CN106252634A - Graphene aerogel load CNT and ZIF 67 electrode material of lithium battery preparation method - Google Patents

Graphene aerogel load CNT and ZIF 67 electrode material of lithium battery preparation method Download PDF

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CN106252634A
CN106252634A CN201610847675.9A CN201610847675A CN106252634A CN 106252634 A CN106252634 A CN 106252634A CN 201610847675 A CN201610847675 A CN 201610847675A CN 106252634 A CN106252634 A CN 106252634A
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zif
gas
cnt
electrode material
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CN106252634B (en
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孙炜伟
王勇
李�浩
梁明
蔡昌
杨秦斯
陈思
张文博
尹晓杰
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University of Shanghai for Science and Technology
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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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • 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
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of 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
    • H01M4/36—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
    • 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
    • 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

Abstract

nullThe invention discloses a kind of graphene aerogel load CNT and ZIF 67 electrode material of lithium battery preparation method，The method is to prepare graphene oxide by natural graphite powder chemical oxidation stripping method，Add CNT (CNTs) ultrasonic，The complex (GAS@CNTs) of porous graphene aeroge (GAS) and CNTs is prepared by hydro-thermal method and freeze-drying，Again by itself and ZIF 67 solution stirring，After standing，Prepare graphene aerogel (GAS) load CNT (CNTs) and ZIF 67 electrode material of lithium battery (GAS@CNTs@ZIF 67)，The method it is crucial that，The complex of GAS Yu CNTs is prepared by hydro-thermal method and freeze-drying，Add ZIF 67，Stir dispersion，Vacuum drying obtains GAS@CNTs@ZIF 67 electrode material of lithium battery,Understand through electro-chemical test,This aerogel carried CNT of novel graphite alkene and the ZIF 67 electrode material of lithium battery capacity that compares is high，Good cycling stability，There is commercialization and can apply to pure electric automobile.

Description

Prepared by graphene aerogel load CNT and ZIF-67 electrode material of lithium battery Method
Technical field
The present invention relates to a kind of graphene aerogel load CNT and ZIF-67 electrode material of lithium battery preparation method, Belong to lithium ion power battery electrode technical field of material.
Background technology
Aeroge is the globality material that a class has flourishing pore structure, and this prosperity pore structure has that density is low, thermal conductance The electricity advantages such as rate is little, hole is flourishing.Graphene aerogel (Graphene aerogel, referred to as GAS) is referred to as Graphene sea Continuous (Graphene sponge), graphene macroform (Graphene monaolith) or grapheme foam (Graphene Foam).It not only has the three-dimensional pore space knot of the advantage of conventional aeroge, the conductive characteristic also with charcoal-aero gel and uniqueness Structure, and the structure of this uniqueness makes it have more electrochemical reaction avtive spot than Graphene, thus greatly improve Its storage lithium performance.CNT and Graphene have similar character at aspects such as electrochemistry and mechanics, but owing to microcosmic is tied The difference of structure, they also have respective performance.In order to combine both advantages, Graphene and CNT are provided commonly for multiple Condensation material, forms three-dimensional porous structure, by cooperative effect between the two so that it is show than wherein any homogenous material more Add the performance of excellence.
Lithium ion battery is widely used in mobile phone, notebook due to its stable cycle performance and high energy density The fields such as computer, electric automobile (EV), but along with the epoch progress and science and technology development, the conventional lithium ion with graphite as electrode Battery has been difficult to the requirement meeting people to energy storage device.Graphene and CNT are because having big surface area, excellence Electric conductivity and mechanical performance and be considered as most potential electrode material.In order to further enhance Graphene and carbon nanometer Pipe and the storage lithium performance of both composites, people are often added to other materials with composition ternary or multiple elements design body System.
Metallic organic framework (MOF) structure is to be formed as connecting line using metal ion as junction point, organic ligand Three-dimensional porous structure.Metal ion in metallic organic framework can serve as redox reaction in electrochemical reaction process Avtive spot, so metallic organic framework is also typically used to the electrode material of lithium ion battery.The gold of zeolite type imidazoles Belonging to organic backbone ZIF-67 is with divalent transition metal Co2+New with the one with zeolite topological that imidazole radicals part is constructed Type porous crystalline material, the metal center Co in its structure2+Ion energy and Li+Ion generation reversible transformation reacts, thus reaches Storage lithium requirement.As Saravanan Kuppan et al. has synthesized a class, there is the metallo-organic framework Zn of diamond structures3 (HCOO)6、Co3(HCOO)6And Zn1.5Co1.5(HCOO)6 , and by them and Li+Conversion reversible reaction realize storage lithium performance, Structure C o therein3(HCOO)6Under conditions of electric current density is 60 mA/g, after 60 circle circulations, still there is the electric discharge of 410 mAh/g Specific capacity, hence it is evident that be better than the specific capacity (J. Mater. Chem. 2010,20,8329-8335) of commercial graphite.But ZIF-67 At deintercalation Li+During metallo-organic framework can be destroyed, it is combined with graphene aerogel and can effectively alleviate knot The destruction of structure, thus show the electrochemistry cyclicity of excellence.And graphene aerogel has more electrochemistry than Graphene Reactivity site, thus there is more preferable chemical property.Ren et al. by hydro-thermal self assembling process on graphene sheet layer Successfully having loaded the adjustable three-dimensional layering porous graphene aeroge of duct size, this composite is close at the electric current of 0.1A/g Under degree, specific discharge capacity reaches 1100 mAh/g, be better than the most far away graphite electrode (Scientific Reports, 2015, 5,14229).
In a word, it is designed with pore passage structure and the carrier of abundant electrochemical reaction avtive spot, is beneficial to solve The electrode material structural damage problem that lithium ion battery causes due to the deintercalation repeatedly of lithium ion in charge and discharge process, thus Advance the development of lithium ion battery electrode material.
Summary of the invention
The present invention is with natural graphite powder as raw material, prepares graphene oxide by chemical oxidation stripping method, adds After CNT (CNTs) ultrasonic mixing, by hydro-thermal method and freeze-drying prepare porous graphene aeroge (GAS) with The complex (GAS@CNTs) of CNTs, then GAS@CNTs is mixed with the stirring of metallic organic framework ZIF-67 precursor solution, quiet After putting a period of time, prepare graphene aerogel load CNT and ZIF-67 electrode material of lithium battery (GAS@CNTs@ZIF- 67), the method is it is crucial that hydro-thermal method to be passed through and freeze-drying prepare the complex of GAS Yu CNTs, answering at GAS with CNTs Compound adds ZIF-67, by the dispersion that stirs, after vacuum drying, obtains GAS@CNTs@ZIF-67 electrode of lithium cell material Material.Understand through electro-chemical test, this aerogel carried CNT of novel graphite alkene and ZIF-67 electrode material of lithium battery, phase To specific capacity height, good cycling stability, preparation method is simple, experiment condition is gentle, has and business-like may and can be applicable to Pure electric automobile.
The present invention is achieved by the following technical solutions.
The present invention is a kind of graphene aerogel load CNT and ZIF-67 electrode material of lithium battery preparation method, its It is characterized by following technical process and step:
A. weigh in the flask that 2-2.5g natural graphite powder pours 1000ml into, add the HNO of 100-150ml concentration 65%3 , Again flask is placed in ice-water bath, is maintained at the H being slowly added to 100-150ml concentration 98% at 0 DEG C2SO4 , after stirring 1-2h, Add 8-15g KMnO4, it is warming up to 30-40 DEG C of reaction 2-3h, then is warming up to 70-90 DEG C of reaction 1-2h；Add after being cooled to room temperature Obtain brown colloidal material after 300-500ml distilled water diluting concentrated acid, add 35% H of 30-50ml2O2And 100- 10% HCl of 150ml cleans, and obtains brown yellow solution；Centrifugal water is washed till neutrality；At 50-60 DEG C, air drying obtains Graphene oxygen Compound；
B. weigh the above-mentioned graphene oxide of 0.04g, add the distilled water of 20ml, after ultrasonic 30-60min, add 0.02g CNT (CNTs) continues ultrasonic disperse 1-1.5h, 180 DEG C of hydro-thermal reactions 12h, then lyophilization, baking temperature is-30- 40 DEG C, prepare graphene aerogel (GAS) and the complex (GAS@CNTs) of CNT (CNTs)；
C. graphene aerogel (GAS) and complex (the GAS@CNTs) addition of CNTs that 0.05g step (b) obtains are weighed In 25ml methanol solution, ultrasonic disperse 20-30min, add 0.249g Co (NO3)2·6H2O；Instill 25ml 2-methyl miaow again The methanol solution of azoles, stirs 10-20min, stands after 24h with ethanol centrifuge washing 6-8 time, the most i.e. obtain GAS@CNTs with ZIF-67 complex；
D. GAS@CNTs@ZIF-67, acetylene black, PVDF adhesive, GAS@CNTs@ZIF-67, acetylene black, PVDF gluing are chosen Agent, then feeds the mixture in N-N dimethyl pyrrolidone than mix homogeneously with the quality of 8:1:1, and ultrasonic disperse, obtains Gluey black liquor；Disperseing serosity with high speed inner-rotary type beater, each one minute repeats 5-10 time, obtains homogeneous GAS CNTs@ZIF-6 black glue slurry；
E. above-mentioned black glue slurry is coated on the metallic copper collector handled well in advance uniformly, is placed in vacuum drying oven In be dried, temperature is set as 60-80 DEG C, drying time 12-24h；Finally give graphene aerogel load CNT and ZIF-67 electrode material of lithium battery.
Compared with prior art, this method pass through hydro-thermal method, freeze-drying and ultrasonic disperse, successfully prepare GAS with It is also effectively combined by the complex of CNTs with ZIF-67, final obtains graphene aerogel load CNT and ZIF-67 lithium Battery electrode material, this material has abundant electrochemical reaction avtive spot and abundant pore passage structure, thus compares Capacity height, good cycling stability, preparation method is simple, experiment condition is gentle feature.
Accompanying drawing explanation
Fig. 1 is graphene aerogel load CNT and X-ray diffraction (XRD) figure of ZIF-67 electrode material of lithium battery Spectrum；
Fig. 2 is scanning electron microscope (SEM) photo of the material of graphene aerogel load CNT；
Fig. 3 is graphene aerogel load CNT and transmission electron microscope (TEM) photo of ZIF-67 electrode material of lithium battery；
Fig. 4 is graphene aerogel load CNT and small area analysis (0.1C) discharge and recharge of ZIF-67 electrode material of lithium battery Cycle performance figure.
Detailed description of the invention
Now the present invention is embodied as after case is described in.
Embodiment 1
A kind of graphene aerogel load CNT and ZIF-67 electrode material of lithium battery preparation method, its step is as follows:
A. weigh 2g natural graphite powder and pour in flask, add the HNO of 100ml concentration 65%3, then flask is placed on ice-water bath In, it is maintained at 0 DEG C and is slowly added to the H that 100ml concentration is 98%2SO4, after stirring 1h, add 10g KMnO4, it is warming up to 35 DEG C Reaction 2h, then it is warming up to 75 DEG C of reaction 1h；Add 500ml distilled water diluting concentrated acid after being cooled to room temperature and obtain brown colloidal Material, adds 35% H of 40ml2O2And 10% HCl of 100ml cleans, obtain brown yellow solution；Centrifugal water is washed till neutrality；60 At DEG C, air drying obtains graphene oxide；
B. weigh the above-mentioned graphene oxide of 0.04g, add the distilled water of 20ml, after ultrasonic 30 min, add 0.02g carbon Nanotube (CNTs) ultrasonic disperse 1h, 180 DEG C of hydro-thermal reactions 12h, then lyophilization, baking temperature is-30-40 DEG C, system Obtain graphene aerogel (GAS) and the complex (GAS@CNTs) of CNT (CNTs)；
C. the complex GAS@CNTs weighing what 0.05g step (b) obtained alkene aeroge (GAS) and CNTs adds 25ml first In alcoholic solution, ultrasonic 30 min, add 0.249g Co (NO3)2·6H2O；Instill the methanol solution of 25ml 2-methylimidazole again, Stirring 20min, uses ethanol centrifuge washing 7 times after standing 24h, the most i.e. obtains GAS@CNTs@ZIF-67 complex；
D. GAS@CNTs@ZIF-67, acetylene black, PVDF adhesive, GAS@CNTs@ZIF-67, acetylene black, PVDF gluing are chosen Agent, then feeds the mixture in N-N dimethyl pyrrolidone than mix homogeneously with the quality of 8:1:1, and ultrasonic disperse, obtains Gluey black serosity；Disperse serosity with high speed inner-rotary type beater, within each one minute, be repeated 10 times, obtain homogeneous GAS CNTs@ZIF-67 black glue slurry；
E. above-mentioned black glue slurry is coated on the metallic copper collector handled well in advance uniformly, is placed in vacuum drying oven In be dried, temperature is set as 80 DEG C, drying time 24h；Finally give graphene aerogel load CNT and ZIF-67 lithium Battery electrode material.
The assembling of battery and test thereof
The above-mentioned electrode to be measured prepared is put in self-control rustless steel battery mould and tests, using high purity lithium sheet as negative pole, poly- Propylene perforated membrane (Celgard 2400) is barrier film, and electrolyte is trifluoromethanesulfonyl chloride LiTFSI and the Polyethylene Glycol of 1mol/L (PEG) mixed solution of/dimethyl ether (DME) (weight ratio is 1:1).The glove box being assembled in full high-purity argon gas of battery enters OK；Test electric current density is 0.1C, and wherein 1C is equal to 1000 mA/g, and test voltage scope is 1-3V.
Shown in accompanying drawing 1: the analysis showed that product is metallic organic framework ZIF-67 that degree of crystallinity is higher and CNT is born The electrode material of lithium battery being loaded on graphene aerogel.Fig. 2 is that the scanning SEM of graphene aerogel load CNT shines Sheet, it can be seen that CNT is interspersed in graphene aerogel；Fig. 3 is graphene aerogel load CNT and ZIF-67 The transmission electron microscope TEM photo of electrode material of lithium battery, it can be seen that be attached with hexagonal on graphene aerogel fold lamella ZIF-67 granule and the CNT of tubulose.In figs. 2 and 3, it appeared that CNT and ZIF-67 are in Graphene airsetting On glue dispersed, form the three-dimensional porous complex of a kind of multi-stage artery structure.Fig. 4 is that graphene aerogel loads carbon nanometer The cycle performance figure of small area analysis (0.1C) discharge and recharge of pipe and ZIF-67 electrode material of lithium battery, figure 4, it can be seen that battery exists After small area analysis charge and discharge circulation 50 circle, specific capacity can be maintained at about 600 mAh/g.This material specific capacity visible is high, stable circulation Performance is good, has business-like potentiality.

Claims (1)

1. a graphene aerogel load CNT and ZIF-67 electrode material of lithium battery preparation method, it is characterised in that The method has steps of:
A. weigh in the flask that 2-2.5g natural graphite powder pours 1000ml into, add the HNO of 100-150ml concentration 65%3, then Flask is placed in ice-water bath, at keeping 0 DEG C, is slowly added to the H of 100-150ml concentration 98%2SO4, after stirring 1-2h, add 8-15g KMnO4, it is warming up to 30-40 DEG C of reaction 2-3h, then is warming up to 70-90 DEG C of reaction 1-2h；300-is added after being cooled to room temperature Obtain brown colloidal material after 500ml distilled water diluting concentrated acid, add 35% H of 30-50ml2O2And 100-150ml 10% HCl cleans, and obtains brown yellow solution；Centrifugal water is washed till neutrality；At 50-60 DEG C, air drying obtains graphene oxide；
B. weigh the above-mentioned graphene oxide of 0.04g, add the distilled water of 20ml, after ultrasonic 30-60min, add 0.02g CNT (CNTs) continues ultrasonic disperse 1-1.5h, 180 DEG C of hydro-thermal reactions 12h, then lyophilization, baking temperature is-30- 40 DEG C, prepare graphene aerogel (GAS) and the complex (GAS@CNTs) of CNT (CNTs)；
C. graphene aerogel (GAS) and complex (the GAS@CNTs) addition of CNTs that 0.05g step (b) obtains are weighed In 25ml methanol solution, ultrasonic disperse 20-30min, add 0.249g Co (NO3)2·6H2O；Instill 25ml 2-methyl miaow again The methanol solution of azoles, stirs 10-20min, stands after 24 h with ethanol centrifuge washing 6-8 time, the most i.e. obtain GAS@CNTs with ZIF-67 complex；
D. GAS@CNTs@ZIF-67, acetylene black, PVDF adhesive, GAS@CNTs@ZIF-67, acetylene black, PVDF gluing are chosen Agent, then feeds the mixture in N-N dimethyl pyrrolidone than mix homogeneously with the quality of 8:1:1, and ultrasonic disperse, obtains Gluey black liquor；Disperseing serosity with high speed inner-rotary type beater, each one minute repeats 5-10 time, obtains homogeneous GAS CNTs@ZIF-6 black glue slurry；
E. above-mentioned black glue slurry is coated on the metallic copper collector handled well in advance uniformly, is placed in vacuum drying oven In be dried, temperature is set as 60-80 DEG C, drying time 12-24h；Finally give graphene aerogel load CNT and ZIF-67 electrode material of lithium battery.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109499493A (en) * 2018-12-07 2019-03-22 武汉工程大学 A kind of polypyrrole/ZIF-67 composite aerogel and preparation method thereof
CN109637835A (en) * 2018-12-07 2019-04-16 武汉工程大学 A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel and preparation method thereof
CN109962218A (en) * 2017-12-25 2019-07-02 南京理工大学 The preparation method of ZIF-67/GO composite material
CN110350206A (en) * 2018-08-27 2019-10-18 哈尔滨工业大学 Vertical graphene-supported carbon nano-tube combination electrode material and preparation method thereof and the application in all solid state zinc-air battery
CN111848892A (en) * 2020-06-11 2020-10-30 上海大学 Preparation method of carbon nanotube-loaded two-dimensional covalent organic framework electrode material
CN114141992A (en) * 2021-11-30 2022-03-04 四川启睿克科技有限公司 Self-propagating alloyed lithium negative electrode and preparation method thereof
CN114864293A (en) * 2022-04-25 2022-08-05 武汉大学 Three-dimensional CNTs/RGO-metal organic framework hydrogel electrode, and preparation method and application thereof
CN115117349A (en) * 2022-06-30 2022-09-27 合肥国轩高科动力能源有限公司 Elastic conductive network conductive agent for silicon-carbon cathode of lithium ion battery, preparation method of slurry of conductive agent and lithium ion battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105129927A (en) * 2015-09-10 2015-12-09 上海大学 Preparing method of graphene/carbon nanotube aerogel composite capacitive type desalting electrode
CN105289695A (en) * 2015-12-08 2016-02-03 武汉理工大学 Graphene loaded Co-N-C oxygen reduction catalyst and preparation method thereof
CN105590757A (en) * 2014-11-18 2016-05-18 中国科学院宁波材料技术与工程研究所 Carbon nanotube/graphene composite gel and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105590757A (en) * 2014-11-18 2016-05-18 中国科学院宁波材料技术与工程研究所 Carbon nanotube/graphene composite gel and preparation method thereof
CN105129927A (en) * 2015-09-10 2015-12-09 上海大学 Preparing method of graphene/carbon nanotube aerogel composite capacitive type desalting electrode
CN105289695A (en) * 2015-12-08 2016-02-03 武汉理工大学 Graphene loaded Co-N-C oxygen reduction catalyst and preparation method thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DONGMING YIN ET AL.: "RGO/Co3O4 Composites Prepared Using GO-MOFs as Precursor for Advanced Lithium-ion Batteries and Supercapacitors Electrodes", 《ELECTROCHIMICA ACTA》 *
QUNTING QU ET AL.: "Graphene oxides-guided growth of ultrafine Co3O4 nanocrystallites from MOFs as high-performance anode of Li-ion batteries", 《CARBON》 *
WENCHAO WAN ET AL.: "Graphene–carbon nanotube aerogel as an ultralight,compressible and recyclable highly efficient absorbent for oil and dyes", 《ENVIRON. SCI.: NANO》 *
ZENG FAN ET AL.: "Thermal and electrical properties of graphene/carbon nanotube aerogels", 《COLLOIDS AND SURFACES A: PHYSICOCHEM. ENG. ASPECTS》 *
ZHIHUA MA ET AL.: "Preparation of a graphene-based composite aerogel and the effects of carbon nanotubes on preserving the porous structure of the aerogel and improving its capacitor performance", 《J. MATER. CHEM. A》 *

Cited By (13)

* Cited by examiner, † Cited by third party
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CN109962218A (en) * 2017-12-25 2019-07-02 南京理工大学 The preparation method of ZIF-67/GO composite material
CN109962218B (en) * 2017-12-25 2022-03-22 南京理工大学 Preparation method of ZIF-67/GO composite material
CN110350206B (en) * 2018-08-27 2022-04-26 哈尔滨工业大学 Vertical graphene loaded carbon nanotube composite electrode material, preparation method thereof and application of vertical graphene loaded carbon nanotube composite electrode material in all-solid-state zinc-air battery
CN110350206A (en) * 2018-08-27 2019-10-18 哈尔滨工业大学 Vertical graphene-supported carbon nano-tube combination electrode material and preparation method thereof and the application in all solid state zinc-air battery
CN109499493B (en) * 2018-12-07 2021-08-13 武汉工程大学 polypyrrole/ZIF-67 composite aerogel and preparation method thereof
CN109637835B (en) * 2018-12-07 2021-08-13 武汉工程大学 Nitrogen-doped carbon nanotube/cobaltosic oxide composite aerogel and preparation method thereof
CN109637835A (en) * 2018-12-07 2019-04-16 武汉工程大学 A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite aerogel and preparation method thereof
CN109499493A (en) * 2018-12-07 2019-03-22 武汉工程大学 A kind of polypyrrole/ZIF-67 composite aerogel and preparation method thereof
CN111848892A (en) * 2020-06-11 2020-10-30 上海大学 Preparation method of carbon nanotube-loaded two-dimensional covalent organic framework electrode material
CN114141992A (en) * 2021-11-30 2022-03-04 四川启睿克科技有限公司 Self-propagating alloyed lithium negative electrode and preparation method thereof
CN114864293A (en) * 2022-04-25 2022-08-05 武汉大学 Three-dimensional CNTs/RGO-metal organic framework hydrogel electrode, and preparation method and application thereof
CN115117349A (en) * 2022-06-30 2022-09-27 合肥国轩高科动力能源有限公司 Elastic conductive network conductive agent for silicon-carbon cathode of lithium ion battery, preparation method of slurry of conductive agent and lithium ion battery
CN115117349B (en) * 2022-06-30 2023-10-10 合肥国轩高科动力能源有限公司 Elastic conductive network conductive agent for silicon-carbon negative electrode of lithium ion battery, preparation method of slurry of elastic conductive network conductive agent and lithium ion battery

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