CN107128902B - A kind of network-like graphene nano material and its preparation method and application - Google Patents
A kind of network-like graphene nano material and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of network-like graphene nano materials and its preparation method and application.The preparation of the network-like graphene nano material includes: 1) to calcine carbon source organic matter at 500~1000 DEG C, obtains calcined material；2) water is added into calcined material to be washed, filter residue is obtained by filtration；3) under protective atmosphere, filter residue is made annealing treatment at 200~1600 DEG C to get.Network-like graphene nano material of the invention, it using carbon source organic matter as raw material, is prepared through calcining, washing, secondary high-temperature annealing process, is not related to additional template and molten mold process, process flow is simple, and the requirement to equipment is low, is easily industrialized production；The network-like graphene nano material has wide interlamellar spacing and superior electrical conductivity, shows excellent storage sodium performance.
Description
Technical field
The present invention relates to the preparation fields of graphene, and in particular to a kind of network-like graphene nano material and its preparation side
Method and application.
Background technique
For graphene as a kind of novel two-dimentional carbon material, unique physicochemical characteristics makes it in electrode material, storage
The fields such as hydrogen material, biosensor, catalyst carrier, energy storage material have broad application prospects, but due to graphene
For size in microcosmic magnitude, there is very strong π-π interaction and van der waals force in graphene between layers, be typically easy to send out
It is raw to reunite and stack, so that its application potential be made to have a greatly reduced quality.The graphene nano chip architecture of network blackboard can be reduced
Reunion and stacking between graphene film, while there is unique porous structure and the intrinsic property of graphene film, thus can be with
More spaces are provided for electrons/ions, gas/liquid transimission and storage.
Authorization Notice No. is that the patent of CN102674321B discloses a kind of graphene bubble with three-dimensional full-mesh network
Foam is to grow three-dimensional connect in three-dimensional porous metallic surface catalytic pyrolysis carbon-source gas by the technology of chemical vapor deposition
Logical graphene, it is subsequent molten except obtaining the graphene three-dimensional macro body of porous foam shape after porous metals substrate.The preparation method
Process flow it is complex, it is difficult to realize industrialized production.
Summary of the invention
The purpose of the present invention is to provide a kind of network-like graphene nano materials, to solve work of the existing technology
Skill is complicated, is difficult to realize the problem of industrialized production.
Second object of the present invention is to provide the preparation method of above-mentioned network-like graphene nano material.
Third object of the present invention is to provide above-mentioned network-like graphene nano material as sodium ions to potassium ions battery electricity
The application of pole material.
To achieve the above object, the technical scheme adopted by the invention is that:
A kind of network-like graphene nano material, is prepared by method comprising the following steps:
1) carbon source organic matter is calcined at 500~1000 DEG C, obtains calcined material；
2) water is added into calcined material to be washed, filter residue is obtained by filtration；
3) under protective atmosphere, filter residue is made annealing treatment at 200~1600 DEG C to get.
Network-like graphene nano material of the invention, using carbon source organic matter as raw material, through calcining, washing, secondary high-temperature
Annealing process is prepared, and is not related to additional template and molten mold process, and process flow is simple, and the requirement to equipment is low, is easy to
Realize industrialized production；The network-like graphene nano material has wide interlamellar spacing and superior electrical conductivity, shows excellent
Store up sodium performance.
In step 1), the carbon source organic matter is glucose, starch, sucrose, gluconic acid, citric acid, salicylic acid, grape
Sodium saccharate, calcium gluconate, zinc gluconate, sodium acetate, enuatrol, sodium tartrate, calcium stearate, sodium benzoate, sorbic acid
One of potassium, sodium citrate, calcium citrate, zinc citrate, lithium citrate, copper citrate, ammonium citrate or multiple combinations.
In step 1), calcination process carries out under air, argon gas or nitrogen atmosphere.Air atmosphere is not suitable for carbohydrate and has
Machine acids, acylate can be calcined in air atmosphere.I.e. carbon source organic matter is selected from sodium gluconate, calcium gluconate, Portugal
Grape saccharic acid zinc, sodium acetate, enuatrol, sodium tartrate, calcium stearate, sodium benzoate, potassium sorbate, sodium citrate, calcium citrate,
When one of zinc citrate, lithium citrate, copper citrate, ammonium citrate or multiple combinations, calcination process can be in air atmosphere
Lower progress.
In step 1), the rate for being warming up to 500~1000 DEG C is 1~20 DEG C/min.When calcining, at 500~1000 DEG C
Keep the temperature 1~10h.Carbon source organic matter be ammonium citrate when, step 1) calcination process generate exhaust gas mass concentration be 2% hydrogen
Ammonium fluoride solution is made after absorbing in fluoric acid, produces for other fluorides.
In step 2), the quality that water is added is 1~6 times of the corresponding carbon source organic matter quality of calcined material.The temperature of washing
It is 30~100 DEG C.It can wash repeatedly 1~10 time, to remove extra salt.Drying carries out subsequent anneal processing again after washing.It is dry
Dry temperature be 60~80 DEG C, the dry time be 12~for 24 hours.
In step 2), when carbon source organic matter contains metal ion, hydrofluoric acid is added into filtering gained filtrate and is reacted,
Prepare metal fluoride.The mass concentration of hydrofluoric acid is preferably 1~60%.
In step 3), the protective atmosphere is the mixed gas of argon gas or nitrogen or hydrogen and argon gas composition.Mixed gas
In, volume ratio shared by hydrogen is 5~50%.
In step 3), the technological parameter of annealing can be adjusted according to the selection of protective atmosphere.Protective atmosphere be argon gas or
When nitrogen, the temperature of annealing is 600~1600 DEG C, is 0.5~6h in the time that 600~1600 DEG C keep the temperature.Preferably, it rises
The rate of temperature to 600~1600 DEG C is 1~20 DEG C/min.When protective atmosphere is the mixed gas that hydrogen and argon gas form, annealing
The temperature of processing is 200~1050 DEG C, is 0.5~6h in the time that 200~1050 DEG C keep the temperature.Preferably, it is warming up to 200~
1050 DEG C of rate is 1~20 DEG C/min.In mixed gas, argon gas can be replaced with nitrogen or other common protective gas
Generation.In the step, perhaps argon gas can further be improved relatively simple nitrogen using nitrogen and hydrogen mixture or argon hydrogen gaseous mixture
The probability of atmospheric CO and carbon dioxide is formed because reacting in residual oxygen pyroprocess with carbon in oxygen in raw material itself and system,
Improving material yield.
Network-like graphene nano material provided by the invention, entire technical process is relatively friendly to environment, is not related to acid
Alkali and inflammable gas are mostly inorganic salts in the waste water of generation, are easily recycled, environmental pollution is small；It is removed using washing process
The extra salt that calcination process generates is conducive to the network-like graphite that subsequent anneal processing prepares wide interlamellar spacing and superior electrical conductivity
Alkene nanometer sheet；It converts the metal ion in filtrate to the metal fluoride of high added value, is mentioned while solving environmentally friendly bottleneck
High element utilization rate, has achieved the purpose that clean manufacturing and has provided new growth engines for enterprise.
A kind of preparation method of network-like graphene nano material, comprising the following steps:
1) carbon source organic matter is calcined at 500~1000 DEG C, obtains calcined material；
2) water is added into calcined material to be washed, filter residue is obtained by filtration；
3) under protective atmosphere, filter residue is made annealing treatment at 200~1600 DEG C to get.
The optimum choice of each step is same as described above.
The preparation method of network-like graphene nano material of the invention, raw materials are abundant, cheap and easy to get, equipment is wanted
Seek simple, environmental-friendly, stable product quality；Network-like graphene nanometer sheet obtained by the preparation method have excellent storage sodium/
Potassium performance can be widely used for the fields such as energy storage, photocatalysis, polymer carrier.
Above-mentioned network-like graphene nano material can be used as the use of sodium ions to potassium ions battery electrode material.Using above-mentioned electricity
The sodium ions to potassium ions battery of pole material, the excellent electrical properties such as reversible capacity, capacity retention ratio, has a vast market application prospect.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is the SEM figure of the 1 network-like graphene nanometer sheet of gained of the embodiment of the present invention；
Fig. 3 is the TEM figure of the 1 network-like graphene nanometer sheet of gained of the embodiment of the present invention；
Fig. 4 is the HR-TEM figure of the 1 network-like graphene nanometer sheet of gained of the embodiment of the present invention；
Fig. 5 is the Raman map of the 1 network-like graphene nanometer sheet of gained of the embodiment of the present invention；
Fig. 6 detects knot for the electrical property of sodium-ion battery prepared by the network-like graphene nanometer sheet using embodiment 1
Fruit.
Specific embodiment
Embodiments of the present invention are described further combined with specific embodiments below.
Embodiment 1
The network-like graphene nano material of the present embodiment, process flow is as shown in Figure 1, using following methods system
It is standby:
1) it weighs 1kg sodium gluconate addition porcelain boat to be placed in argon gas atmosphere stove, is warming up to 500 with the rate of 10 DEG C/min
DEG C, 4h is kept the temperature, is cooled to room temperature, is obtained black block and crush, as calcined material；
2) distilled water that 6kg temperature is 30 DEG C is added into calcined material and carries out filtering and washing, is repeated 8 times, will wash
The dry 12h at 60 DEG C of filter residue afterwards, obtains network-like amorphous carbon nanometer sheet；
3) network-like amorphous carbon nanometer sheet under an argon atmosphere, is warming up to 600 DEG C of progress with the rate of 20 DEG C/min
Annealing, keeps the temperature 6h at 600 DEG C, is cooled to room temperature up to the network-like graphene nanometer sheet of 50g.
In the embodiment, the filtrate 5.5kg that step 2) washing generates, after detecting metal ion content, by theoretical amount plus
Enter the hydrofluoric acid that mass concentration is 10% to be reacted, 85g sodium fluoride product is made.
Embodiment 2
The network-like graphene nano material of the present embodiment, process flow is as shown in Figure 1, using following methods system
It is standby:
1) it weighs 1kg calcium stearate addition porcelain boat to be placed in nitrogen atmosphere stove, is warming up to 1000 with the rate of 8 DEG C/min
DEG C, 2h is kept the temperature, is cooled to room temperature, is obtained black block and crush, as calcined material；
2) distilled water that 2kg temperature is 60 DEG C is added into calcined material and carries out filtering and washing, is repeated 2 times, will wash
The dry 20h at 60 DEG C of filter residue afterwards, obtains network-like amorphous carbon nanometer sheet；
3) network-like amorphous carbon nanometer sheet under an argon atmosphere, is warming up to 1600 DEG C of progress with the rate of 15 DEG C/min
Annealing, keeps the temperature 1h at 1600 DEG C, is cooled to room temperature up to the network-like graphene nanometer sheet of 30g.
In the embodiment, the filtrate 1.5kg that step 2) washing generates, after detecting metal ion content, by theoretical amount plus
Enter the hydrofluoric acid that mass concentration is 20% to be reacted, 105g is made and is fluorinated calcium product.
Embodiment 3
The network-like graphene nano material of the present embodiment, process flow is as shown in Figure 1, using following methods system
It is standby:
1) it weighs 1kg lithium citrate addition porcelain boat to be placed in air atmosphere stove, is warming up to 700 with the rate of 3 DEG C/min
DEG C, 1h is kept the temperature, is cooled to room temperature, is obtained black block and crush, as calcined material；
2) distilled water that 3kg temperature is 70 DEG C is added into calcined material and carries out filtering and washing, is repeated 5 times, will wash
The dry 20h at 60 DEG C of filter residue afterwards, obtains network-like amorphous carbon nanometer sheet；
3) network-like amorphous carbon nanometer sheet under an argon atmosphere, is warming up to 900 DEG C with the rate of 5 DEG C/min to move back
Fire processing, keeps the temperature 1h at 900 DEG C, is cooled to room temperature up to the network-like graphene nanometer sheet of 40g.
In the embodiment, the filtrate 2.45kg that step 2) washing generates, after detecting metal ion content, by theoretical amount plus
Enter the hydrofluoric acid that mass concentration is 20% to be reacted, 110g lithium fluoride product is made.
Embodiment 4
The network-like graphene nano material of the present embodiment, process flow is as shown in Figure 1, using following methods system
It is standby:
1) it weighs 1kg ammonium citrate addition porcelain boat to be placed in argon gas atmosphere stove, is warming up to 500 with the rate of 1 DEG C/min
DEG C, 1h is kept the temperature, is cooled to room temperature, is obtained black block and crush, as calcined material；
2) distilled water that 4kg temperature is 80 DEG C is added into calcined material and carries out filtering and washing, is repeated 3 times, will wash
The drying at 80 DEG C of filter residue afterwards for 24 hours, obtains network-like amorphous carbon nanometer sheet；
3) under argon hydrogen mixed atmosphere (hydrogen volume content be 10%), by network-like amorphous carbon nanometer sheet with 10 DEG C/
The rate of min is warming up to 950 DEG C and is made annealing treatment, and keeps the temperature 1h at 950 DEG C, is cooled to room temperature up to the network-like graphite of 35g
Alkene nanometer sheet.
In the embodiment, the hydrofluoric acid that the exhaust gas mass concentration that step 1) calcination process generates is 2% is made after absorbing
Ammonium fluoride solution is produced for other fluorides.
Embodiment 5
The network-like graphene nano material of the present embodiment, process flow is as shown in Figure 1, using following methods system
It is standby:
1) addition porcelain boat is placed in argon gas atmosphere stove after weighing 0.5kg sodium tartrate and the mixing of 0.5kg sodium acetate, with 20
DEG C/rate of min is warming up to 1000 DEG C, 4h is kept the temperature, is cooled to room temperature, is obtained black block and crush, as calcined material；
2) distilled water that 5kg temperature is 100 DEG C is added into calcined material and carries out filtering and washing, is repeated 10 times, will wash
Filter residue after washing is dried for 24 hours at 80 DEG C, obtains network-like amorphous carbon nanometer sheet；
3) under argon hydrogen mixed atmosphere (hydrogen volume content be 30%), by network-like amorphous carbon nanometer sheet with 10 DEG C/
The rate of min is warming up to 600 DEG C and is made annealing treatment, and keeps the temperature 0.5h at 600 DEG C, is cooled to room temperature up to the network-like stone of 38g
Black alkene nanometer sheet.
In the embodiment, the filtrate 4.65kg that step 2) washing generates, after detecting metal ion content, by theoretical amount plus
Enter the hydrofluoric acid that mass concentration is 60% to be reacted, 880g sodium fluoride product is made.
Embodiment 6
The network-like graphene nano material of the present embodiment, process flow is as shown in Figure 1, using following methods system
It is standby:
1) addition porcelain boat is placed in nitrogen atmosphere stove after weighing 0.5kg sodium benzoate and the mixing of 0.5kg sodium citrate, with
The rate of 12 DEG C/min is warming up to 700 DEG C, keeps the temperature 5h, is cooled to room temperature, obtains black block and crush, as calcined material；
2) distilled water that 3kg temperature is 30 DEG C is added into calcined material and carries out filtering and washing, is repeated 5 times, will wash
The dry 20h at 60 DEG C of filter residue afterwards, obtains network-like amorphous carbon nanometer sheet；
3) network-like amorphous carbon nanometer sheet under an argon atmosphere, is warming up to 1200 DEG C of progress with the rate of 10 DEG C/min
Annealing, keeps the temperature 4h at 1200 DEG C, is cooled to room temperature up to the network-like graphene nanometer sheet of 37g.
In the embodiment, the filtrate 2.55kg that step 2) washing generates, after detecting metal ion content, by theoretical amount plus
Enter the hydrofluoric acid that mass concentration is 40% to be reacted, 365g sodium fluoride product is made.
In other embodiments of the invention, carbon source organic matter be glucose, starch, sucrose, gluconic acid, citric acid,
When salicylic acid, grape acid acid calcium, zinc gluconate, network-like graphene nanometer sheet can be prepared as described in Example 1；Carbon source has
When machine object is enuatrol, potassium sorbate, network-like graphene nanometer sheet can be prepared as described in Example 6；Carbon source organic matter is
When calcium citrate, zinc citrate, copper citrate, network-like graphene nanometer sheet can be prepared as described in Example 3.
Test example 1
This test example carries out SEM, TEM and Raman Characterization to the 1 network-like graphene nanometer sheet of gained of test example, as a result
As shown in Fig. 2~Fig. 5, material prepared known to the characterization result of Fig. 2~Fig. 4 is network-like graphene nano material, lamella
Relatively thin, degree of graphitization is higher, and three-dimensional network-like structure, graphene sheet layer is presented in the network-like graphene nanometer sheet of embodiment 1
Interlamellar spacing it is wider；By the Raman spectrum of Fig. 5 it is found that material prepared is the grapheme material of few layer, defect is less, graphitization
Degree is high.
Test example 2
This test example assembles sodium using network-like graphene nanometer sheet obtained by each embodiment as sodium ion battery electrode material
Ion half-cell: select sodium piece for electrode, 1.0M NaClO4EC/DMC (1:1 volume ratio) is dissolved in as electrolyte, in gloves
It is tested after case (water content is less than 1.0ppm, and oxygen content is less than 1.0ppm) inner progress CR2032 half-cell assembling.When test, first with
5 circle of 0.1A/g activation, shown in testing result table 1, the sodium electrical property of embodiment 1 is as shown in Figure 6.
The sodium electrical property testing result of the network-like graphene nanometer sheet of each embodiment of table 1
By the testing result of table 1 and Fig. 6 it is found that the sodium ion electricity prepared using network-like graphene nanometer sheet of the invention
Pond after 1000 circulations, has good since network-like graphene nanometer sheet has wide interlamellar spacing and superior electrical conductivity
Reversible capacity and capacity retention ratio performance show that network-like graphene nanometer sheet storage sodium is functional, and with the network-like graphite
The sodium-ion battery excellent electrical property that alkene nano material is prepared as electrode material has good industrial applications prospect.
Claims (4)
1. a kind of network-like graphene nano material, which is characterized in that be prepared by method comprising the following steps:
1) carbon source organic matter is calcined at 500~1000 DEG C, obtains calcined material；
2) water is added into calcined material to be washed, filter residue is obtained by filtration；
3) under protective atmosphere, by filter residue make annealing treatment to get；
In step 1), when calcination process carries out under argon gas or nitrogen atmosphere, the carbon source organic matter is glucose, starch, sugarcane
Sugar, gluconic acid, citric acid, salicylic acid, sodium gluconate, calcium gluconate, zinc gluconate, sodium acetate, enuatrol, winestone
Sour sodium, calcium stearate, sodium benzoate, potassium sorbate, sodium citrate, calcium citrate, zinc citrate, lithium citrate, copper citrate,
One of ammonium citrate or multiple combinations；
When calcination process carries out in air atmosphere, the carbon source organic matter is sodium gluconate, calcium gluconate, gluconic acid
Zinc, sodium acetate, enuatrol, sodium tartrate, calcium stearate, sodium benzoate, potassium sorbate, sodium citrate, calcium citrate, citric acid
One of zinc, lithium citrate, copper citrate, ammonium citrate or multiple combinations；
In step 1), when calcining, 1~10h is kept the temperature at 500~1000 DEG C；
In step 3), when protective atmosphere is argon gas or nitrogen, the temperature of annealing is 600~1600 DEG C, and the time of heat preservation is
0.5~6h；
In step 3), when protective atmosphere is the mixed gas that hydrogen and argon gas or hydrogen and nitrogen form, the temperature of annealing
It is 200~1050 DEG C, the time of heat preservation is 0.5~6h.
2. network-like graphene nano material as described in claim 1, which is characterized in that in step 2, to filtering gained filter
Hydrofluoric acid is added in liquid to be reacted, metal fluoride is prepared.
3. a kind of preparation method of network-like graphene nano material, which comprises the following steps:
1) carbon source organic matter is calcined at 500~1000 DEG C, obtains calcined material；
2) water is added into calcined material to be washed, filter residue is obtained by filtration；
3) under protective atmosphere, by filter residue make annealing treatment to get；
In step 1), when calcination process carries out under argon gas or nitrogen atmosphere, the carbon source organic matter is glucose, starch, sugarcane
Sugar, gluconic acid, citric acid, salicylic acid, sodium gluconate, calcium gluconate, zinc gluconate, sodium acetate, enuatrol, winestone
Sour sodium, calcium stearate, sodium benzoate, potassium sorbate, sodium citrate, calcium citrate, zinc citrate, lithium citrate, copper citrate,
One of ammonium citrate or multiple combinations；
When calcination process carries out in air atmosphere, the carbon source organic matter is sodium gluconate, calcium gluconate, gluconic acid
Zinc, sodium acetate, enuatrol, sodium tartrate, calcium stearate, sodium benzoate, potassium sorbate, sodium citrate, calcium citrate, citric acid
One of zinc, lithium citrate, copper citrate, ammonium citrate or multiple combinations；
In step 1), when calcining, 1~10h is kept the temperature at 500~1000 DEG C；
In step 3), when protective atmosphere is argon gas or nitrogen, the temperature of annealing is 600~1600 DEG C, and the time of heat preservation is
0.5~6h；
In step 3), when protective atmosphere is the mixed gas that hydrogen and argon gas or hydrogen and nitrogen form, the temperature of annealing
It is 200~1050 DEG C, the time of heat preservation is 0.5~6h.
4. a kind of network-like graphene nano material answering as sodium ions to potassium ions battery electrode material as described in claim 1
With.
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| CN110449149A (en) * | 2019-06-27 | 2019-11-15 | 天津大学 | A kind of preparation method of carbon network supported noble metals nano-particle material |
| CN111036219B (en) * | 2019-12-31 | 2020-11-24 | 武汉理工大学 | Foam carbon blended ZIF-67 pyrolysis derived carbon material and preparation method thereof |
| CN111864204A (en) * | 2020-05-28 | 2020-10-30 | 武汉理工大学 | Self-supporting graphene carbon conductive network material and preparation method and application thereof |
| CN113948683B (en) * | 2020-07-17 | 2023-03-03 | 河南省氟基新材料科技有限公司 | Silicon monoxide composite negative electrode material and preparation method and application thereof |
| CN112186363A (en) * | 2020-09-24 | 2021-01-05 | 武汉汉烯科技有限公司 | Flexible macroscopic graphene frequency selective surface |
| CN115262035A (en) * | 2021-04-30 | 2022-11-01 | 中国科学院宁波材料技术与工程研究所 | Graphene nanofiber material and preparation method and application thereof |
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| CN105152167A (en) * | 2015-10-16 | 2015-12-16 | 合肥工业大学 | Large-scale synthesis method of two-dimensional graphene-like carbon material by using sodium citrate |
| US20160060123A1 (en) * | 2014-11-03 | 2016-03-03 | Alimorad Rashidi | Producing graphene and nanoporous graphene |
| CN105776171A (en) * | 2014-12-26 | 2016-07-20 | 广西师范大学 | Three-dimensional net structure carbon nanosheet material and preparation method thereof |
| CN106587017A (en) * | 2016-12-14 | 2017-04-26 | 中国石油大学(北京) | Porous graphene and preparation method thereof |
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| US20160060123A1 (en) * | 2014-11-03 | 2016-03-03 | Alimorad Rashidi | Producing graphene and nanoporous graphene |
| CN105776171A (en) * | 2014-12-26 | 2016-07-20 | 广西师范大学 | Three-dimensional net structure carbon nanosheet material and preparation method thereof |
| CN105152167A (en) * | 2015-10-16 | 2015-12-16 | 合肥工业大学 | Large-scale synthesis method of two-dimensional graphene-like carbon material by using sodium citrate |
| CN106587017A (en) * | 2016-12-14 | 2017-04-26 | 中国石油大学(北京) | Porous graphene and preparation method thereof |
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