GB2616800A - Preparation method for and application of composite material containing graphite and MOF - Google Patents
Preparation method for and application of composite material containing graphite and MOF Download PDFInfo
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- GB2616800A GB2616800A GB2310070.4A GB202310070A GB2616800A GB 2616800 A GB2616800 A GB 2616800A GB 202310070 A GB202310070 A GB 202310070A GB 2616800 A GB2616800 A GB 2616800A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 24
- 239000010439 graphite Substances 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 238000004729 solvothermal method Methods 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 239000007822 coupling agent Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 239000012621 metal-organic framework Substances 0.000 claims description 41
- 239000012924 metal-organic framework composite Substances 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 6
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052744 lithium Inorganic materials 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000007773 negative electrode material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002002 slurry Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000010405 anode material Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000013086 titanium-based metal-organic framework Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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- 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
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
A preparation method for and application of a composite material containing graphite and MOF. The preparation method comprises: adding an amino-containing organic substance into a mixed solution, performing stirring, adding a titanium-containing coupling agent, and continuing stirring to obtain a suspension; performing solvothermal reaction on the suspension, performing filtering, taking filter residues, alternately cleaning the filter residues by using organic solvents in sequence, and performing extraction to obtain MOF; and grinding graphite into powder, mixing the powder with alcohol, performing oscillating, then adding MOF, continuing oscillating, performing refluxing, standing, and centrifuging, taking precipitate, and performing drying to obtain the composite material containing graphite and MOF. The composite material containing graphite and MOF is good in structural stability, can be used as a basic framework of a negative electrode material, and can eliminate the volume expansion effect of a battery in a charging/discharging process when being applied to a negative electrode of the lithium battery, thereby improving capacity.
Description
PREPARATION METHOD FOR AND APPLICATION OF COMPOSITE MATERIAL
CONTAINING GRAPHITE AND MOF
TECHNICAL FIELD
[0001] The present disclosure belongs to the field of battery materials, and specifically relates to a preparation method and use of a graphite-metal organic framework (MOF) composite.
BACKGROUND
[0002] With the advancement of internet technology, the use of more and more technical applications relies on electronic devices. The use of electronic devices requires lithium batteries with high capacity and convenient use for continuous operation. In addition, with the large-scale use of electric vehicles and other electric tools promoted by various policies in recent years, lithium batteries have become an indispensable device in social development from all walks of life to daily life. At present, anode materials in lithium-ion batteries (LIBs) mainly include: carbons, such as graphite, soft carbon, and hard carbon; or new electrode materials, such as silicon-carbon anodes or transition metal oxides. As the market requirements on battery capacity tend to become higher and higher, LIBs with traditional anodes can no longer meet current. requirements. In view of this, the preparation of new materials and use thereof in LIBs has become a research hotspot.
[9993] MOFs are crystalline frameworks with intramolecular pores, which are formed by self-assembly of metal ions or clusters with organic ligands via coordination bonds under specified conditions. This type of materials has large specific surface area (SSA) and adjustable pore size and shape, and is easy to modify. Proton-conducting and electron-conducting MOFs have shown potential application value in fuel cells, electrocatalysis, LIBs, supercapacitors, and other fields. MOFs have attracted widespread attention due to having a unique channel structure and containing transition metal elements. An electrode with MOF as an active material or as an active material carrier has been successfully prepared, and an electrode that has an active material or active material carrier prepared with MOF as a precursor has also been prepared. However, MOF, when serving as an electrode, shows slightly-lower conductivity than other electrode materials. Moreover, a preparation process of the MOF itself is relatively-complicated, which affects the morphology controllability of the MOF, makes the MOF have poor stability, and limits the wide application of MOF in electrode materials.
[0004] So far, the use of various MOFs as anodes for lithium batteries has been reported. However, most MOFs show the disadvantage of low capacity when used as anodes for lithium batteries. Therefore, it is of great significance to find a composite with stable structure, large SSA, wide application range, and greatly-improved charge and discharge coulombic efficiency and cycling performance.
SUMMARY
[0005] The present disclosure is intended to provide a preparation method and use of a graphite-MOF composite. The composite prepared by the preparation method of the present disclosure has prominent structural stability. The composite, when used in an anode for a lithium battery, can eliminate the volume expansion effect of the lithium battery during a charging and discharging process caused by the structural collapse of an anode material due to the lithium insertion-deinsertion cycle of the lithium battery during the charging and discharging process, thereby improving the capacity and other electrochemical properties.
[0006] To achieve the above objective, the present disclosure adopts the following technical solutions: [0007] The present disclosure provides a preparation method of a graphite-MOF composite, including the following steps: [0008] (1) adding an amino-containing organic substance to a mixed liquid, stirring, stirring at an increased speed, adding a titanium-containing coupling agent, and continuing stirring to obtain a suspension; [0009] (2) subjecting the suspension to a solvothermal reaction and filtration, washing a resulting filter cake alternately with organic solvents, and conducting extraction to obtain an MOF; and [0010] (3) grinding graphite into a powder, mixing the powder with an alcohol, shaking, adding the MOF, and continuing shaking* allowing a resulting mixture to react under reflux and then to stand, and centrifuging a resulting system; and drying a resulting precipitate to obtain the graphite-MOF composite.
[0011] Preferably, the mixed liquid may be obtained by mixing N,N-dirnethylformarnide (DMF) and methanol in a mass ratio of 1:(6-9).
[0012] Preferably, the DMF and methanol may both he in an anhydrous state.
[0013] Preferably, the DMF may be distilled out at 50°C to 60°C; and the methanol may be distilled out at 55°C to 65°C.
[0014] Preferably, the amino-containing organic substance in step (1) may he 2-a m noterephth al ic acid; and in step (1), a mass ratio of the amino-containing organic substance to the mixed liquid may be 1:(3-6).
[0015] Preferably, in step (1), the stirring may be first conducted for 10 min to 30 min at a temperature of 15°C to 35°C and a stirring speed of 500 r/min to 800 r/min.
[0016] Preferably, in step (1), the stirring at an increased speed may be conducted at 1,000 r/min to 1,500 r/min, and then the stirring may be further conducted for 10 min to 30 min [0017] Preferably, in step (1), the titanium-containing coupling agent may he tetrahutyl titanate (TBT).
[0018] Preferably, in step (1), a mass ratio of the mixed liquid to the titanium-containing coupling agent may be 1:(15-35).
[0019] More preferably, in step (1), a mass ratio of the mixed liquid to the titanium-containing coupling agent may be 1:(20-30).
[0020] Preferably, in step (2), the organic solvents may be DMF and methanol.
[0021] Preferably, in step (2), the washing may be conducted alternately with DMF and methanol 3 to 5 times.
[0022] Preferably, in step (2), the solvothermal reaction may he conducted at 130°C to 150°C for 24 h to 72 h. [0023] Preferably, in step (2), the extraction may be conducted with a Soxhlet extractor.
[0024] Preferably, in step (3), the graphite may be ground into a powder of 100 to 200 mesh. [0025] Preferably, in step (3), the alcohol may be anhydrous methanol.
[0026] Preferably, in step (3), a mass ratio of the graphite to the alcohol may he 1:(10-20).
[0027] More preferably, in step (3), a mass ratio of the graphite to the alcohol may be 1:(15-20).
[0028] Preferably, in step (3), a mass ratio of the MOF to the alcohol may be 1:(10-20).
[0029] More preferably, in step (3), a mass ratio of the MOF to the alcohol may he 1:(15-20).
[0030] Preferably, in step (3), the shaking may refer to ultrasonic shaking; and the ultrasonic shaking may be first conducted for 20 min to 40 min and further conducted for 20 min to 40 min. [0031] Preferably, in step (3), the resulting mixture may react under reflux at 60°C to 70°C for 12 h to 18 h; and the standing may be conducted for 12 h to 18 h. [0032] The present disclosure also provides a graphite-MOF composite prepared by the preparation method described above, and the graphite-MOF composite has a specific capacity of 460 mAh/g to 495 mAh/g, a porosity of 32% to 37%, and an SSA of 2.7 m2/g to 3.5 m2/g.
[0033] The present disclosure also provides a negative electrode sheet, including the graphite-MOF composite described above.
[0034] The present disclosure also provides a preparation method of the negative electrode sheet, including the following steps: [0035] mixing the graphite-MOF composite with acetylene black, and conducting ball-milling to obtain a mixture; mixing the mixture, PVDF, and N-methylpyrrolidone (NMP) to obtain a slurry; and coating and drying the slurry to obtain the negative electrode sheet.
[0036] Preferably, a weight ratio of the graphite-MOF composite to the acetylene black may be 1:(0.1-0.3).
[0037] Preferably, the ball-milling may be conducted for 10 min to 20 min at a rotational speed of 3,000 r/min to 6,000 r/min [0038] Preferably, the mixture, PVDF, and NMP may have a mass ratio of 1:(0.1-0.15):(0.1-0.5). [0039] The present disclosure also provides a battery including the negative electrode sheet described above.
[0040] Advantages of the present disclosure:
[0041] 1. The present disclosure uses the prepared graphite-MOF composite (graphite-coated MOF) as a basic structure for anode materials, which exhibits prominent structural stability. The composite, when used in an anode for a lithium battery, can eliminate the volume expansion effect of the lithium battery during a charging and discharging process caused by the structural collapse of an anode material due to the lithium insertion-deinsertion cycle of the lithium battery during the charging and discharging process (volume expansion will lead to the collapse of a material structure and the deterioration of electrochemical properties), thereby improving the capacity and other electrochemical properties.
[0042] 2. The composite designed in the present disclosure not only exhibits better charge and discharge capacity and conductivity than graphite, but also has the excellent structural stability of MOF.
[0043] 3. The present disclosure introduces NH2-into an MOF, which not only enhances the electron density of a material such that the conductivity of the material is increased to some extent, but also provides lithium insertion sites such that the charge and discharge capacity of the material is significantly increased. The composite of the present disclosure has an initial specific discharge capacity as high as 492.3 mAh/a and a capacity retention as high as 96.6%.
BRIEF DESCRIPTION OF DRAWINGS
[0044] FIG. I is an X-ray diffraction (XRD) pattern of the graphite-MOF composite prepared in
Example 1; and
[0045] FIG. 2 is a transmission electron microscopy (TEM) image of the graphite-MOF composite prepared in Example 1.
DETAILED DESCRIPTION
[0046] In order to have a thorough understanding of the present disclosure, preferred experimental schemes of the present disclosure are described below with reference to examples to further illustrate the characteristics and advantages of the present disclosure. Any change or modification made without departing from the subject of the present disclosure can he understood by those skilled in the art. The protection scope of the present disclosure is determined by the claims.
[0047] If no specific conditions are specified in the examples of the present disclosure, conventional conditions or the conditions recommended by a manufacturer will be adopted. All of the raw materials, reagents, or the like which are not specified with manufacturers are conventional commercially-available products.
[0048] Example 1
[0049] A preparation method of a graphite-MOF composite was provided in this example, including the following steps: [0050] (1) anhydrous DMF and anhydrous methanol were distilled out at 50°C and 55°C, respectively, and then mixed in a ratio of 1:6 to obtain a mixed liquid; [0051] (2) 2-aminoterephthalic acid was added in a mass-to-volume ratio of 1:3, and a resulting mixture was stirred for 10 min at a stirring speed of 500 r/min and a temperature of 15°C; and the stirring speed was increased to 1,000 r/min, then TBT was added in a volume ratio of 1:15, and a resulting mixture was further stirred for 10 min to obtain a suspension; [0052] (3) the suspension was transferred to a dry hydrothermal reactor, and a solvothermalreaction was conducted at 130°C for 24 h; then a product of the solvothermal reaction was filtered out and washed alternately with anhydrous DMF and anhydrous methanol, each 3 times; and extraction was conducted with a Soxhlet extractor to obtain a white-solid MOF; and [0053] (4) graphite was ground into a powder (which was sieved through a 100-mesh sieve), the powder was mixed with anhydrous methanol in a mass-volume ratio of 1:10, and a resulting mixture was ultrasonically shaken for 20 min; then the white-solid MOF was added in a mass-volume ratio of 1:10, and a resulting mixture was further ultrasonically shaken for 20 min; a resulting mixture reacted under reflux at 60°C for 12 h, then stood for 12 h, and then centrifuged; and a resulting filter cake was dried to obtain the graphite-MOF composite (graphite-coated MOF).
[0054] A preparation method of a negative electrode sheet was provided in this example, including the following steps: the graphite-MOF composite was mixed with acetylene black in a weight ratio of 1:0.1, and a resulting mixture was then ball-milled at 3,000 r/min for 10 min; a resulting mixture powder was mixed with PVDF and NMP in a ratio of 1:0.1:0.1 to obtain a slurry; and the slurry was coated and dried to obtain the negative electrode sheet.
[0055] Example 2
[0056] A preparation method of a graphite-MOF composite was provided in this example, including the following steps: [0057] (1) anhydrous DMF and anhydrous methanol were distilled out at 50°C and 60°C, respectively, and then mixed in a ratio of 1:7 to obtain a mixed liquid; [0058] (2) 2-aminoterephthalic acid was added in a mass-to-volume ratio of 1:5, and a resulting mixture was stirred for 20 min at a stirring speed of 700 r/min and a temperature of 20°C; and the stirring speed was increased to 1,200 r/min, then TBT was added in a volume ratio of 1:25, and a resulting mixture was further stirred for 20 min to obtain a suspension; [0059] (3) the suspension was transferred to a dry hydrothermal reactor, and a solvothermal reaction was conducted at 140°C for 48 h; then a product of the solvothermal reaction was filtered out and washed alternately with anhydrous DMF and anhydrous methanol, each 3 times; and extraction was conducted with a Soxhlet extractor to obtain a while-solid MOF; and [0060] (4) graphite was ground into a powder (which was sieved through a 150-mesh sieve), the powder was mixed with anhydrous methanol in a mass-volume ratio of 1:15, and a resulting mixture was ultrasonically shaken for 30 min; then the white-solid MOF was added in a mass-volume ratio of 1:15, and a resulting mixture was further ultrasonically shaken for 30 min; a resulting mixture reacted under reflux at 65°C for 15 h, then stood for 15 h, and then centrifuged; and a resulting filter cake was dried to obtain the graphite-MOF composite (graphite-coated MOF).
[0061] A preparation method of a negative electrode sheet was provided in this example, including the following steps: the graphite-MOF composite (graphite-coated MOF) was mixed with acetylene black in a weight ratio of 1:02, and a resulting mixture was then ball-milled at 4,500 r/min for 15 min; a resulting mixture powder was mixed with PVDF and NMP in a ratio of 1:0.12:0.3 to obtain a slurry; and the slurry was coated and dried to obtain the negative electrode sheet.
[0062] Example 3
[0063] A preparation method of a graphite-MOF composite was provided in this example, including the following steps: [0064] (1) anhydrous DMF and anhydrous methanol were distilled out at 60°C and 65°C, respectively, and then mixed in a ratio of 1:9 to obtain a mixed liquid; [0065] (2) 2-aminoterephthalic acid was added in a mass-to-volume ratio of 1:6, and a resulting mixture was stirred for 30 min at a stirring speed of 800 r/min and a temperature of 35°C; and the stin-ing speed was increased to 1,500 r/min, then TBT was added in a volume ratio of 1:35, and a resulting mixture was further stirred for 30 min to obtain a suspension; [0066] (3) the suspension was transferred to a dry hydrothermal reactor, and a solvothermal reaction was conducted at 150°C for 72 h; then a product of the solvothermal reaction was filtered out and washed alternately with anhydrous DMF and anhydrous methanol, each 3 times; and extraction was conducted with a Soxhlet extractor to obtain a white-solid MOF; and [0067] (4) graphite was ground into a powder (which was sieved through a 200-mesh sieve), the powder was mixed with anhydrous methanol in a mass-volume ratio of 1:20, and a resulting mixture was ultrasonically shaken for 40 min; then the white-solid MOF was added in a mass-volume ratio of 1:20, and a resulting mixture was further ultrasonically shaken for 40 min; a resulting mixture reacted under reflux at 70°C for 18 h, then stood for 18 h, and then centrifuged; and a resulting filter cake was dried to obtain the graphite-MOF composite (graphite-coated MOF).
[0068] A preparation method of a negative electrode sheet was provided in this example, including the following steps: the graphite-MOF composite was mixed with acetylene black in a weight ratio of 1:0.3, and a resulting mixture was then ball-milled at 6,000 r/min for 20 min; a resulting mixture powder was mixed with PVDF and N MP in a ratio of 1:0.15:0.5 to obtain a slurry; and the slurry was coated and dried to obtain the negative electrode sheet.
[0069] Comparative Example 1 [0070] A preparation method of an anode material for a titanium-based MOF LIB was provided, including the following steps: 2,5-dihydroxyterephthalic acid (DHTA) was dispersed in an i-propanol solution, a resulting solution was added dropwise to a solution of titanium tetraisopropoxide in acetonitrile to obtain an orange-brown slurry at room temperature, and the slurry was stirred for 30 min; then the slurry was transferred to a Teflon high-pressure reactor, heated to 120°C, and kept at the temperature for 24 h to obtain a dark-red crystal; and the crystal was then filtered out by suction filtration in an air atmosphere, washed 3 times with each of DMF and ethanol, and dried under vacuum to obtain the electrode material.
[0071] Comparative Example 2 [0072] A preparation method of a graphite-MOF composite was provided, including the following steps: commercial graphite was ground into a powder, the powder was mixed with anhydrous methanol in a mass-volume ratio of 1:20, and a resulting mixture was ultrasonically shaken for 40 min; then the MOF obtained in Comparative Example 1 was added in a mass-volume ratio of 1:20, and a resulting mixture was further ultrasonically shaken for 40 min; a resulting mixture reacted under reflux at 70°C for 18 h, then stood for 18 h, and then centrifuged; and a resulting filter cake was dried to obtain a graphite-coated MOF.
[0073] Performance test: [0074] The anode materials (graphite-MOF composites) prepared in Examples 1 to 3 and the anode materials prepared in the Comparative Examples 1 to 2 were used to prepare negative electrode sheets, and a lithium sheet was used as a positive electrode to assemble button batteries. The initial discharge test was conducted at a rate of 1 C, and results were shown in Table 1 and Table 2. It can be seen from Table 1 that, at a rate of 1 C, the graphite-MOF composites of the present disclosure show a higher initial specific discharge capacity than that of the MOF materials of Comparative Examples 1 and 2; and the Example 2 shows an initial specific discharge capacity of 492.3 mAh/g, while the Comparative Example 1 shows an initial specific discharge capacity only of 333.1 mAh/g and the Comparative Example 2 shows an initial specific discharge capacity only of 367.2 mAh/g. It can be seen from Table 2 that, at a rate of 1 C, the graphite-MOF composites of the present disclosure show a longer cycling life than that of the MOF materials of the comparative examples; and after 1,600 cycles at 1 C, the Example 2 shows a capacity retention of 96.6%, while the Comparative Examples 1 to 2 show a capacity retention only of 92.8% and 90.2%, respectively. [0075] Table 1 Performance of button batteries prepared from the graphite-MOF composites Item Example Example Example Comparative Comparative 1 2 3 Example 1 Example 2 Initial specific 461.9 492.3 462.1 333.1 367.2 discharge capacity (mAh/g) Initial charge and 93.8 93.9 93.9 82.2 84.5 discharge efficiency (%) Table 2 Cycling performance of full batteries prepared ft om the graphite-MOF composites Item Example 1 Example 2 Example 3 Comparative Comparative
Example 1 Example 2
Discharge capacity 95.9 96.6 93.3 92.8 90.2 retention (%) after 1,600 cycles at 1C [0076] FIG. 1 is an XRD pattern of the graphite-MOF composite, which reflects the characteristic peaks of the composite. FIG. 2 is a TEM image of the graphite-MOF composite, showing a hulk morphology.
[0077] The preparation method and use of a graphite-MOF composite provided in the present disclosure are described in detail above, and specific examples are used herein to illustrate the principle and implementation of the present disclosure. The examples are illustrated above merely to help understand the method and core ideas thereof (including the optimal mode) of the present disclosure and allow any person skilled in the art to practice the present disclosure, including manufacturing and using any device or system and implementing any combined method. It should be noted that several improvements and modifications may be made by persons of ordinary skill in the art without departing from the principle of the present disclosure, and these improvements and modifications should also fall within the protection scope of the present disclosure. The protection scope of the present disclosure is defined by the claims and may encompass other examples that those skilled in the art can think of. If these other examples have structural elements that arc not different from the literal expression in the claims or include equivalent structural elements that are not substantially different from the literal expression in the claims, they should also be included in the scope of the claims.
Claims (10)
- CLAIMS: 1. A preparation method of a graphite-metal organic framework (MOF) composite, comprising the following steps: (1) adding an amino-containing organic substance to a mixed liquid, stirring, stirring at an increased speed, adding a titanium-containing coupling agent, and continuing stirring to obtain a suspension; (2) subjecting the suspension to a solvothermal reaction and filtration, washing a resulting filter cake alternately with organic solvents, and conducting extraction to obtain an MOF; and (3) grinding graphite into a powder, mixing the powder with an alcohol, shaking, adding the MOF, and continuing shaking; allowing a resulting mixture to react under reflux and then to stand, and centrifuging a resulting system; drying a resulting precipitate to obtain the graphite-MOF composite.
- 2. The preparation method according to claim 1, wherein the mixed liquid in step (1) is obtained by mixing N,N-dimethylformamide (DMF) and methanol in a mass ratio of 1:(6-9).
- 3. The preparation method according to claim 1, wherein the amino-containing organic substance in step (1) is 2-aminoterephthalic acid; and in step (1), a mass ratio of the amino-containing organic substance to the mixed liquid is 1:(3-6).
- 4. The preparation method according to claim 1, wherein the stirring is first conducted for 10 min to 30 min at a temperature of 15°C to 35°C and a stirring speed of 500 r/rnin to 800 r/min in step (1); and in step (1), the stirring at the increased speed is conducted at 1,000 r/min to 1,500 r/min, and then the stirring is further conducted for 10 min to 30 min
- 5. The preparation method according to claim 1, wherein the titanium-containing coupling agent in step (1) is tetrabutyl titanate (TBT); and in step (1), a mass ratio of the mixed liquid to the titanium-containing coupling agent is 1:(15-35).
- 6. The preparation method according to claim 1, wherein the organic solvents in step (2) are DMF and methanol.
- 7. The preparation method according to claim 1, wherein the alcohol in step (3) is anhydrous methanol; a mass ratio of the graphite to the alcohol is 1:(10-20); and in step (3), a mass ratio of the MOF to the alcohol is 1:(10-20).
- 8. The preparation method according to claim 1, wherein the solvothermal reaction in step (2) is conducted at 130°C to 150°C for 24 h to 72 h; in step (3), the resulting mixture reacts under reflux at 60°C to 70°C for 12 h to 18 h, and is left to stand for 12 h to 18 h.
- 9. A graphite-MOF composite prepared by the preparation method according to any one of claims 1 to 8, wherein the graphite-MOF composite has a specific capacity of 460 rnAh/g to 495 rnAh/g, a porosity of 32% to 37%, and a specific surface area (SSA) of 2.7 m2/g to 3.5 rn2/g.
- 10. A negative electrode sheet comprising the graphite-MOF composite according to claim 9.
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