CN114477155B - Porous graphene/lamellar graphene composite material and preparation method and application thereof - Google Patents
Porous graphene/lamellar graphene composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114477155B CN114477155B CN202011162539.9A CN202011162539A CN114477155B CN 114477155 B CN114477155 B CN 114477155B CN 202011162539 A CN202011162539 A CN 202011162539A CN 114477155 B CN114477155 B CN 114477155B
- Authority
- CN
- China
- Prior art keywords
- graphene
- lamellar
- composite material
- dispersion liquid
- porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 247
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 219
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007788 liquid Substances 0.000 claims description 36
- 239000006185 dispersion Substances 0.000 claims description 35
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- 239000003990 capacitor Substances 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000013543 active substance Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000004299 exfoliation Methods 0.000 claims description 2
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000006255 coating slurry Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 6
- 239000011833 salt mixture Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 229910003481 amorphous carbon Inorganic materials 0.000 description 5
- 239000007770 graphite material Substances 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
Abstract
The application discloses a porous graphene/lamellar graphene composite material, and a preparation method and application thereof, wherein the porous graphene/lamellar graphene composite material comprises lamellar graphene and porous graphene; the porous graphene is coated on the surface of the lamellar graphene. The material has higher specific capacity, excellent multiplying power performance and good cycle stability.
Description
Technical Field
The application relates to a porous graphene/lamellar graphene composite material, and a preparation method and application thereof, and belongs to the field of lithium ion capacitors.
Background
The lithium ion capacitor is a novel energy storage device between the super capacitor and the lithium ion battery. Compared with a lithium ion battery, the lithium ion capacitor has higher energy density and longer cycle life; compared with super capacitor, the super capacitor has higher energy density, is considered as the most promising new generation of energy storage device, and is the focus of research and development in the energy storage field of various countries worldwide. Therefore, the lithium ion capacitor has great potential application value in the field of military industry, public transportation and industrial energy conservation.
The negative electrode material is an important factor for restricting the improvement of the power density of the lithium ion capacitor. Therefore, development of a negative electrode material having high specific capacity, excellent rate performance, long cycle life, and safety and reliability has been urgent. Currently, modification of graphite-based negative electrode materials, such as surface oxidation modification, doping treatment or coating modification, is an important way to improve the performance of the negative electrode materials. The coating modification is to coat a layer of amorphous carbon on the surface of graphite to form a core-shell, and the high-platform capacity of the graphite material and the high-rate performance of the amorphous carbon are effectively combined, so that the method is a simple and effective modification method. However, the size of graphite particles is larger, the specific surface area is small, the amount of coated amorphous carbon is smaller, and if the amount of amorphous carbon is further increased, the coating layer is too thick, so that the capacity of a graphite platform cannot be utilized efficiently. The thickness of the coating layer formed by commonly used coating precursors such as glucose, phenolic resin, epoxy resin, tar, etc. is difficult to control. In the process of preparing the amorphous carbon coated graphite material, the porous carbon and the graphite material are generally carbonized after being physically mixed, so that the porous carbon is difficult to effectively coat the graphite material and an effective lithium storage interface cannot be formed. Therefore, selecting proper core and shell materials and developing an effective preparation method to effectively compound the graphite material and the porous carbon is important to improving the overall performance of the cathode material.
Disclosure of Invention
According to a first aspect of the present application there is provided a porous graphene/platelet graphene composite comprising platelet graphene and porous graphene; the porous graphene is coated on the surface of the lamellar graphene, and the material has higher specific capacity, excellent rate performance and good cycle stability.
Optionally, the lamellar graphene contains doping elements; the doping element includes any one of fluorine element and oxygen element.
Optionally, the thickness of the lamellar graphene is more than 3 layers and less than 10 nm.
Specifically, the lamellar graphene includes a multilayer graphene and a few-layer graphene.
According to a second aspect of the present application, there is provided a method of preparing a porous graphene/platelet graphene composite material, comprising at least the steps of:
1) Mixing dispersion liquid containing lamellar graphene and a surface modifier to obtain surface modified graphene;
2) Mixing dispersion liquid containing graphene oxide and the surface-modified graphene to obtain a graphene oxide coated lamellar graphene composite material;
3) And reacting the mixture containing the graphene oxide coated lamellar graphene composite material and the activating agent to obtain the porous graphene/lamellar graphene composite material.
Optionally, the lamellar graphene in the step 1) is graphene prepared by a exfoliation method.
Preferably, the peeling method is at least one selected from electrochemical anodic peeling method, electrochemical cathodic peeling method, and chemical intercalation peeling method.
Optionally, the surface modifier of step 1) is selected from the group consisting of polycationic electrolytes.
Optionally, the polycation electrolyte is at least one selected from polydimethyl diallyl ammonium chloride, polyacrylamide hydrochloride, polyacrylamide and polyethyleneimine.
Optionally, step 1) includes: firstly carrying out ultrasonic treatment on the lamellar graphene for 30-90 min, then adding the lamellar graphene into a solution containing a surface modifier to obtain a dispersion liquid, and stirring the dispersion liquid for 0.5-2.0 h to obtain the surface modified graphene.
Optionally, the concentration of the surface modifier in the solution containing the surface modifier is 0.2-2 wt%.
Specifically, in the solution containing the surface modifier, the upper limit of the concentration of the surface modifier may be selected from 2wt%, 1.5wt%, 0.5wt%, and the lower limit may be selected from 0.2wt%, 0.3wt%, 0.4wt%.
Optionally, the mass ratio of the graphene oxide to the surface modified graphene in the step 2) is 1:0.5 to 50.
Optionally, the upper limit of the mass ratio of the graphene oxide to the surface modified graphene in the step 2) is selected from 1:0.5, 1: 2. 1:4. 1:5, the lower limit is selected from 1: 2. 1:4. 1:5. 1:50.
optionally, the dispersion liquid containing graphene oxide and the surface-modified graphene in step 2) is obtained by the following method:
preparing graphene oxide dispersion liquid and surface modified graphene dispersion liquid respectively;
and (3) dropwise adding the graphene oxide dispersion liquid into the surface modified graphene dispersion liquid, and obtaining the graphene oxide dispersion liquid after the dropwise adding is finished.
Optionally, the mass concentration of the graphene oxide dispersion liquid is 0.1-5.0 mg/ml.
Specifically, the upper limit of the mass concentration of the graphene oxide dispersion liquid is selected from 5mg/mL, 1.0mg/mL, 0.5mg/mL and 0.2mg/mL, and the lower limit of the mass concentration of the graphene oxide dispersion liquid is selected from 1.0mg/mL, 0.5mg/mL, 0.2mg/mL and 0.1mg/mL.
Alternatively, the drop rate is 30 to 120 drops/min.
Optionally, the mixing in the step 2) is performed under stirring conditions, and the stirring time is 0.5-2 h.
Optionally, the activator in step 3) is at least one selected from potassium hydroxide, potassium carbonate, sodium hydroxide, sodium sulfate and zinc chloride.
Optionally, the mass ratio of the graphene oxide coated platelet graphene composite material to the activator in step 3) is 1:0.1 to 50.
Optionally, the upper limit of the mass ratio of the graphene oxide coated platelet graphene composite material to the activator is selected from 1:0.1, 1:4. 1:5. 1:10, the lower limit is selected from 1:4. 1:5. 1:10. 1:50.
optionally, the mixture containing the graphene oxide coated platelet graphene composite material and the activating agent in the step 3) is obtained by the following method:
and (3) mixing an activating agent with the wet graphene oxide coated lamellar graphene composite material obtained in the step (2), and freeze-drying to obtain the mixture.
Optionally, the drying treatment is freeze-drying or oven drying;
optionally, the temperature of the oven drying is 80-120 ℃ and the time is 6-20 hours.
Optionally, the reaction conditions of step 3) include:
under an inert atmosphere;
the reaction temperature is 700-1100 ℃;
the reaction time is 0.5-8 h.
In the present application, the inert atmosphere means a nitrogen atmosphere or an inert atmosphere.
Optionally, step 3) further comprises, after the reaction:
and grinding the reaction product into powder and carrying out acid washing treatment to obtain the powdery porous graphene/lamellar graphene composite material.
Optionally, the washing liquid used for the acid washing is hydrochloric acid solution, sulfuric acid solution or nitric acid solution, and the concentration is preferably 0.5-5 mol/L hydrochloric acid solution.
In a specific embodiment, the preparation method of the porous graphene/lamellar graphene composite material comprises the following steps:
a, step A; and preparing a lamellar graphene dispersion liquid. Carrying out ultrasonic treatment on the lamellar graphene with a certain mass for 10 minutes to 90 minutes, adding the lamellar graphene into a polycation electrolyte solution, stirring for 10 minutes to 1 hour, then carrying out filtration or centrifugation treatment, carrying out ultrasonic treatment on the lamellar graphene subjected to surface treatment again for 10 minutes to 60 minutes, and stirring for 0 minutes to 1 hour to obtain a surface modified graphene dispersion liquid;
and B, step B: preparing graphene oxide prepared by Hummers into a dispersion liquid with the concentration of 0.1-1.0 mg/ml, mixing the dispersion liquid with the surface modified graphene dispersion liquid obtained in the step A, continuously stirring for 10 minutes to 2 hours, and filtering and collecting the mixture to obtain a graphene oxide coated sheet graphene composite material;
and C, step C: fully mixing the graphene oxide coated lamellar graphene composite material obtained in the step B with an activating agent, and drying to obtain a graphene activating agent mixture; placing the obtained graphene activator mixture in inert atmosphere, and performing activation treatment at 700-1100 ℃ for 0.5-8 hours to obtain an activated sample;
and D, step D: and C, grinding the activated sample obtained in the step, washing with deionized water to neutrality, filtering, collecting, and drying to obtain the porous graphene in-situ coated lamellar graphene.
According to the method, the lamellar graphene is used as a processing object, the in-situ coating of the lamellar graphene by the graphene oxide is realized after the surface treatment of the lamellar graphene, and the porous graphene in-situ coated lamellar graphene material is obtained after high-temperature activation.
In a third aspect of the present application, there is provided an electrode comprising:
an active substance; a conductive agent; a binder; a current collector;
the active substance is at least one of the porous graphene/lamellar graphene composite material and the porous graphene/lamellar graphene composite material prepared by the preparation method.
Wherein the conductive agent is at least one selected from ketjen black, conductive carbon black and carbon nanotubes.
The binder is at least one selected from tetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethyl cellulose, sodium alginate, polyacrylic acid and styrene-butadiene rubber.
The current collector is at least one of copper foil and stainless steel mesh.
Optionally, the mass ratio of the electrode active material, the conductive agent and the binder is 8:1:1.
alternatively, the loading of the active material in the electrode is 1.0-2.0 mg/cm 2 。
In a fourth aspect of the present application, there is provided a method of manufacturing an electrode, comprising:
and compositing slurry containing an active substance, a conductive agent and a binder on a current collector to obtain the electrode, wherein the active substance is at least one of the porous graphene/lamellar graphene composite material and the porous graphene/lamellar graphene composite material prepared by the preparation method.
Optionally, the compounding comprises at least one of coating, rolling, extrusion.
Optionally, the mass ratio of the electrode active material, the conductive agent and the binder is 8:1:1.
in a fifth aspect of the present application, there is provided a half cell comprising:
the positive electrode is at least one of the electrode and the electrode prepared by the preparation method;
an electrolyte; and
and a negative electrode, a metal lithium sheet.
Optionally, the electrolyte is a solution containing lithium ions;
preferably, the electrolyte consists of a lithium source and a solvent, wherein the lithium source is LiPF 6 The solvent consists of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate according to the volume ratio of 1:1:1.
Optionally, the half cell further comprises a separator, which is Celgard2400.
The sixth aspect of the application provides an application of at least one of the porous graphene/lamellar graphene composite material and the porous graphene/lamellar graphene composite material prepared by the preparation method in any one of the above aspects in a lithium ion capacitor.
The application has the beneficial effects that:
the in-situ coating of the porous graphene on the surface of the lamellar graphene is realized, and the lithium ion capacitor anode material with high specific capacity (the specific capacity at 0.1A/g can reach 460 mAh/g), excellent rate performance (the specific capacity at 2.0A/g is 250 mAh/g) and long cycle life is obtained.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a scanning electron microscope image of a porous graphene coated platelet graphene prepared in example 1 of the present application;
fig. 2 is a graph showing the rate of the lithium ion capacitor in example 1 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The porous graphene in-situ coated lamellar graphene lithium ion capacitor negative electrode material and the preparation method thereof are specifically described below.
The features and capabilities of the present application are described in further detail below in connection with the examples.
The fluorine-doped graphene in the embodiment 1 is prepared according to an electrochemical anode sheet layer method described in the literature of Electrochemically Scalable Production of Fluorine-Modified Graphene for Flexible and High-Energy Ionogel-Based Microsupercapacitors, the number of layers of the obtained fluorine-doped graphene is concentrated in 3-10 layers, and the fluorine doping amount is 0.5-3 at%;
in the embodiment 2, the oxygen doped graphene is provided by Ningbo material technology and engineering institute of China academy of sciences, and the number of layers of the graphene is concentrated in 10-20 layers;
in the embodiment 3, the oxygen doped graphene is provided by Ningbo material technology and engineering institute of China academy of sciences, and the number of layers of the graphene is concentrated in 15-30 layers.
Example 1
After 100mg of lamellar graphene (namely fluorine doped graphene) is subjected to ultrasonic treatment for 1 hour, the lamellar graphene is added into 200mL of polydiallyl dimethyl ammonium chloride aqueous solution with the concentration of 0.2wt%, and the mixture is stirred for 1 hour and then filtered, so that the lamellar graphene with the surface modified is obtained. And re-dispersing the collected surface-modified lamellar graphene into 400mL of water, and continuing stirring for 0.5 hour after ultrasonic treatment for 0.5 hour again to obtain a surface-modified lamellar graphene dispersion liquid.
Preparing graphene oxide solution with the mass concentration of 0.5mg/ml, dropwise adding the graphene oxide solution into the prepared surface modification lamellar graphene dispersion liquid, wherein the dripping speed is 30 drops/min, continuously stirring for 2 hours, filtering and collecting to obtain the graphene oxide coated lamellar graphene composite material, and controlling the mass ratio of graphene oxide to surface modification lamellar graphene to be 1:4.
Uniformly mixing the obtained wet graphene oxide coated lamellar graphene composite material with potassium hydroxide with a certain mass, and controlling the mass ratio of the total mass of the graphene oxide coated lamellar graphene composite material to the mass of the potassium hydroxide to be 1:4. and (3) freeze-drying a mixture of the graphene oxide coated lamellar graphene composite material and potassium hydroxide to obtain a graphene/metal salt mixture, placing the freeze-dried graphene metal salt mixture in an argon atmosphere, performing activation treatment (the heating rate is 5 ℃/min) at 800 ℃ for 1 hour, grinding into powder, treating the activated sample with 1.0M hydrochloric acid, washing with deionized water to be neutral, and drying in a 100 ℃ oven for 8 hours to obtain the porous graphene/lamellar graphene composite material, which is marked as a product 1.
Example 2
After 100mg of lamellar graphene (namely oxygen doped graphene) is subjected to ultrasonic treatment for 1 hour, the lamellar graphene is added into 200mL of polyacrylamide aqueous solution with the concentration of 0.2wt%, and the mixture is stirred for 1 hour and then filtered, so that the lamellar graphene with the surface modified is obtained. And adding the collected surface-modified lamellar graphene into 400mL of water, and continuing stirring for 0.5 hour after ultrasonic treatment for 0.5 hour again to obtain a surface-modified lamellar graphene dispersion liquid.
Preparing graphene oxide solution with the mass concentration of 0.5mg/ml, dropwise adding the graphene oxide solution into the prepared surface-modified lamellar graphene dispersion liquid, wherein the dripping speed is 30 drops/min, continuously stirring for 0.5 hour, filtering and collecting to obtain a wet graphene oxide coated lamellar graphene composite material, and controlling the mass ratio of graphene oxide to surface-modified lamellar graphene to be 1:3.
uniformly mixing the obtained wet graphene oxide coated lamellar graphene composite material with potassium hydroxide with a certain mass, and controlling the mass ratio of the total mass of the graphene oxide coated lamellar graphene composite material to the mass of the potassium hydroxide to be 1:5. and (3) drying the graphene oxide coated lamellar graphene composite material and potassium hydroxide mixture in a vacuum drying oven at 65 ℃ to obtain a graphene metal salt mixture, placing the dried graphene metal salt mixture in an argon atmosphere, performing activation treatment (the heating rate is 5 ℃/min) at 800 ℃ for 1 hour, grinding into powder, treating the activated sample with 1M hydrochloric acid, washing with deionized water to be neutral, and drying in an oven at 100 ℃ for 8 hours to obtain the porous graphene/lamellar graphene composite material, which is marked as a product 2.
Example 3
And (3) adding 100mg of lamellar graphene (namely oxygen doped graphene) into 200mL of polydiallyl dimethyl ammonium chloride aqueous solution with the concentration of 0.5wt% after ultrasonic treatment for 1 hour, stirring for 1 hour, and filtering to obtain the lamellar graphene with the surface modified. And adding the collected surface-modified lamellar graphene into 400mL of water, and continuing stirring for 0.5 hour after ultrasonic treatment for 0.5 hour again to obtain a surface-modified lamellar graphene dispersion liquid.
Preparing graphene oxide solution with the mass concentration of 1.0mg/ml, dropwise adding the graphene oxide solution into the prepared surface-modified lamellar graphene dispersion liquid, continuously stirring for 0.5 hour at the dropping speed of 60 drops/min, filtering and collecting to obtain the wet graphene oxide coated lamellar graphene composite material, and controlling the mass ratio of graphene oxide to surface-modified lamellar graphene to be 1:1.
Uniformly mixing the obtained wet graphene oxide coated lamellar graphene composite material with zinc chloride with a certain mass, and controlling the mass ratio of the total amount of the graphene oxide coated lamellar graphene composite material to the zinc chloride to be 1:10. and (3) freeze-drying the mixture of the graphene oxide coated lamellar graphene composite material and zinc chloride to obtain a graphene metal salt mixture, placing the freeze-dried graphene metal salt mixture in an argon atmosphere, performing activation treatment (the heating rate is 5 ℃/min) at 1000 ℃ for 1 hour, grinding into powder, treating an activated sample with 2.0M hydrochloric acid, washing with deionized water to be neutral, and drying in an oven at 120 ℃ for 6 hours to obtain the porous graphene/lamellar graphene composite material, which is marked as a product 3.
Example 4 characterization of the products
As shown in fig. 1, SEM images of the product of example 1. As can be seen from fig. 1, the graphene oxide on the surface of the layered graphene forms porous graphene under the action of the pore-forming agent, and is tightly wrapped on the surface of the lamellar graphene, thus proving the synthesis of the porous graphene/lamellar graphene composite material.
Example 5 performance testing of the products of the examples
1. Preparation of electrodes
Mixing the product with ketjen black and polyvinylidene fluoride according to the mass ratio of 80:10:10, adding N-methyl pyrrolidone, mixing to obtain uniform slurry, uniformly coating on copper foil by coating method, oven drying at 100deg.C, and punching to obtain round electrode plate with diameter of 12mm, and the load of electrode material (product) is 1.0-1.5mg/cm 2 。
2. Preparation of half-cell corresponding to lithium ion capacitor
The half cell uses the obtained round electrode plate as a positive electrode and metal lithium as a counter electrode, and the electrolyte is 1M LiPF 6 Ethylene carbonate/methyl ethyl carbonate/dimethyl carbonate (volume ratio 1:1:1), the diaphragm was Celgard2400. After standing for 12 hours, electrochemical performance test was performed. The voltage interval is 0.02-3V, and the current density is 0.1,0.2,0.5,1.0,2.0,5.0,8.0 and 10.0A/g.
As a representative example of the product 1, the result was shown in FIG. 2, wherein the specific capacity of the product 1 as a negative electrode active material was 460mAh/g at a current density of 0.1A/g and 250mAh/g at an increase in current density to 2.0A/g.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (6)
1. The porous graphene/lamellar graphene composite material is characterized by comprising lamellar graphene and porous graphene;
the porous graphene is coated on the surface of the lamellar graphene;
the lamellar graphene contains doping elements;
the doping element comprises any one of fluorine element and oxygen element;
the thickness of the lamellar graphene is more than 3 layers and less than 10 nm;
the preparation method of the porous graphene/lamellar graphene composite material comprises the following steps:
1) Mixing dispersion liquid containing lamellar graphene and a surface modifier to obtain surface modified graphene;
2) Mixing dispersion liquid containing graphene oxide and the surface-modified graphene to obtain a graphene oxide coated lamellar graphene composite material;
3) Reacting the mixture containing the graphene oxide coated lamellar graphene composite material and an activating agent to obtain the porous graphene/lamellar graphene composite material;
the mass ratio of the graphene oxide to the surface modified graphene in the step 2) is 1: 0.5-50;
the mass concentration of the graphene oxide dispersion liquid is 0.1-5.0 mg/ml;
step 3) the mass ratio of the graphene oxide coated lamellar graphene composite material to the activator is 1: 0.1-50;
the reaction conditions of step 3) include:
under an inert atmosphere;
the reaction temperature is 700-1100 ℃;
the reaction time is 0.5-8 h.
2. The porous graphene/lamellar graphene composite material according to claim 1, characterized in that the lamellar graphene in step 1) is graphene prepared by a exfoliation method;
the surface modifier in the step 1) is selected from polycation electrolyte;
the polycation electrolyte is at least one selected from polydimethyl diallyl ammonium chloride, polyacrylamide hydrochloride, polyacrylamide and polyethyleneimine;
step 1) comprises: firstly carrying out ultrasonic treatment on the lamellar graphene for 30-90 min, then adding the lamellar graphene into a solution containing a surface modifier to obtain a dispersion liquid, and stirring the dispersion liquid for 0.5-2.0 h to obtain the surface modified graphene;
in the solution containing the surface modifier, the concentration of the surface modifier is 0.2-2wt%;
the dispersion liquid containing graphene oxide and the surface modified graphene in the step 2) is obtained by the following steps:
preparing graphene oxide dispersion liquid and surface modified graphene dispersion liquid respectively;
dropwise adding the graphene oxide dispersion liquid into the surface modified graphene dispersion liquid, and obtaining the graphene oxide dispersion liquid after the dropwise adding is finished;
the dropping speed is 30-120 drops/min;
step 2), mixing is carried out under the stirring condition, and the stirring time is 0.5-2 h;
step 3) the activator is at least one selected from potassium hydroxide, potassium carbonate, sodium hydroxide, sodium sulfate and zinc chloride;
the mixture containing the graphene oxide coated lamellar graphene composite material and the activating agent in the step 3) is obtained by the following method:
mixing an activating agent with the wet graphene oxide coated lamellar graphene composite material obtained in the step 2), and freeze-drying to obtain a mixture;
the reaction of step 3) further comprises the following steps:
and grinding the reaction product into powder and carrying out acid washing treatment to obtain the powdery porous graphene/lamellar graphene composite material.
3. An electrode, comprising:
an active substance;
a conductive agent;
a binder; and
a current collector;
wherein the active material is the porous graphene/lamellar graphene composite material according to any one of claims 1-2.
4. A method of making an electrode comprising:
and coating slurry containing an active substance, a conductive agent and a binder on a current collector to obtain the electrode, wherein the active substance is the porous graphene/lamellar graphene composite material according to any one of claims 1-2.
5. A half cell comprising:
a positive electrode which is at least one of the electrode of claim 3 and the electrode prepared by the preparation method of claim 4;
an electrolyte; and
and a negative electrode, a metal lithium sheet.
6. The use of the porous graphene/lamellar graphene composite material according to any one of claims 1-2 in lithium ion capacitors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011162539.9A CN114477155B (en) | 2020-10-27 | 2020-10-27 | Porous graphene/lamellar graphene composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011162539.9A CN114477155B (en) | 2020-10-27 | 2020-10-27 | Porous graphene/lamellar graphene composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114477155A CN114477155A (en) | 2022-05-13 |
| CN114477155B true CN114477155B (en) | 2023-11-10 |
Family
ID=81470291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011162539.9A Active CN114477155B (en) | 2020-10-27 | 2020-10-27 | Porous graphene/lamellar graphene composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114477155B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106847534A (en) * | 2016-12-16 | 2017-06-13 | 宁波中车新能源科技有限公司 | A kind of preparation method of Graphene/absorbent charcoal composite material, Graphene/active carbon combined electrode piece and ultracapacitor |
| CN107611394A (en) * | 2017-09-08 | 2018-01-19 | 成都硅宝科技股份有限公司 | A kind of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating and preparation method thereof |
| CN107887581A (en) * | 2017-10-30 | 2018-04-06 | 北京万源工业有限公司 | Porous graphene coated graphite, preparation and the application on lithium ion battery |
| CN109081333A (en) * | 2017-12-05 | 2018-12-25 | 中国科学院大连化学物理研究所 | A kind of method that electrochemical stripping prepares Fluorin doped graphene |
-
2020
- 2020-10-27 CN CN202011162539.9A patent/CN114477155B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106847534A (en) * | 2016-12-16 | 2017-06-13 | 宁波中车新能源科技有限公司 | A kind of preparation method of Graphene/absorbent charcoal composite material, Graphene/active carbon combined electrode piece and ultracapacitor |
| CN107611394A (en) * | 2017-09-08 | 2018-01-19 | 成都硅宝科技股份有限公司 | A kind of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating and preparation method thereof |
| CN107887581A (en) * | 2017-10-30 | 2018-04-06 | 北京万源工业有限公司 | Porous graphene coated graphite, preparation and the application on lithium ion battery |
| CN109081333A (en) * | 2017-12-05 | 2018-12-25 | 中国科学院大连化学物理研究所 | A kind of method that electrochemical stripping prepares Fluorin doped graphene |
Non-Patent Citations (1)
| Title |
|---|
| Porous graphene sandwich/poly(vinylidene fluoride) composites with high dielectric properties;Liangyong Chu等;Composites Science and Technology;70–75 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114477155A (en) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111554919B (en) | Positive electrode active material, preparation method thereof and sodium ion battery | |
| Yang et al. | Graphitic carbon materials extracted from spent carbon cathode of aluminium reduction cell as anodes for lithium ion batteries: Converting the hazardous wastes into value-added materials | |
| JP5557564B2 (en) | Nitrogen-containing carbon alloy and carbon catalyst using the same | |
| CN113328068B (en) | Carbon nanotube hard carbon composite negative electrode material with core-shell structure, and preparation method and application thereof | |
| Gao et al. | TiO2@ Porous carbon nanotubes modified separator as polysulfide barrier for lithium-sulfur batteries | |
| CN114050265B (en) | Nickel selenide/manganese selenide nanocomposite loaded by crosslinked nano carbon sheet, preparation method of nickel selenide/manganese selenide nanocomposite and sodium ion battery negative electrode | |
| Saroha et al. | Asymmetric separator integrated with ferroelectric-BaTiO3 and mesoporous-CNT for the reutilization of soluble polysulfide in lithium-sulfur batteries | |
| CN108767203B (en) | Titanium dioxide nanotube-graphene-sulfur composite material and preparation method and application thereof | |
| CN115763717A (en) | Sodium ion battery positive electrode material, preparation method thereof, sodium ion battery positive electrode piece and sodium ion battery | |
| CN114400309A (en) | Sodium ion positive electrode material and preparation method and application thereof | |
| Mao et al. | Advanced Aqueous Zinc‐Ion Batteries Enabled by 3D Ternary MnO/Reduced Graphene Oxide/Multiwall Carbon Nanotube Hybrids | |
| CN111554905B (en) | Preparation method, product and application of zinc oxide-based carbon composite nano material | |
| CN111063549B (en) | Two-dimensional MOFs nanosheet-derived full-electrode material for hybrid capacitor | |
| CN113178571A (en) | Hierarchical porous Fe3Se4@ NC @ CNTs composite material and preparation method and application thereof | |
| CN109449440B (en) | Microporous ultrathin soft carbon nanosheet and preparation method and application thereof | |
| KR20140023858A (en) | Anodes active material containing si composite for lithium secondary batteries and its preparation method and lithium secondary batteries comprising the same | |
| CN112768679A (en) | One-dimensional pea-shaped bimetallic ferric vanadate nanowire material and preparation method and application thereof | |
| CN114477155B (en) | Porous graphene/lamellar graphene composite material and preparation method and application thereof | |
| Wang et al. | A unique two-phase heterostructure with cubic NiSe 2 and orthorhombic NiSe 2 for enhanced lithium ion storage and electrocatalysis | |
| CN108258227B (en) | Preparation method of silicon-carbon composite material based on silicon-based molecular sieve structure and lithium battery | |
| EP4203109A1 (en) | Conductive carbon, method for producing same, method for producing conductive carbon mixture containing said conductive carbon, and method for producing electrode using said conductive carbon or conductive carbon mixture | |
| Tian et al. | Recombination and Electrochemical Performance of Iodine and Mesoporous Carbon | |
| CN115472801B (en) | Preparation method and application of hydrogenated titanium dioxide modified core-shell structure carbon coated porous ferroferric oxide and nickel oxide | |
| CN112670502B (en) | Antimony telluride nanosheet and application thereof in water-based zinc ion battery | |
| CN113277516B (en) | Porous spherical graphene-coated silicon negative electrode composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |