CN108807944A - Hollow porous C o3O4The preparation method and application of nanometer box/redox graphene composite material - Google Patents
Hollow porous C o3O4The preparation method and application of nanometer box/redox graphene composite material Download PDFInfo
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Abstract
A kind of hollow porous C o3O4The preparation method and application of nanometer box/redox graphene composite material, belongs to ion cathode material lithium preparing technical field.It is mainly comprised the following steps：(1) cobalt-based metal organic frame ZIF-67 is prepared；(2) under protection of argon gas 400 DEG C heat preservation 2h, in air 400 DEG C heat preservation 2h, prepare hollow porous C o3O4Nanometer box；(3) by a hydro-thermal by hollow porous C o3O4Nanometer box and graphene oxide are compound, and make graphene oxide that reduction reaction occur in water-heat process.The material preparation method is relatively new, simple for process, structure relatively easily controls, and as lithium ion battery negative material, shows high capacity, outstanding high rate performance, excellent cyclical stability has boundless application prospect.
Description
Technical field
The invention belongs to lithium ion battery negative material fields, and in particular to hollow porous C o3O4Nanometer box/reduction-oxidation
Graphene composite material is in the application of lithium ion battery negative material, and the material is using ZIF-67 as template preparation Co3O4, and with also
Former graphene oxide is compound, effectively improves the electric conductivity of metal oxide, makes it have high capacity, outstanding high rate performance,
Excellent cyclical stability.
Background technology
It is continuously increased with the rapid growth and economic sustainable development, energy-output ratio of world population.Devoting Major Efforts To Developing and
Development new energy is the inexorable trend of sustainable development.Lithium ion battery as a kind of efficient electrochemical cell energy storage device,
With high-energy density, long circulation life, environmental-friendly, flexible power and energy response, to meet different functional requirements.
Transition metal oxide shows higher theoretical specific capacity of twice or three times compared to conventional graphite material as negative material
(500~1000mA h g-1), it has a good application prospect.In numerous transition metal oxides, Co3O4Due to possessing
Higher theoretical specific capacity (about 1000mA h g-1) and excellent cycle performance have received widespread attention.However, due to
Co3O4There is the shortcomings of larger irreversible capacity loss and poor high rate performance to significantly limit it as lithium for material
The practical application of ion battery cathode material.In order to overcome these inherent shortcomings, it is hollow more micro/nano level can be designed by (1)
Pore structure：Increase electrode and electrolyte liquor contact area, discharge structural stress during embedding and removing, shortens lithium ion diffusion path
Deng to effectively improve the high rate performance and whole volume of electrode；(2) with the grapheme material of high conductivity it is compound improve its
High rate performance is to improve capacity.
In recent years, Main Branches of the zeolite imidazole skeleton (ZIFs) as metal organic framework have permanent hole, high table
Area, hydrophobicity, the metallic site of opening and excellent water stability, have been used for the numerous areas such as gas storage, catalysis.ZIFs derives
Metal oxide possess abundant reaction site, shorter ion diffusion length and during the reaction in electrochemical reaction
Bulk strain can effectively be discharged, but when as lithium ion battery negative material, the stability of ZIFs derived materials still needs to be carried
It is high.Graphene with high specific surface area, mechanical strength and high electric conductivity is used as Co because of it3O4Ideal substrate material it
One.
Invention content
The present invention provides a kind of hollow porous C o3O4Nanometer box/redox graphene composite material preparation method and its
In cathode of lithium battery application, its object is to effectively by redox graphene and hollow porous C o3O4Nanometer box passes through electrostatic
Attraction is combined together, the Co prepared after ZIF-67 is annealed3O4Remain the high porosity of metal organic frame, at the same with also
Volume change of the electrode material in charge and discharge process can be effectively relieved in the synergistic effect of former graphene oxide, and improves specific volume
Amount and cyclical stability.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of hollow porous C o of the present invention3O4The preparation method of nanometer box/redox graphene composite material,
Using cobalt-based metal organic frame ZIF-67 as template, calcined under inert gas protection to maintain its good octahedral
Then volume morphing is calcined under air, obtain the hollow porous C o of nano-scale3O4Nanometer box structure, and pass through a hydro-thermal method
By hollow porous C o3O4Nanometer box is combined with redox graphene, and ZIF-67 is calcined as presoma and can be made at high temperature
For large specific surface area, porous and metal ion presentation atomic size metal oxide electrode material is gone out, porous structure provides foot
Enough electrolyte ion diffusion admittances, meanwhile, there is redox graphene high specific surface area to provide more effective actives
The synergistic effect in site, the two is fully played.
It is as follows：
Step 1, the polyhedral preparations of cobalt-based metal organic frame ZIF-67：0.747g~2.988g Co (NO3)2·
6H2O is dissolved in 60 ml methanols, forms pink clear solution；By the first containing 0.164~0.656g 2-methylimidazoles
Alcoholic solution is quickly poured into above-mentioned solution；The mixed solution is placed 24 hours at 25 DEG C, the product of gained is washed through methanol
Product is obtained after washing；
Step 2, hollow porous C o3O4The synthesis of nanometer box：By prepared cobalt-based metal organic frame ZIF-67 powder
It is placed in tubular heater, is heated to 300 DEG C~500 DEG C, heating rate is 5 DEG C/min, and heat preservation is continuing sky after 1~3 hour
1~3 hour, which is kept the temperature, in gas obtains hollow porous C o3O4Nanometer box；
Step 3, hollow porous C o3O4The preparation of nanometer box/redox graphene composite material：Using improvement Hummer
Method prepares graphene oxide, and 10~30mg graphene oxides are dispersed in 100mL deionized waters and are ultrasonically treated 2 hours,
By the hollow porous C o of 50~150mg3O4Nanometer box is scattered in 100mL deionized waters, is ultrasonically treated 15 minutes, then will be upper
It states solution to be added in the solution containing graphene oxide, and ultrasound 15min makes it be uniformly dispersed, then by mixture in 45mL
180 DEG C of hydro-thermal reactions collect black powder after 1~3 hour in stainless steel autoclave.
The polyhedral preparations of the ZIF-67 of cobalt-based metal organic frame described in step 1：Co(NO3)2·6H2The quality of O is
1.494g；The quality of 2-methylimidazole is 0.328g.
Hollow porous C o described in step 23O4The synthesis of nanometer box：Heating temperature by prepared ZIF-67 powder is
400 DEG C, soaking time is 2h under protection of argon gas, and soaking time is 2 hours in air.
Hollow porous C o described in step 33O4The preparation of nanometer box/redox graphene composite material：Graphene oxide
Quality be 20mg, hollow porous C o3O4The quality of nanometer box is 100mg, and mixture is in 45mL stainless steel autoclaves
180 DEG C of the hydro-thermal reaction times are 2 hours.
A kind of hollow porous C o3O4The application of nanometer box/redox graphene composite material：The composite wood
Material is used as cathode of lithium battery.
The technique effect of the present invention：Reaction process of the present invention is simple, and experimental implementation is easy, dangerous small, has good
Repeatability can be mass.
Description of the drawings
Fig. 1：Hollow porous C o prepared by embodiment 13O4The X-ray diffraction of nanometer box/redox graphene composite material
Collection of illustrative plates
Fig. 2：Hollow porous C o prepared by embodiment 13O4The Flied emission figure of nanometer box/redox graphene composite material.
Fig. 3：Hollow porous C o prepared by embodiment 13O4Nanometer box/redox graphene composite material is in 0.1Ag-1Electricity
The cycle performance collection of illustrative plates flowed down.
Fig. 4：Hollow porous C o prepared by embodiment 13O4Nanometer box/redox graphene composite material is in 0.1Ag-1Electricity
Charging and discharging curve under current density.
Fig. 5：Hollow porous C o prepared by embodiment 13O4Nanometer box/redox graphene composite material is in 0.5mV s-1
Sweep the CV curves measured under speed.
Fig. 6：Hollow porous C o prepared by embodiment 13O4Nanometer box/redox graphene composite material exists respectively
0.1Ag-1、0.2Ag-1、0.4Ag-1、0.8Ag-1、1Ag-1Electricity, 2Ag-1And return to 0.1Ag-1The high rate performance measured under current density
Collection of illustrative plates.
Fig. 7：Hollow porous C o prepared by embodiment 13O4The impedance diagram of nanometer box/redox graphene composite material.
Fig. 8：Hollow porous C o prepared by embodiment 13O4Nanometer box/redox graphene composite material is in 3Ag-1Electric current
Cycle performance collection of illustrative plates under density.
Specific implementation mode
The present invention is expanded on further with reference to embodiment：
Embodiment 1
(1) preparation of cobalt-based metal organic frame ZIF-67：1.494g Co(NO3)2·6H2O is dissolved in 60 ml methanols
In, form pink clear solution.Then, under magnetic stirring, the methanol solution containing 0.328g 2-methylimidazoles is quick
It pours into above-mentioned solution.The mixed solution is placed 24 hours at 25 DEG C, the product of gained is washed and centrifuged several through methanol
It is secondary, obtain product after 12 hours dry under 60 DEG C of vacuum.
(2) hollow porous C o3O4The synthesis of nanometer box：Prepared cobalt-based metal organic frame ZIF-67 powder is placed in
In tubular heater, 400 DEG C are heated to, temperature is 5 DEG C of min-1, soaking time 2h, then in air keep the temperature 2 hours, see
Observe powder becomes black from purple.
(3) hollow porous C o3O4The preparation of nanometer box/redox graphene composite material：Using the improved side Hummer
Method prepares graphene oxide.In order to synthesize hollow porous C o3O4Nanometer box/redox graphene composite material, 20mg is aoxidized
Graphene dispersion is in 100mL deionized waters and is ultrasonically treated 2 hours.By the hollow porous C o of 100mg3O4Nanometer box is scattered in
In 100mL deionized waters, it is ultrasonically treated 15 minutes.Then above-mentioned solution is added in the solution containing graphene oxide, and
Ultrasonic 15min makes it be uniformly dispersed.Then by mixture in 45mL stainless steel autoclaves 180 DEG C of hydro-thermal reactions 2 hours,
And black powder is collected with water and ethyl alcohol centrifugation several times and after 12 hours dry in 60 DEG C of vacuum drying oven respectively.
Embodiment 2
(1) preparation of cobalt-based metal organic frame ZIF-67：0.747g Co(NO3)2·6H2O is dissolved in 60 ml methanols
In, form pink clear solution.Then, under magnetic stirring, the methanol solution containing 0.164g 2-methylimidazoles is quick
It pours into above-mentioned solution.The mixed solution is placed 24 hours at 25 DEG C, the product of gained is washed and centrifuged several through methanol
It is secondary, obtain product after 12 hours dry under 60 DEG C of vacuum.
(2) hollow porous C o3O4The synthesis of nanometer box：Prepared cobalt-based metal organic frame ZIF-67 powder is placed in
In tubular heater, 300 DEG C are heated to, temperature is 5 DEG C of min-1, soaking time 1h, then in air keep the temperature 1 hour, see
Observe powder becomes black from purple.
(3) hollow porous C o3O4The preparation of nanometer box/redox graphene composite material：Using the improved side Hummer
Method prepares graphene oxide.In order to synthesize hollow porous C o3O4Nanometer box/redox graphene composite material, 10mg is aoxidized
Graphene dispersion is in 100mL deionized waters and is ultrasonically treated 2 hours.By the ZIF-Co of 50mg3O4Polyhedron is scattered in 100mL
In deionized water, it is ultrasonically treated 15 minutes.Then above-mentioned solution is added in the solution containing graphene oxide, and ultrasound
15min makes it be uniformly dispersed.Then by mixture in 45mL stainless steel autoclaves 180 DEG C of hydro-thermal reactions 1 hour, and point
Black powder is not collected with water and ethyl alcohol centrifugation several times and after 12 hours dry in 60 DEG C of vacuum drying oven.
Embodiment 3
(1) preparation of cobalt-based metal organic frame ZIF-67：2.988g Co(NO3)2·6H2O is dissolved in 60 ml methanols
In, form pink clear solution.Then, under magnetic stirring, the methanol solution containing 0.656g 2-methylimidazoles is quick
It pours into above-mentioned solution.The mixed solution is placed 24 hours at 25 DEG C, the product of gained is washed and centrifuged several through methanol
It is secondary, obtain product after 12 hours dry under 60 DEG C of vacuum.
(2) hollow porous C o3O4The synthesis of nanometer box：Prepared cobalt-based metal organic frame ZIF-67 powder is placed in
In tubular heater, 500 DEG C are heated to, temperature is 5 DEG C of min-1, soaking time 3h, then in air keep the temperature 3 hours, see
Observe powder becomes black from purple.
(3) hollow porous C o3O4The preparation of nanometer box/redox graphene composite material：Using the improved side Hummer
Method prepares graphene oxide.In order to synthesize hollow porous C o3O4Nanometer box/redox graphene composite material, 30mg is aoxidized
Graphene dispersion is in 100mL deionized waters and is ultrasonically treated 2 hours.By the ZIF-Co of 150mg3O4Polyhedron is scattered in 100mL
In deionized water, it is ultrasonically treated 15 minutes.Then above-mentioned solution is added in the solution containing graphene oxide, and ultrasound
15min makes it be uniformly dispersed.Then by mixture in 45mL stainless steel autoclaves 180 DEG C of hydro-thermal reactions 2 hours, and point
Black powder is not collected with water and ethyl alcohol centrifugation several times and after 12 hours dry in 60 DEG C of vacuum drying oven.
Embodiment 4
(1) preparation of lithium ion battery working electrode：By hollow porous C o prepared in embodiment one3O4Nanometer box/also
Former graphene oxide composite material assembles 2016 type button cells as working electrode and carries out electrochemical property test.By will in
Empty porous C o3O4Nanometer box/redox graphene composite material (80%), acetylene black (10%) and polyvinylidene fluoride
(PVDF, 10%) is mixed into uniform slurry with n-methyl-2-pyrrolidone (NMP), and mixture is coated in clean copper foil
On, 110 DEG C of dryings 12 hours in a vacuum.Using metal lithium sheet as reference electrode, with hollow porous C o3O4Nanometer box/reduction-oxidation
Graphene composite material is working electrode.Electrolyte is LBC305-01 (LiPF6), ethylene carbonate (EC)/dimethyl carbonate
(DMC)/diethyl carbonate (DEC), mass ratio 1:1:1.Assembled battery (the H in argon gas fills glove box2O < 0.1ppm, O2
< 0.1ppm).
(2) multi-channel battery test system (Land CT2001 1A) is used to carry out electro-chemical test, wherein voltage cut-off
Window is from 0.01V to 3V.Cyclic voltammetry (CV, 0.01~3V, 0.5mVs are carried out using electrochemical work station (PARSTAT4000)-1) and electrochemical impedance spectroscopy (EIS) test.
(3) performance of lithium ion battery of electrode material is as shown in Figure 3, and the first circle discharge capacity of electrode material is 2205mAh
g-1, charging capacity is 1500mAh g-1, illustrate it with higher cycle specific capacity.In addition, the electric conductivity of material obtains effectively
It improves and there is preferable high rate performance.
Claims (5)
1. a kind of hollow porous C o3O4The preparation method of nanometer box/redox graphene composite material, it is characterised in that：
Using cobalt-based metal organic frame ZIF-67 as template, calcined under inert gas protection to maintain its good octahedral bodily form
Then state is calcined under air, obtain the hollow porous C o of nano-scale3O4Nanometer box structure, and by hydro-thermal method will in
Empty porous C o3O4Nanometer box is combined with redox graphene, is as follows：
Step 1, the polyhedral preparations of cobalt-based metal organic frame ZIF-67：0.747g~2.988g Co (NO3)2·6H2O is molten
Solution forms pink clear solution in 60 ml methanols；By the methanol solution containing 0.164~0.656g 2-methylimidazoles
It is quickly poured into above-mentioned solution；The mixed solution is placed 24 hours at 25 DEG C, by the product of gained after methanol washs
To product；
Step 2, hollow porous C o3O4The synthesis of nanometer box：Prepared cobalt-based metal organic frame ZIF-67 powder is placed in
In tubular heater, 300 DEG C~500 DEG C are heated to, heating rate is 5 DEG C/min, after keeping the temperature 1~3 hour in continuing air
Heat preservation obtains hollow porous C o in 1~3 hour3O4Nanometer box；
Step 3, hollow porous C o3O4The preparation of nanometer box/redox graphene composite material：Using improvement Hummer methods
Graphene oxide is prepared, 10~30mg graphene oxides are dispersed in 100mL deionized waters and are ultrasonically treated 2 hours, by 50
The hollow porous C o of~150mg3O4Nanometer box is scattered in 100mL deionized waters, is ultrasonically treated 15 minutes, then will be above-mentioned molten
Liquid is added in the solution containing graphene oxide, and ultrasound 15min makes it be uniformly dispersed, then that mixture is stainless in 45mL
180 DEG C of hydro-thermal reactions collect black powder after 1~3 hour in steel autoclave.
2. a kind of hollow porous C o as described in claim 13O4The preparation side of nanometer box/redox graphene composite material
Method, it is characterised in that：The polyhedral preparations of the ZIF-67 of cobalt-based metal organic frame described in step 1：Co(NO3)2·6H2O's
Quality is 1.494g；The quality of 2-methylimidazole is 0.328g.
3. a kind of hollow porous C o as described in claim 13O4The preparation side of nanometer box/redox graphene composite material
Method, which is characterized in that hollow porous C o described in step (2)3O4The synthesis of nanometer box：By adding for prepared ZIF-67 powder
Hot temperature is 400 DEG C, and soaking time is 2h under protection of argon gas, and soaking time is 2 hours in air.
4. a kind of hollow porous C o as described in claim 13O4The preparation side of nanometer box/redox graphene composite material
Method, it is characterised in that：Step (3) the hollow porous C o3O4The preparation of nanometer box/redox graphene composite material：Oxidation
The quality of graphene is 20mg, hollow porous C o3O4The quality of nanometer box is 100mg, and mixture is in 45mL stainless steel reaction under high pressures
180 DEG C of the hydro-thermal reaction times are 2 hours in kettle.
5. a kind of hollow porous C o as described in Claims 1-43O4Nanometer box/redox graphene composite material is answered
With, it is characterised in that：The composite material is used as cathode of lithium battery.
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| CN109652815A (en) * | 2019-01-11 | 2019-04-19 | 河南师范大学 | A kind of preparation method of the layered double-hydroxide elctro-catalyst as derived from MOF with hollow structure |
| CN109742439A (en) * | 2018-12-24 | 2019-05-10 | 肇庆市华师大光电产业研究院 | A kind of novel lithium-sulfur cell porous interlayer material, preparation method and application |
| CN109755041A (en) * | 2018-12-06 | 2019-05-14 | 桂林理工大学 | A kind of preparation method of porous oxidation cobalt electrode material |
| CN110136993A (en) * | 2019-05-08 | 2019-08-16 | 武汉大学 | A method of super capacitor electrode slice is prepared using hydro-thermal method |
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| CN109755041A (en) * | 2018-12-06 | 2019-05-14 | 桂林理工大学 | A kind of preparation method of porous oxidation cobalt electrode material |
| CN109755041B (en) * | 2018-12-06 | 2020-10-09 | 桂林理工大学 | Preparation method of porous cobalt oxide electrode material |
| CN109742439A (en) * | 2018-12-24 | 2019-05-10 | 肇庆市华师大光电产业研究院 | A kind of novel lithium-sulfur cell porous interlayer material, preparation method and application |
| CN109652815A (en) * | 2019-01-11 | 2019-04-19 | 河南师范大学 | A kind of preparation method of the layered double-hydroxide elctro-catalyst as derived from MOF with hollow structure |
| CN110136993A (en) * | 2019-05-08 | 2019-08-16 | 武汉大学 | A method of super capacitor electrode slice is prepared using hydro-thermal method |
| CN110299530B (en) * | 2019-07-22 | 2022-04-01 | 福州大学 | ZIF-67-based cobalt molybdenum oxide hollow nanocage/graphene composite material and preparation method and application thereof |
| CN110299530A (en) * | 2019-07-22 | 2019-10-01 | 福州大学 | A kind of ZIF-67 base cobalt molybdenum oxide hollow Nano cage/graphene composite material and the preparation method and application thereof |
| CN111082047A (en) * | 2019-12-26 | 2020-04-28 | 上海应用技术大学 | Preparation method and application of two-dimensional carbide crystal base Zif-67 derived cobalt oxide material |
| CN111162264A (en) * | 2020-01-17 | 2020-05-15 | 上海应用技术大学 | Graphene-based carbon-coated ZIF-67-derived cobalt oxide composite material and preparation method and application thereof |
| CN112490422A (en) * | 2020-11-10 | 2021-03-12 | 华南理工大学 | Rod-shaped porous cobaltosic oxide/nanotube manganese dioxide cathode material and preparation method and application thereof |
| CN112993257A (en) * | 2021-03-11 | 2021-06-18 | 杭州电子科技大学 | rGO coated Co3O4Microsphere composite material and preparation method thereof |
| CN113097490A (en) * | 2021-04-02 | 2021-07-09 | 扬州大学 | Dodecahedral ZIF-67/Co3O4Composite material, preparation method and application thereof |
| CN114592210A (en) * | 2022-01-22 | 2022-06-07 | 温州大学新材料与产业技术研究院 | Co3O4-RuO2Preparation method and application of composite material |
| CN114592210B (en) * | 2022-01-22 | 2024-05-14 | 温州大学新材料与产业技术研究院 | Co (cobalt)3O4-RuO2Preparation method and application of composite material |
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Application publication date: 20181113 |