CN106252634B - Graphene aerogel loads carbon nanotube and ZIF-67 electrode material of lithium battery preparation method - Google Patents

Graphene aerogel loads carbon nanotube and ZIF-67 electrode material of lithium battery preparation method Download PDF

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CN106252634B
CN106252634B CN201610847675.9A CN201610847675A CN106252634B CN 106252634 B CN106252634 B CN 106252634B CN 201610847675 A CN201610847675 A CN 201610847675A CN 106252634 B CN106252634 B CN 106252634B
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carbon nanotube
graphene
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CN106252634A (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

The invention discloses a kind of graphene aerogel load carbon nanotube and ZIF-67 electrode material of lithium battery preparation methods, this method is to prepare graphene oxide by natural graphite powder chemical oxidation stripping method, add carbon nanotube (CNTs) ultrasound, the compound (GAS@CNTs) of porous graphene aeroge (GAS) Yu CNTs are prepared by hydro-thermal method and freeze-drying, it is stirred with ZIF-67 solution again, after standing, graphene aerogel (GAS) load carbon nanotube (CNTs) and ZIF-67 electrode material of lithium battery (GAS@CNTs@ZIF-67) is made, the key of this method is, the compound of GAS and CNTs are prepared by hydro-thermal method and freeze-drying, add ZIF-67, stir evenly dispersion, very Sky is dried to obtain GAS@CNTs@ZIF-67 electrode material of lithium battery, through known to electro-chemical test, with respect to specific capacity height, good cycling stability has and is commercialized and can apply to pure electric automobile for the aerogel carried carbon nanotube of the novel graphene and ZIF-67 electrode material of lithium battery.

Description

Graphene aerogel loads carbon nanotube and the preparation of ZIF-67 electrode material of lithium battery Method
Technical field
The present invention relates to a kind of graphene aerogels to load carbon nanotube and ZIF-67 electrode material of lithium battery preparation method, Belong to lithium ion power battery electrode technical field of material.
Background technique
Aeroge is a kind of globality material with flourishing pore structure, the developed pore structure low, thermal conductivity with density The advantages that electric rate is small, 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 advantages that conventional aeroge, also with the conductive characteristic and unique three-dimensional pore space knot of charcoal-aero gel Structure, and this unique structure makes it have more electrochemical reaction active sites than graphene, to greatly improve Its storage lithium performance.Carbon nanotube and graphene electrochemistry and in terms of have similar property, but due to microcosmic knot The difference of structure, they also have respective performance.Graphene and carbon nanotube are provided commonly for multiple by the advantages of in order to combine the two Condensation material, forming three-dimensional porous structure shows it than wherein any homogenous material more by synergistic effect between the two Add excellent performance.
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 car (EV), but with the development of the progress in epoch and science and technology, using graphite as the conventional lithium ion of electrode Battery has been difficult the requirement for meeting people to energy storage device.Graphene and carbon nanotube are because have big surface area, excellent Electric conductivity and mechanical performance and be considered as most potential electrode material.In order to further enhance graphene and carbon nanometer The storage lithium performance of pipe and the two composite material, people add other substances thereto often to form ternary or multiple elements design body System.
Metal organic framework (MOF) structure is using metal ion as tie point, and organic ligand is formed as connecting line Three-dimensional porous structure.Metal ion in metal organic framework can serve as redox reaction in electrochemical reaction process Active site, so metal 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+The one kind with zeolite topological constructed with imidazoles ylidene ligands is new Type porous crystalline material, the metal center Co in structure2+Ion energy and Li+Reversible transformation reaction occurs for ion, to reach Store up lithium requirement.As Saravanan Kuppan et al. has synthesized a kind of metallo-organic framework Zn with diamond structures3 (HCOO)6、Co3(HCOO)6And Zn1.5Co1.5(HCOO)6 , and pass through they and Li+Conversion reversible reaction realize storage lithium performance, Structure C o therein3(HCOO)6Under conditions of current density is 60 mA/g, still there is the electric discharge of 410 mAh/g after 60 circle circulations Specific capacity, hence it is evident that better than the specific capacity (J. Mater. Chem. 2010,20,8329-8335) of commercial graphite.But ZIF-67 In deintercalation Li+During metallo-organic framework can be destroyed, knot can be effectively relieved in it in conjunction with graphene aerogel The destruction of structure, to show excellent electrochemistry cyclicity.And graphene aerogel has more electrochemistry than graphene Reactivity site, to have better chemical property.Ren et al. is by hydro-thermal self assembling process on graphene sheet layer The adjustable three-dimensional layering porous graphene aeroge in duct is successfully loaded, electric current of this composite material in 0.1A/g is close Under degree, specific discharge capacity reaches 1100 mAh/g, be also much better than graphite electrode (Scientific Reports, 2015, 5,14229).
In short, being designed to the carrier with cellular structure and electrochemical reaction active site abundant, it is beneficial to solve The electrode material structural damage problem that lithium ion battery causes in charge and discharge process due to the deintercalation repeatedly of lithium ion, thus Promote the development of lithium ion battery electrode material.
Summary of the invention
The present invention is to prepare graphene oxide using natural graphite powder as raw material by chemical oxidation stripping method, add After carbon nanotube (CNTs) ultrasonic mixing, by hydro-thermal method and freeze-drying prepare porous graphene aeroge (GAS) with The compound (GAS@CNTs) of CNTs, then GAS@CNTs and metal organic framework ZIF-67 precursor solution are stirred, it is quiet After setting a period of time, graphene aerogel load carbon nanotube and ZIF-67 electrode material of lithium battery (GAS@CNTs@ZIF- is made 67), this method key is the compound that GAS and CNTs are prepared by hydro-thermal method and freeze-drying, in answering for GAS and CNTs It closes in object and adds ZIF-67, be dispersed evenly by stirring, GAS@CNTs@ZIF-67 electrode of lithium cell material is obtained after vacuum drying Material.By electro-chemical test it is found that the aerogel carried carbon nanotube of the novel graphene and ZIF-67 electrode material of lithium battery, phase To specific capacity height, good cycling stability, preparation method is simple, experiment condition is mild, may and can be applied to commercialized Pure electric automobile.
The present invention is achieved by the following technical solutions.
The present invention is a kind of graphene aerogel load carbon nanotube and ZIF-67 electrode material of lithium battery preparation method, It is characterized by having technical process and step below:
A. it weighs 2-2.5g natural graphite powder to pour into the flask of 1000ml, 100-150ml concentration 65% is added HNO3 , then flask is placed in ice-water bath, it is maintained at the H that 100-150ml concentration 98% is slowly added at 0 DEG C2SO4 , stir 1- After 2h, 8-15g KMnO is added4, it is warming up to 30-40 DEG C of reaction 2-3h, then be warming up to 70-90 DEG C of reaction 1-2h；After being cooled to room temperature Brown colloidal substance is obtained after 300-500ml distilled water dilution concentrated acid is added, adds 35% H of 30-50ml2O2And 100- 10% HCl of 150ml is cleaned, and obtains brown yellow solution；Centrifugation is washed to neutrality；Air drying obtains graphene oxygen at 50-60 DEG C Compound；
B. the above-mentioned graphene oxide of 0.04g is weighed, is added the distilled water of 20ml, after ultrasonic 30-60min, is added 0.02g carbon nanotube (CNTs) continues ultrasonic disperse 1-1.5h, in 180 DEG C of hydro-thermal reaction 12h, then is freeze-dried, drying temperature It is -30-40 DEG C, the compound (GAS@CNTs) of graphene aerogel (GAS) and carbon nanotube (CNTs) is made；
C. the compound (GAS@CNTs) for weighing graphene aerogel (GAS) and CNTs that 0.05g step (b) obtains adds Enter in 25ml methanol solution, ultrasonic disperse 20-30min, 0.249g Co (NO is added3)2·6H2O；25ml 2- methyl is instilled again The methanol solution of imidazoles stirs 10-20min, stands and uses ethyl alcohol centrifuge washing 6-8 times afterwards for 24 hours, up to GAS@CNTs after drying With ZIF-67 compound；
D. GAS@CNTs@ZIF-67, acetylene black, PVDF adhesive, GAS@CNTs@ZIF-67, acetylene black, PVDF are chosen Adhesive is uniformly mixed with the mass ratio of 8:1:1, is then fed the mixture into N-N dimethyl pyrrolidone, and ultrasonic disperse, Obtain gluey black liquor；Disperse slurries with high speed inner-rotary type beater, one minute repetition 5-10 times every time obtains uniform GAS@CNTs@ZIF-6 black glue slurry；
E. above-mentioned black glue slurry is uniformly coated on the metal copper current collector handled well in advance, is placed in vacuum Dry in baking oven, temperature is set as 60-80 DEG C, drying time 12-24h；Finally obtain graphene aerogel load carbon nanometer Pipe and ZIF-67 electrode material of lithium battery.
Compared with prior art, this method is by hydro-thermal method, freeze-drying and ultrasonic disperse, successfully prepare GAS with The compound of CNTs is simultaneously effectively combined it with ZIF-67, final to obtain graphene aerogel load carbon nanotube and ZIF-67 lithium Battery electrode material, which has electrochemical reaction active site abundant and cellular structure abundant, to compare Capacity height, good cycling stability, the feature that preparation method is simple, experiment condition is mild.
Detailed description of the invention
Fig. 1 is the X-ray diffraction (XRD) figure that graphene aerogel loads carbon nanotube and ZIF-67 electrode material of lithium battery Spectrum；
Fig. 2 is scanning electron microscope (SEM) photo for the material that graphene aerogel loads carbon nanotube；
Fig. 3 is that graphene aerogel loads carbon nanotube and the transmission electron microscope (TEM) of ZIF-67 electrode material of lithium battery shines Piece；
Fig. 4 is low current (0.1C) charge and discharge that graphene aerogel loads carbon nanotube and ZIF-67 electrode material of lithium battery The cycle performance figure of electricity.
Specific embodiment
After now specific implementation case of the invention is described in.
Embodiment 1
A kind of graphene aerogel load carbon nanotube and ZIF-67 electrode material of lithium battery preparation method, step is such as Under:
A. it weighs 2g natural graphite powder to pour into flask, the HNO of 100ml concentration 65% is added3, then flask is placed on ice water In bath, it is maintained at and is slowly added to the H that 100ml concentration is 98% at 0 DEG C2SO4, 10g KMnO is added after stirring 1h4, it is warming up to 35 DEG C reaction 2h, then is warming up to 75 DEG C of reaction 1h；Addition 500ml distilled water dilution concentrated acid obtains brown colloid after being cooled to room temperature Shape substance adds 35% H of 40ml2O2And the 10% HCl cleaning of 100ml, obtain brown yellow solution；Centrifugation is washed to neutrality； Air drying obtains graphene oxide at 60 DEG C；
B. the above-mentioned graphene oxide of 0.04g is weighed, is added the distilled water of 20ml, after 30 min of ultrasound, is added 0.02g carbon nanotube (CNTs) ultrasonic disperse 1h, in 180 DEG C of hydro-thermal reaction 12h, then is freeze-dried, and drying temperature is -30- 40 DEG C, the compound (GAS@CNTs) of graphene aerogel (GAS) and carbon nanotube (CNTs) is made；
C. the compound GAS CNTs for weighing alkene aeroge (GAS) and CNTs that 0.05g step (b) obtains is added In 25ml methanol solution, 0.249g Co (NO is added in 30 min of ultrasound3)2·6H2O；The first of 25ml 2-methylimidazole is instilled again Alcoholic solution stirs 20min, stands and uses ethyl alcohol centrifuge washing 7 times afterwards for 24 hours, up to GAS@CNTs@ZIF-67 compound after drying；
D. GAS@CNTs@ZIF-67, acetylene black, PVDF adhesive, GAS@CNTs@ZIF-67, acetylene black, PVDF are chosen Adhesive is uniformly mixed with the mass ratio of 8:1:1, is then fed the mixture into N-N dimethyl pyrrolidone, and ultrasonic disperse, Obtain gluey black slurries；Disperse slurries with high speed inner-rotary type beater, is repeated 10 times within one minute every time, obtains uniform GAS CNTs@ZIF-67 black glue slurry；
E. above-mentioned black glue slurry is uniformly coated on the metal copper current collector handled well in advance, is placed in vacuum Dry in baking oven, temperature is set as 80 DEG C, and drying time is for 24 hours；Finally obtain graphene aerogel load carbon nanotube and ZIF- 67 electrode material of lithium battery.
The assembling and its test of battery
The above-mentioned electrode to be measured prepared be put into self-control stainless steel battery mould in test, using high-purity lithium piece as bear Pole, polypropylene porous film (Celgard 2400) are diaphragm, the trifluoromethanesulfonyl chloride LiTFSI and gather that electrolyte is 1mol/L Ethylene glycol (PEG)/dimethyl ether (DME) (weight ratio 1:1) mixed solution.Battery is assembled in the gloves full of high-purity argon gas It is carried out in case；Test current density is 0.1C, and wherein 1C is equal to 1000 mA/g, and test voltage range is 1-3V.
Shown in attached drawing 1: the analysis showed that product is that the higher metal organic framework ZIF-67 of crystallinity and carbon nanotube are negative The electrode material of lithium battery being loaded on graphene aerogel.Fig. 2 is the scanning SEM photograph that graphene aerogel loads carbon nanotube Piece, it can be seen that carbon nanotube is interspersed in graphene aerogel；Fig. 3 is that graphene aerogel loads carbon nanotube and ZIF-67 The transmission electron microscope TEM photo of electrode material of lithium battery, it can be seen that be attached with hexagon on graphene aerogel fold lamella The carbon nanotube of ZIF-67 particle and tubulose.In figure 2 and figure 3, it can be found that carbon nanotube and ZIF-67 are in graphene airsetting It is evenly dispersed on glue, form a kind of three-dimensional porous compound of multi-stage artery structure.Fig. 4 is that graphene aerogel loads carbon nanometer The cycle performance figure of low current (0.1C) charge and discharge of pipe and ZIF-67 electrode material of lithium battery, figure 4, it can be seen that battery exists Specific capacity is able to maintain in 600 mAh/g or so after low current charge-discharge cycle 50 is enclosed.It can be seen that the material specific capacity is high, stable circulation Performance is good, has commercialized potentiality.

Claims (1)

1. a kind of graphene aerogel load carbon nanotube and ZIF-67 electrode material of lithium battery preparation method, which is characterized in that This method has follow steps:
A. it weighs 2-2.5g natural graphite powder to pour into the flask of 1000ml, the HNO of 100-150ml concentration 65% is added3, then will Flask is placed in ice-water bath, keeps the H that 100-150ml concentration 98% is slowly added at 0 DEG C2SO4, after stirring 1-2h, 8- is added 15g KMnO4, it is warming up to 30-40 DEG C of reaction 2-3h, then be warming up to 70-90 DEG C of reaction 1-2h；300- is added after being cooled to room temperature Brown colloidal substance is obtained after 500ml distilled water dilution concentrated acid, adds the 35%H of 30-50ml2O2And 100-150ml 10%HCl cleaning, obtains brown yellow solution；Centrifugation is washed to neutrality；Air drying obtains graphene oxide at 50-60 DEG C；
B. the above-mentioned graphene oxide of 0.04g is weighed, is added the distilled water of 20ml, after ultrasonic 30-60min, adds 0.02g carbon Nanotube (CNTs) continues ultrasonic disperse 1-1.5h, in 180 DEG C of hydro-thermal reaction 12h, then is freeze-dried, and drying temperature is -30-40 DEG C, the compound of graphene aerogel (GAS) and carbon nanotube (CNTs) is made；
C. 25ml methanol solution is added in the compound for weighing graphene aerogel (GAS) and CNTs that 0.05g step (b) obtains In, 0.249g Co (NO is added in ultrasonic disperse 20-30min3)2·6H2O；The methanol solution of 25ml 2-methylimidazole is instilled again, 10-20min is stirred, stands and uses ethyl alcohol centrifuge washing 6-8 times afterwards for 24 hours, up to graphene aerogel (GAS)/carbon nanometer after drying Manage (CNTs)/ZIF-67 compound；
D. graphene aerogel (GAS)/carbon nanotube (CNTs)/ZIF-67 compound, acetylene black, PVDF adhesive are chosen, it will Graphene aerogel (GAS)/carbon nanotube (CNTs)/ZIF-67 compound, acetylene black, PVDF adhesive are with the quality of 8:1:1 Than being uniformly mixed, then feeds the mixture into N-N dimethyl pyrrolidone, and ultrasonic disperse, obtain gluey black liquor；With High speed inner-rotary type beater disperses slurries, and repetition 5-10 times in each minute obtains uniform graphene aerogel (GAS)/carbon and receives Mitron (CNTs)/ZIF-67 compound black glue slurry；
E. above-mentioned black glue slurry is uniformly coated on the metal copper current collector handled well in advance, is placed in vacuum drying oven Dry, temperature is set as 60-80 DEG C, drying time 12-24h；Finally obtain graphene aerogel load carbon nanotube and ZIF- 67 electrode material of lithium battery.
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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
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CN109499493B (en) * 2018-12-07 2021-08-13 武汉工程大学 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
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