CN107128902A - 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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- CN107128902A CN107128902A CN201710295610.2A CN201710295610A CN107128902A CN 107128902 A CN107128902 A CN 107128902A CN 201710295610 A CN201710295610 A CN 201710295610A CN 107128902 A CN107128902 A CN 107128902A
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of network-like graphene nano material and its preparation method and application.The preparation of the network-like graphene nano material includes：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, be filtrated to get filter residue；3) under protective atmosphere, filter residue is made annealing treatment at 200~1600 DEG C, produced.The network-like graphene nano material of the present invention, using carbon source organic matter as raw material, it is prepared from through calcining, washing, secondary high-temperature annealing process, extra template and molten mold process is not related to, technological process is simple, and the requirement to equipment is low, be easily achieved industrialized production；The network-like graphene nano material, with wide interlamellar spacing and superior electrical conductivity, shows excellent storage sodium performance.
Description
Technical field
The present invention relates to the preparation field of graphene, and in particular to a kind of network-like graphene nano material and its preparation side
Method and application.
Background technology
Graphene is as a kind of new two-dimentional carbon material, and its unique physicochemical characteristics makes it in electrode material, storage
The fields such as hydrogen material, biology sensor, catalyst carrier, energy storage material have broad application prospects, but due to graphene
Size is in microcosmic magnitude, and graphene has very strong π-π and interacted and van der waals force between layers, is typically easy to hair
It is raw to reunite and stack, so that its application potential is had a greatly reduced quality.The graphene nano chip architecture of network blackboard can be reduced
Reunion and stacking between graphene film, while there is the loose structure and the intrinsic property of graphene film of uniqueness, thus can be with
More spaces are provided for electrons/ions, gas/liquid transmission and storage.
Authorization Notice No. discloses a kind of graphene with three-dimensional full-mesh network for CN102674321B patent and steeped
Foam, it is to grow three-dimensional in three-dimensional porous metallic surface catalytic pyrolysis carbon-source gas by the technology of chemical vapor deposition to connect
Logical graphene, it is follow-up molten except the graphene three-dimensional macro body that porous foam shape is obtained after porous metals substrate.The preparation method
Technological process it is complex, it is difficult to realize industrialized production.
The content of the invention
It is an object of the invention to provide a kind of network-like graphene nano material, so as to solve the work of prior art presence
Skill is complicated, the problem of be difficult to industrialized production.
Second object of the present invention is the preparation method for providing 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 solution adopted in the present invention is：
A kind of network-like graphene nano material, is prepared from by the method comprised 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, be filtrated to get filter residue；
3) under protective atmosphere, filter residue is made annealing treatment at 200~1600 DEG C, produced.
The network-like graphene nano material of the present invention, using carbon source organic matter as raw material, through calcining, washing, secondary high-temperature
Annealing process is prepared from, and extra template and molten mold process are not related to, and technological process is simple, and the requirement to equipment is low, be easy to
Realize industrialized production；The network-like graphene nano material, with wide interlamellar spacing and superior electrical conductivity, shows excellent
Store up sodium performance.
Step 1) in, the carbon source organic matter is glucose, starch, sucrose, gluconic acid, citric acid, salicylic acid, grape
Sodium saccharate, calcium gluconae, zinc gluconate, sodium acetate, enuatrol, sodium tartrate, calcium stearate, sodium benzoate, sorbic acid
One or more combinations in potassium, sodium citrate, calcium citrate, zinc citrate, lithium citrate, copper citrate, ammonium citrate.
Step 1) in, calcination process is carried out under air, argon gas or nitrogen atmosphere.Air atmosphere is not suitable for carbohydrate and had
Machine acids, acylate can be calcined in air atmosphere.I.e. carbon source organic matter is selected from sodium gluconate, calcium gluconae, Portugal
Grape saccharic acid zinc, sodium acetate, enuatrol, sodium tartrate, calcium stearate, sodium benzoate, potassium sorbate, sodium citrate, calcium citrate,
When one or more in zinc citrate, lithium citrate, copper citrate, ammonium citrate are combined, calcination process can be in air atmosphere
It is lower to carry out.
Step 1) in, the speed for being warming up to 500~1000 DEG C is 1~20 DEG C/min.During calcining, at 500~1000 DEG C
It is incubated 1~10h.Carbon source organic matter be ammonium citrate when, step 1) calcination process produce waste gas mass concentration be 2% hydrogen
Ammonium fluoride solution is made after absorbing in fluoric acid, for the production of other fluorides.
Step 2) in, the quality for adding water is 1~6 times of the corresponding carbon source organic matter quality of calcined material.The temperature of washing
For 30~100 DEG C.Can cyclic washing 1~10 time, to remove unnecessary salt.Drying carries out subsequent anneal processing again after washing.It is dry
Dry temperature is 60~80 DEG C, and the dry time is 12~24h.
Step 2) in, when carbon source organic matter contains metal ion, into filtering gained filtrate, addition hydrofluoric acid is reacted,
Prepare metal fluoride.The mass concentration of hydrofluoric acid is preferably 1~60%.
Step 3) in, the protective atmosphere is the mixed gas of argon gas or nitrogen or hydrogen and argon gas composition.Mixed gas
In, the volume ratio shared by hydrogen is 5~50%.
Step 3) in, the technological parameter of annealing according to the selection of protective atmosphere, can be adjusted.Protective atmosphere be argon gas or
During nitrogen, the temperature of annealing is 600~1600 DEG C, is 0.5~6h in the time of 600~1600 DEG C of insulations.It is preferred that, rise
The speed 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 are constituted, annealing
The temperature of processing is 200~1050 DEG C, is 0.5~6h in the time of 200~1050 DEG C of insulations.It is preferred that, it is warming up to 200~
1050 DEG C of speed 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, relatively simple nitrogen or argon gas, using nitrogen and hydrogen mixture or argon hydrogen gaseous mixture, can further improve
The probability that atmospheric CO and carbon dioxide are formed because being reacted in residual oxygen pyroprocess in oxygen in raw material itself and system with carbon,
Improving material yield.
The network-like graphene nano material that the present invention is provided, whole technical process is relatively friendly to environment, is not related to acid
It is mostly inorganic salts in alkali and inflammable gas, the waste water of generation, it is easy to reclaim, environmental pollution is small；Removed using washing process
The unnecessary salt that calcination process is produced, is conducive to subsequent anneal processing to prepare the network-like graphite of wide interlamellar spacing and superior electrical conductivity
Alkene nanometer sheet；Metal ion in filtrate is converted into the metal fluoride of high added value, carried while environmentally friendly bottleneck is solved
High element utilization rate, has reached the purpose of clean manufacturing and has provided new growth engines for enterprise.
A kind of preparation method of network-like graphene nano material, 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, be filtrated to get filter residue；
3) under protective atmosphere, filter residue is made annealing treatment at 200~1600 DEG C, produced.
The optimum choice of each step is same as described above.
The preparation method of the network-like graphene nano material of the present invention, raw materials are abundant, cheap and easy to get, equipment is wanted
Seek simple, environment-friendly, product quality stabilization；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 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 property such as reversible capacity, capability retention, with wide market application foreground.
Brief description of the drawings
Fig. 1 is process chart of the invention；
Fig. 2 is the SEM figures of the network-like graphene nanometer sheet of the gained of the embodiment of the present invention 1；
Fig. 3 is the TEM figures of the network-like graphene nanometer sheet of the gained of the embodiment of the present invention 1；
Fig. 4 is the HR-TEM figures of the network-like graphene nanometer sheet of the gained of the embodiment of the present invention 1；
Fig. 5 is the Raman collection of illustrative plates of the network-like graphene nanometer sheet of the gained of the embodiment of the present invention 1；
Fig. 6 is the electrical property detection knot of the sodium-ion battery prepared by the network-like graphene nanometer sheet using embodiment 1
Really.
Embodiment
Embodiments of the present invention are described further with reference to specific embodiment.
Embodiment 1
The network-like graphene nano material of the present embodiment, technological process is as shown in figure 1, using following methods system
It is standby：
1) weigh 1kg sodium gluconates addition porcelain boat to be placed in argon gas atmosphere stove, 500 are warming up to 10 DEG C/min speed
DEG C, 4h is incubated, is down to after room temperature, is obtained black block and crush, as calcined material；
2) 6kg temperature is added into calcined material and carries out filtering and washing for 30 DEG C of distilled water, is repeated 8 times, will wash
Filter residue afterwards dries 12h at 60 DEG C, 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 20 DEG C/min speed
Annealing, is incubated 6h at 600 DEG C, is down to after room temperature and produces the network-like graphene nanometer sheets of 50g.
In the embodiment, step 2) the filtrate 5.5kg that produces of washing, after testing after metal ion content, by theoretical amount plus
Enter the hydrofluoric acid that mass concentration is 10% to be reacted, 85g sodium fluoride products are made.
Embodiment 2
The network-like graphene nano material of the present embodiment, technological process is as shown in figure 1, using following methods system
It is standby：
1) weigh 1kg calcium stearates addition porcelain boat to be placed in nitrogen atmosphere stove, 1000 are warming up to 8 DEG C/min speed
DEG C, 2h is incubated, is down to after room temperature, is obtained black block and crush, as calcined material；
2) 2kg temperature is added into calcined material and carries out filtering and washing for 60 DEG C of distilled water, is repeated 2 times, will wash
Filter residue afterwards dries 20h at 60 DEG C, 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 15 DEG C/min speed
Annealing, is incubated 1h at 1600 DEG C, is down to after room temperature and produces the network-like graphene nanometer sheets of 30g.
In the embodiment, step 2) the filtrate 1.5kg that produces of washing, after testing after metal ion content, by theoretical amount plus
Enter the hydrofluoric acid that mass concentration is 20% to be reacted, 105g fluorination calcium products are made.
Embodiment 3
The network-like graphene nano material of the present embodiment, technological process is as shown in figure 1, using following methods system
It is standby：
1) weigh 1kg lithium citrates addition porcelain boat to be placed in air atmosphere stove, 700 are warming up to 3 DEG C/min speed
DEG C, 1h is incubated, is down to after room temperature, is obtained black block and crush, as calcined material；
2) 3kg temperature is added into calcined material and carries out filtering and washing for 70 DEG C of distilled water, is repeated 5 times, will wash
Filter residue afterwards dries 20h at 60 DEG C, obtains network-like amorphous carbon nanometer sheet；
3) network-like amorphous carbon nanometer sheet under an argon atmosphere, is warming up into 900 DEG C with 5 DEG C/min speed to be moved back
Fire processing, is incubated 1h at 900 DEG C, is down to after room temperature and produces the network-like graphene nanometer sheets of 40g.
In the embodiment, step 2) the filtrate 2.45kg that produces of washing, after testing after metal ion content, by theoretical amount plus
Enter the hydrofluoric acid that mass concentration is 20% to be reacted, 110g lithium fluoride products are made.
Embodiment 4
The network-like graphene nano material of the present embodiment, technological process is as shown in figure 1, using following methods system
It is standby：
1) weigh 1kg ammonium citrates addition porcelain boat to be placed in argon gas atmosphere stove, 500 are warming up to 1 DEG C/min speed
DEG C, 1h is incubated, is down to after room temperature, is obtained black block and crush, as calcined material；
2) 4kg temperature is added into calcined material and carries out filtering and washing for 80 DEG C of distilled water, is repeated 3 times, will wash
Filter residue afterwards dries 24h at 80 DEG C, 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/
Min speed is warming up to 950 DEG C and made annealing treatment, and 1h is incubated at 950 DEG C, is down to after room temperature and produces the network-like graphite of 35g
Alkene nanometer sheet.
In the embodiment, step 1) the waste gas mass concentration that produces of calcination process is made after being absorbed for 2% hydrofluoric acid
Ammonium fluoride solution, for the production of other fluorides.
Embodiment 5
The network-like graphene nano material of the present embodiment, technological process is as shown in figure 1, using following methods system
It is standby：
1) weigh addition porcelain boat after 0.5kg sodium tartrates and the mixing of 0.5kg sodium acetates to be placed in argon gas atmosphere stove, with 20
DEG C/min speed is warming up to 1000 DEG C, 4h is incubated, is down to after room temperature, is obtained black block and crush, as calcined material；
2) 5kg temperature is added into calcined material and carries out filtering and washing for 100 DEG C of distilled water, is repeated 10 times, will wash
Filter residue after washing dries 24h 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/
Min speed is warming up to 600 DEG C and made annealing treatment, and 0.5h is incubated at 600 DEG C, is down to after room temperature and produces the network-like stones of 38g
Black alkene nanometer sheet.
In the embodiment, step 2) the filtrate 4.65kg that produces of washing, after testing after metal ion content, by theoretical amount plus
Enter the hydrofluoric acid that mass concentration is 60% to be reacted, 880g sodium fluoride products are made.
Embodiment 6
The network-like graphene nano material of the present embodiment, technological process is as shown in figure 1, using following methods system
It is standby：
1) addition porcelain boat after 0.5kg sodium benzoates and the mixing of 0.5kg sodium citrates is weighed to be placed in nitrogen atmosphere stove, with
12 DEG C/min speed is warming up to 700 DEG C, is incubated 5h, is down to after room temperature, obtains black block and crush, as calcined material；
2) 3kg temperature is added into calcined material and carries out filtering and washing for 30 DEG C of distilled water, is repeated 5 times, will wash
Filter residue afterwards dries 20h at 60 DEG C, 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 10 DEG C/min speed
Annealing, is incubated 4h at 1200 DEG C, is down to after room temperature and produces the network-like graphene nanometer sheets of 37g.
In the embodiment, step 2) the filtrate 2.55kg that produces of washing, after testing after metal ion content, by theoretical amount plus
Enter the hydrofluoric acid that mass concentration is 40% to be reacted, 365g sodium fluoride products are made.
In other embodiments of the invention, carbon source organic matter be glucose, starch, sucrose, gluconic acid, citric acid,
When salicylic acid, the sour calcium of grape acid, zinc gluconate, network-like graphene nanometer sheet can be prepared as described in Example 1；Carbon source has
When machine thing 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 network-like graphene nanometer sheet of the gained of test example 1, as a result
As shown in Fig. 2~Fig. 5, understand that prepared material is network-like graphene nano material, lamella by Fig. 2~Fig. 4 characterization result
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；From Fig. 5 Raman spectrum, prepared material is the grapheme material of few layer, and defect is less, graphitization
Degree is high.
Test example 2
Network-like graphene nanometer sheet obtained by each embodiment is assembled sodium by this test example as sodium ion battery electrode material
Ion half-cell：It is to electrode, 1.0M NaClO to select sodium piece4It is dissolved in EC/DMC (1：1 volume ratio) as electrolyte, in gloves
Tested after case (water content is less than 1.0ppm, and oxygen content is less than 1.0ppm) inner progress CR2032 half-cell assemblings.During test, first with
0.1A/g activation 5 is enclosed, and 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
From the testing result of table 1 and Fig. 6, the sodium ion electricity prepared using the network-like graphene nanometer sheet of the present invention
Pond, because network-like graphene nanometer sheet has wide interlamellar spacing and superior electrical conductivity, after 1000 times circulate, with good
Reversible capacity and capability retention 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, with good industrial applications prospect.
Claims (9)
1. a kind of network-like graphene nano material, it is characterised in that be prepared from by the method comprised 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, be filtrated to get filter residue；
3) under protective atmosphere, filter residue is made annealing treatment at 200~1600 DEG C, produced.
2. network-like graphene nano material as claimed in claim 1, it is characterised in that step 1) in, the carbon source is organic
Thing be glucose, starch, sucrose, gluconic acid, citric acid, salicylic acid, sodium gluconate, calcium gluconae, zinc gluconate,
Sodium acetate, enuatrol, sodium tartrate, calcium stearate, sodium benzoate, potassium sorbate, sodium citrate, calcium citrate, zinc citrate,
One or more combinations in lithium citrate, copper citrate, ammonium citrate.
3. network-like graphene nano material as claimed in claim 1, it is characterised in that step 1) in, calcination process is in sky
Carried out under gas, argon gas or nitrogen atmosphere.
4. network-like graphene nano material as claimed in claim 1, it is characterised in that step 1) in, during calcining, 500
1~10h is incubated at~1000 DEG C.
5. network-like graphene nano material as claimed in claim 1, it is characterised in that step 2) in, filtered to filtering gained
Hydrofluoric acid is added in liquid to be reacted, and prepares metal fluoride.
6. network-like graphene nano material as claimed in claim 1, it is characterised in that step 3) in, protective atmosphere is argon
Gas or nitrogen, the temperature of annealing is 600~1600 DEG C, is 0.5~6h in the time of 600~1600 DEG C of insulations.
7. network-like graphene nano material as claimed in claim 1, it is characterised in that step 3) in, protective atmosphere is hydrogen
The mixed gas of gas and argon gas composition, the temperature of annealing is 200~1050 DEG C, is in the time of 200~1050 DEG C of insulations
0.5~6h.
8. a kind of preparation method of network-like graphene nano material, it is characterised in that comprise 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, be filtrated to get filter residue；
3) under protective atmosphere, filter residue is made annealing treatment at 200~1600 DEG C, produced.
9. a kind of network-like graphene nano material as claimed in claim 1 answering as sodium ions to potassium ions battery electrode material
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 |
| CN111036219A (en) * | 2019-12-31 | 2020-04-21 | 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 |
| CN112186363A (en) * | 2020-09-24 | 2021-01-05 | 武汉汉烯科技有限公司 | Flexible macroscopic graphene frequency selective surface |
| CN113948683A (en) * | 2020-07-17 | 2022-01-18 | 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 |
| 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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