as a cathode material for lithium ion batteries.
上述实施例均用来解释说明与补充本发明的实施细节，本发明的实施方式不受限于上述实施例中内容的范围，其他在本发明原理与基础上做出的组合、替换、修改均为可同等替代的置换方式，都包含在本发明要求的保护范围之内。The above embodiments are used to explain and supplement the implementation details of the present invention. The implementation of the present invention is not limited to the scope of the contents of the above embodiments. Other combinations, substitutions and modifications made on the principle and basis of the present invention are Equivalent substitutions are included in the protection scope of the present invention.
Claims (10)
- 金属-有机配位聚合物M 2CA X，其特征在于，所述金属-有机配位聚合物M 2CA X的结构通式如下： Metal-organic coordination polymer M 2 CA X is characterized in that the general structural formula of the metal-organic coordination polymer M 2 CA其中，Y为H、羟基OH、Cl、Br、F中的一种；M为Fe、Mn、Ni、Cu中的一种；X为2-3；n表示重复单元数。Among them, Y is one of H, hydroxyl OH, Cl, Br, and F; M is one of Fe, Mn, Ni, and Cu; X is 2-3; n represents the number of repeating units.
- 金属-有机配位聚合物M 2CA X的制备方法，其特征在于，包括如下步骤： The preparation method of metal-organic coordination polymer M 2 CA X is characterized by including the following steps:（1）将有机配体酸H 2CA和碱ZOH加入水中，通过酸碱中和反应合成得到有机配体盐Z 2CA的水溶液； (1) Add the organic ligand acid H 2 CA and the alkali ZOH into water, and synthesize it through an acid-base neutralization reaction to obtain an aqueous solution of the organic ligand salt Z 2 CA;（2）将步骤（1）得到的有机配体盐Z 2CA的水溶液与不同种类过渡金属离子M X+盐溶液搅拌进行共沉淀反应，经过离心洗涤后过滤，最终干燥后得到金属-有机配位聚合物M 2CA X。 (2) Stir the aqueous solution of the organic ligand salt Z 2 CA obtained in step (1) with different types of transition metal ion M Polymer M 2 CA X .
- 根据权利要求2所述的金属-有机配位聚合物M 2CA X的制备方法，其特征在于，制备得到金属-有机配位聚合物M 2CA X的反应过程如下： The preparation method of metal-organic coordination polymer M 2 CA X according to claim 2, characterized in that the reaction process for preparing metal-organic coordination polymer M 2 CA X is as follows:其中，碱ZOH为氢氧化钾KOH、氢氧化钠NaOH中的一种，分别对应Z为K和Na；R.T.表示室温，室温为25-35 ˚C；H 2O表示在水溶液反应条件下。 Among them, the base ZOH is one of potassium hydroxide KOH and sodium hydroxide NaOH, corresponding to Z is K and Na respectively; RT means room temperature, and room temperature is 25-35 ˚C; H 2 O means under aqueous solution reaction conditions.
- 根据权利要求2所述的金属-有机配位聚合物M 2CA X的制备方法，其特征在于，步骤（1）所述有机配体酸H 2CA的结构通式如下： The preparation method of metal-organic coordination polymer M 2 CA X according to claim 2, characterized in that the general structural formula of the organic ligand acid H 2 CA in step (1) is as follows:其中，有机配体酸H 2CA为2, 5-二羟基对苯醌、四羟基苯醌、2, 5-二氯-3, 6-二羟基对苯醌、2, 5-二溴-3, 6-二羟基对苯醌、2, 5-二氟-3, 6-二羟基对苯醌中的一种，分别对应Y为H、羟基OH、Cl、Br、F中的一种。 Among them, the organic ligand acid H 2 CA is 2, 5-dihydroxy-p-benzoquinone, tetrahydroxy-p-benzoquinone, 2, 5-dichloro-3, 6-dihydroxy-p-benzoquinone, and 2, 5-dibromo-3 , one of 6-dihydroxy-p-benzoquinone and 2, 5-difluoro-3, 6-dihydroxy-p-benzoquinone, corresponding to Y being one of H, hydroxyl OH, Cl, Br, and F respectively.
- 根据权利要求2所述的金属-有机配位聚合物M 2CA X的制备方法，其特征在于，步骤（1）所述有机配体酸H 2CA和碱ZOH的摩尔比为1:(2-3)。 The preparation method of metal-organic coordination polymer M 2 CA -3).
- 根据权利要求2所述的金属-有机配位聚合物M 2CA X的制备方法，其特征在于，步骤（2）有机配体盐Z 2CA与不同种类过渡金属离子M X+的摩尔比为(1-4):2。 The preparation method of metal-organic coordination polymer M 2 CA 1-4):2.
- 根据权利要求2所述的金属-有机配位聚合物M 2CA X的制备方法，其特征在于，步骤（2）所述过渡金属离子M X+盐溶液和有机配体盐Z 2CA的水溶液的浓度范围为0.1-2 mol/L。 The preparation method of metal-organic coordination polymer M 2 CA X according to claim 2, characterized in that, in step (2), the transition metal ion M The concentration range is 0.1-2 mol/L.
- 根据权利要求2所述的金属-有机配位聚合物M 2CA X的制备方法，其特征在于，步骤（2）中过渡金属离子M X+为Fe 3+、Mn 3+、Ni 2+和Cu 2+中的一种。 The preparation method of metal - organic coordination polymer M 2 CA X according to claim 2, characterized in that in step ( 2 ), the transition metal ions M One of 2+ .
- 根据权利要求2所述的金属-有机配位聚合物M 2CA X的制备方法，其特征在于，步骤（2）中，所述搅拌的转速为300-400 r/min，所述共沉淀反应的温度为室温25-35 ˚C，共沉淀反应的时间为2-10 h；所述离心的转速为6000-8000 r/min；所述干燥的条件为120-150 ˚C真空干燥6-12 h。 The preparation method of metal-organic coordination polymer M 2 CA The temperature is room temperature 25-35 ˚C, the co-precipitation reaction time is 2-10 h; the centrifugal speed is 6000-8000 r/min; the drying conditions are 120-150 ˚C vacuum drying 6-12 h.
- 权利要求1所述金属-有机配位聚合物M 2CA X用作锂离子电池的正极材料。 The metal-organic coordination polymer M 2 CA X described in claim 1 is used as a cathode material for lithium ion batteries.
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| CN115010946B (en) * | 2022-06-23 | 2024-03-15 | 华南理工大学 | Metal-organic coordination polymer M 2 CA X Preparation method and application thereof |
| CN116333327A (en) * | 2023-02-20 | 2023-06-27 | 华中科技大学 | Water-based sodium ion battery anode material and preparation method and application thereof |
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| CN112042019A (en) * | 2018-05-24 | 2020-12-04 | 日本瑞翁株式会社 | Electrode material, electrode, electricity storage device, and slurry composition |
| CN113024347A (en) * | 2021-02-03 | 2021-06-25 | 浙江大学 | Method for separating mixed xylene |
| CN113563594A (en) * | 2020-04-28 | 2021-10-29 | 中国科学院化学研究所 | Air-stable n-type thermoelectric material and preparation method thereof |
| CN115010946A (en) * | 2022-06-23 | 2022-09-06 | 华南理工大学 | Metal-organic coordination polymer M 2 CA X And preparation method and application thereof |
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| CN110357068B (en) * | 2019-08-15 | 2021-08-13 | 中国科学技术大学 | Synthetic method of hierarchical porous carbon nano material |
| CN114621290B (en) * | 2022-03-09 | 2023-08-22 | 华南理工大学 | Phosphorus-carbole compound with different spatial structures, and preparation method and application thereof |
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| CN112042019A (en) * | 2018-05-24 | 2020-12-04 | 日本瑞翁株式会社 | Electrode material, electrode, electricity storage device, and slurry composition |
| CN113563594A (en) * | 2020-04-28 | 2021-10-29 | 中国科学院化学研究所 | Air-stable n-type thermoelectric material and preparation method thereof |
| CN113024347A (en) * | 2021-02-03 | 2021-06-25 | 浙江大学 | Method for separating mixed xylene |
| CN115010946A (en) * | 2022-06-23 | 2022-09-06 | 华南理工大学 | Metal-organic coordination polymer M 2 CA X And preparation method and application thereof |
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