CN112490441B - Graphene-hexa-mercapto-benzene-copper electrode material and preparation method and application thereof - Google Patents
Graphene-hexa-mercapto-benzene-copper electrode material and preparation method and application thereof Download PDFInfo
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 36
- 239000010949 copper Substances 0.000 title claims abstract description 36
- 239000007772 electrode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 58
- 239000000843 powder Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 23
- NVGVNJDFTHQFQR-UHFFFAOYSA-N benzene-1,2,3,4,5,6-hexathiol Chemical compound SC1=C(S)C(S)=C(S)C(S)=C1S NVGVNJDFTHQFQR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 229940005740 hexametaphosphate Drugs 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000003495 polar organic solvent Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- LCKGTNNNZAWFSI-UHFFFAOYSA-N OC(C(C(C1(S)S)(S)S)(C=CC1S)S)=O Chemical compound OC(C(C(C1(S)S)(S)S)(C=CC1S)S)=O LCKGTNNNZAWFSI-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- RTCQLINRDVLXLC-UHFFFAOYSA-N C1(=C(C(=C(C(=C1S)S)S)S)S)S.[Cu] Chemical compound C1(=C(C(=C(C(=C1S)S)S)S)S)S.[Cu] RTCQLINRDVLXLC-UHFFFAOYSA-N 0.000 abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000012621 metal-organic framework Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- -1 hexa-mercapto copper benzoate Chemical compound 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Substances SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- VWPUAXALDFFXJW-UHFFFAOYSA-N benzenehexol Chemical compound OC1=C(O)C(O)=C(O)C(O)=C1O VWPUAXALDFFXJW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical compound SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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
- H01M4/36—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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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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- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a graphene-copper hexa-mercapto benzene electrode material and a preparation method and application thereof, and the material comprises matrix graphene, wherein copper hexa-mercapto benzene nanoparticles are attached to a matrix graphene sheet layer, and the mass ratio of the matrix graphene to the copper hexa-mercapto benzene nanoparticles is 3: 1-30, and the preparation method of the material comprises the following steps: (1) preparing a graphene dispersion liquid; (2) dissolving a copper salt in graphene dispersion liquid, adding hexa-mercaptobenzene powder under the protection of inert gas, and rapidly stirring until a black precipitate is separated out; (3) soaking the black precipitate in ethanol, washing for multiple times, and drying in vacuum to obtain the graphene-copper hexa-mercapto benzene electrode material; the material can be used as an electrode in a lithium ion battery. The material has better lithium storage performance and good rate capability.
Description
Technical Field
The invention relates to an electrode material and a preparation method and application thereof, and more particularly relates to a graphene-copper hexa-mercapto-benzene electrode material and a preparation method and application thereof.
Background
In recent years, with the development of electric automobiles, mobile devices, deep sea exploration and aerospace fields, the performance of power batteries has become a factor for restricting the scientific and technical progress. The development of electrode materials with high specific capacity, good rate performance and long cycle life is an important direction for the development and fusion of disciplines such as physics, chemistry, materials and the like. Compared with common carbon materials, the metal organic framework material has the characteristics of rich active sites, large specific surface area, easy design and synthesis, multi-level pore channel structure and the like, and becomes a research hotspot in the electrochemical field. At present, the application prospect of the metal organic framework and the composite material thereof in the field of electrochemical energy storage is greatly concerned, however, the metal organic framework material generally has extremely low conductivity, and the transmission of electrons in the material is seriously limited, so that the comprehensive electrochemical performance of the metal organic framework material is poor; meanwhile, the metal organic framework used as the electrode material of the lithium ion battery often shows serious performance attenuation in the process of lithium intercalation and lithium deintercalation.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a graphene-hexa-mercapto benzene copper electrode material which has excellent electrochemical performance, lithium storage performance, rate capability and long cycle life; another object of the present invention is to provide a method for preparing the material; it is another object of the present invention to provide applications of the material.
The technical scheme is as follows: the graphene-copper hexametaphosphate electrode material comprises matrix graphene, wherein copper hexametaphosphate nanoparticles are attached to a graphene sheet layer of the matrix, and the mass ratio of the matrix graphene to the copper hexametaphosphate particles is 3:1 to 30.
Wherein the particle size of the copper hexamercapto-benzene nanoparticles is less than 20 nm.
The preparation method of the graphene-copper hexahydrosulphydryl benzene electrode material comprises the following steps of:
(1) preparing a graphene dispersion liquid;
(2) dissolving a copper salt in graphene dispersion liquid, adding hexa-mercaptobenzene powder under the protection of inert gas, and rapidly stirring until a black precipitate is separated out from the solution and the solution becomes clear;
(3) precipitating and filtering the solution, soaking the solution in ethanol, washing the black precipitate for multiple times, and drying the obtained black precipitate in vacuum to obtain the graphene-copper hexametaphosphate electrode material.
Wherein, step 1 includes the following steps:
(11) preparing a graphene oxide dispersion liquid by adopting a typical Hummers method;
(12) carrying out thermal reduction to obtain graphene powder;
(13) adding sodium dodecyl benzene sulfonate into graphene powder, adding a polar organic solvent, performing ultrasonic treatment until the graphene powder is uniformly dispersed in the solvent, and standing until no obvious solid precipitate is generated to obtain the graphene dispersion liquid.
Wherein, in the step 13, the polar organic solvent is one of N, N-dimethylformamide, ethanol or N-methylpyrrolidone, and the mass of the sodium dodecyl benzene sulfonate is 5-15% of that of the graphene; the concentration of graphene in the graphene dispersion liquid in the step 1 is 0.2-2 mg/mL; in the step 2, the copper salt is one of copper chloride, copper sulfate or copper acetate, the mass concentration of the dissolved copper salt in the graphene dispersion liquid is 0.1-5 g/mL, and the molar ratio of the copper salt to the hexahydroxybenzene is 3-8: 1.
the graphene-copper hexahydrothiobenzoate electrode material is applied to a lithium ion battery as an electrode.
The hexa-mercapto copper benzoate is a two-dimensional metal organic framework material with extremely high conductivity, has abundant lithium storage sites, is extremely easy to agglomerate into compact powder, and is not beneficial to permeation and transmission of electrolyte. The hexa-mercapto benzene copper is dispersed on a single-layer or few-layer graphene sheet, so that the particle size of the hexa-mercapto benzene copper is reduced, the permeation of the electrolyte can be accelerated, and the volume change of the electrolyte in the charge-discharge process can be reduced, therefore, the hexa-mercapto benzene copper serving as an electrode material has excellent lithium storage performance and rate capability and long cycle life.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: 1. the hexa-mercapto benzene copper is formed by stacking graphene-like lamellar structures formed by copper ions and hexa-mercapto benzene in the same plane through coordination bonds, the valence of copper and sulfur contained in the hexa-mercapto benzene copper are respectively +1 and-0.5, the copper and the sulfur can participate in reduction reaction to store lithium, and meanwhile, a benzene ring is used as an active site to store lithium; 2. the conductivity of the hexa-mercapto copper benzoate is up to 1580S/cm, which is beneficial to the transmission of electrons in the material and gives full play to the function of each active site, so that the material has better rate capability.
Drawings
FIG. 1 is a transmission electron micrograph of example 2;
fig. 2 is a plot of the charge and discharge cycling performance of graphene, copper hexamercapto-phenyl and example 2.
Detailed Description
Example 1
Preparing graphene oxide dispersion liquid by a typical Hummers method, and carrying out thermal reduction to obtain graphene powder. Adding 5mg of sodium dodecyl benzene sulfonate into 100mg of graphene powder, adding 500mL of ethanol, and performing ultrasonic treatment until the graphene powder is uniformly dispersed in a solvent to prepare a graphene dispersion liquid with the mass concentration of 0.2 mg/mL;
dissolving 100mg of copper chloride in 50mL of graphene dispersion liquid, introducing nitrogen for 30 minutes, then adding 60mg of hexa-mercapto-benzene powder under the protection of nitrogen, rapidly stirring at room temperature, separating out a black product from the solution, clarifying the solution, fully soaking and washing the black product after precipitation and filtration for multiple times by using ethanol, and drying the obtained black product at the temperature of 60 ℃ in vacuum to obtain the graphene-hexa-mercapto-benzene copper electrode material with the mass ratio of graphene to hexa-mercapto-benzene copper of 1:10, wherein the particle size of the hexa-mercapto-benzene copper nanoparticles is about 10 nm.
Example 2
Preparing graphene oxide dispersion liquid by a typical Hummers method, and carrying out thermal reduction to obtain graphene powder. Adding 5mg of sodium dodecyl benzene sulfonate into 100mg of graphene powder, adding 50mL of ethanol, and performing ultrasonic treatment until the graphene powder is uniformly dispersed in a solvent to prepare a graphene dispersion liquid with the mass concentration of 2 mg/mL;
dissolving 120mg of copper chloride in 50mL of graphene dispersion liquid, introducing nitrogen for 30 minutes, then adding 60mg of hexa-mercapto-benzene powder under the protection of nitrogen, rapidly stirring at room temperature, separating a black product from the solution, clarifying the solution, precipitating the black product, filtering, fully soaking and washing with ethanol for multiple times, drying the obtained black product at the temperature of 60 ℃ in vacuum, and obtaining the graphene-hexa-mercapto-benzene copper electrode material with the mass ratio of graphene to hexa-mercapto-benzene copper of 1:1, wherein the particle size of the hexa-mercapto-benzene copper nanoparticles is about 10 nm.
Example 3
Preparing graphene oxide dispersion liquid by a typical Hummers method, and carrying out thermal reduction to obtain graphene powder. Adding 15mg of sodium dodecyl benzene sulfonate into 100mg of graphene powder, adding 50mL of ethanol, and performing ultrasonic treatment until the graphene powder is uniformly dispersed in a solvent to prepare a graphene dispersion liquid with the mass concentration of 2 mg/mL;
dissolving 150mg of copper chloride in 90mL of the graphene dispersion liquid, introducing nitrogen for 30 minutes, then adding 35.4mg of hexa-mercapto-benzene powder under the protection of nitrogen, rapidly stirring at room temperature, separating out a black product from the solution, clarifying the solution, precipitating the black product, filtering, fully soaking and washing with ethanol for multiple times, drying the obtained black product at the temperature of 80 ℃ in vacuum, and obtaining the graphene-hexa-mercapto-benzene-copper electrode material with the mass ratio of graphene to hexa-mercapto-benzene-copper of 3:1, wherein the particle size of the hexa-mercapto-benzene-copper nanoparticles is about 15 nm.
Comparative example
Preparation of pure copper hexamercaptobenzote powder:
dissolving 120mg of copper chloride in 10mL of N, N-dimethylformamide, introducing argon for 30 minutes, then adding 60mg of hexamercaptobenzene powder under the protection of argon, rapidly stirring at room temperature, separating out a black product from the solution, precipitating and filtering the black product, fully soaking and washing the black product with ethanol for multiple times, and drying the obtained solid product at 60 ℃ in vacuum to obtain the hexamercaptobenzene copper powder.
As shown in fig. 1, the granular copper hexametaphosphate is distributed on the graphene to form a graphene-copper hexametaphosphate material, and the particle size of the copper hexametaphosphate nanoparticle is about 10 nm. As shown in fig. 2, the graphene-hexa-mercapto-copper benzene material has a specific mass capacity of 1080mAh/g after circulating for 150 circles under the current density of 0.01-3V and 0.1A/g, and compared with pure hexa-mercapto-copper benzene and graphene, the composite material has a higher specific mass capacity.
Claims (8)
1. The graphene-copper hexametaphosphate electrode material is characterized by comprising matrix graphene, wherein copper hexametaphosphate nanoparticles are attached to a matrix graphene sheet layer, and the mass ratio of the matrix graphene to the copper hexametaphosphate particles is 3:1 to 30.
2. The graphene-copper hexametaphosphate electrode material of claim 1, wherein the particle size of the copper hexametaphosphate nanoparticles is less than 20 nm.
3. The preparation method of the graphene-copper hexamercaptobenzoate electrode material of claim 1, characterized by comprising the following steps:
(1) preparing a graphene dispersion liquid;
(2) dissolving a copper salt in graphene dispersion liquid, adding hexa-mercaptobenzene powder under the protection of inert gas, and rapidly stirring until a black precipitate is separated out from the solution and the solution becomes clear;
(3) precipitating and filtering the solution, soaking the solution in ethanol, washing the black precipitate for multiple times, and drying the obtained black precipitate in vacuum to obtain the graphene-copper hexametaphosphate electrode material.
4. The method for preparing the graphene-copper hexametaphosphate electrode material according to claim 3, wherein the step 1 comprises the following steps:
(11) preparing a graphene oxide dispersion liquid by adopting a typical Hummers method;
(12) carrying out thermal reduction to obtain graphene powder;
(13) adding sodium dodecyl benzene sulfonate into graphene powder, adding a polar organic solvent, performing ultrasonic treatment until the graphene powder is uniformly dispersed in the solvent, and standing until no obvious solid precipitate is generated to obtain the graphene dispersion liquid.
5. The method for preparing the graphene-hexa-mercapto-benzene-copper electrode material according to claim 4, wherein the polar organic solvent in the step 13 is one of N, N-dimethylformamide, ethanol or N-methyl pyrrolidone, and the mass of the sodium dodecyl benzene sulfonate is 5% to 15% of the mass of the graphene.
6. The method for preparing the graphene-copper hexametaphosphate electrode material according to claim 3, wherein the graphene concentration in the graphene dispersion liquid in the step 1 is 0.2-2 mg/mL.
7. The method for preparing the graphene-copper hexametaphosphate electrode material of claim 3, wherein the copper salt in the step 2 is one of copper chloride, copper sulfate and copper acetate, the mass concentration of the dissolved copper salt in the graphene dispersion liquid is 0.1-5 g/mL, and the molar ratio of the copper salt to the copper hexametaphosphate is 3-8: 1.
8. the use of the graphene-copper hexakismercapto-benzene electrode material of claim 1 as an electrode in a lithium ion battery.
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| PCT/CN2021/124630 WO2022089248A1 (en) | 2020-10-30 | 2021-10-19 | Graphene-hexamercapto benzene copper electrode material, preparation method therefor and use thereof |
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| CN113087920B (en) * | 2021-03-29 | 2021-11-16 | 江苏科技大学 | Preparation method of metal organic framework composite material |
| CN114106356A (en) * | 2021-12-30 | 2022-03-01 | 复旦大学 | Conductive MOFs tubular material with hexamercaptobenzene as ligand and preparation method thereof |
| CN114507357A (en) * | 2022-03-21 | 2022-05-17 | 中国科学院化学研究所 | Hexamercapto-silver benzene coordination polymer and preparation method thereof |
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| CN109037615A (en) * | 2018-07-08 | 2018-12-18 | 启东祥瑞建设有限公司 | A kind of preparation method of Cu-MOF/rGO lithium ion battery negative material |
| CN109935818A (en) * | 2019-03-28 | 2019-06-25 | 中南大学 | A kind of ferroso-ferric oxide/rGO nanometer anode material and preparation method thereof |
| CN111004403A (en) * | 2019-11-05 | 2020-04-14 | 复旦大学 | Method for in-situ growth of large-area Cu-BHT conductive thin film MOFs on silicon oxide surface |
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| CN111451491B (en) * | 2020-04-29 | 2022-04-19 | 西安稀有金属材料研究院有限公司 | Preparation method of graphene reinforced copper-based composite material |
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| CN109037615A (en) * | 2018-07-08 | 2018-12-18 | 启东祥瑞建设有限公司 | A kind of preparation method of Cu-MOF/rGO lithium ion battery negative material |
| CN109935818A (en) * | 2019-03-28 | 2019-06-25 | 中南大学 | A kind of ferroso-ferric oxide/rGO nanometer anode material and preparation method thereof |
| CN111004403A (en) * | 2019-11-05 | 2020-04-14 | 复旦大学 | Method for in-situ growth of large-area Cu-BHT conductive thin film MOFs on silicon oxide surface |
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