CN105060288B - A kind of method that Graphene is prepared for raw material with biomass waste material - Google Patents
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Abstract
The invention discloses a kind of method that Graphene is prepared for raw material with biomass waste material, obtain biomass residue including by biomass waste material Calx pretreatment；Then, biomass residue is carried out desiliconization hydrolysis, carbonization, be rapidly heated after carbonized stock decalcification remove impurity and carry out high temperature graphitization.The Graphene that the present invention prepares has the number of plies few (2 10 layers), defect is few, oxy radical is few, electrical conductivity is high, the closely spaced advantage of carbon-coating.The few layer graphene of biomass of present invention preparation has certain meso-hole structure, is particularly suitable for the fields such as lithium ion battery, ultracapacitor.Present invention process is simple and convenient to operate, low cost, Graphene yield high, be easily achieved industrialization large-scale production.
Description
Technical field
The present invention relates to technical field of graphene preparation, particularly to one kind, Graphene is prepared for raw material with biomass waste material
Method.
Background technology
Graphene (Graphene) is a kind of monolayer laminated structure being made up of carbon atom, and only one of which carbon atom is thick
The two-dimensional material of degree.Graphene all shows more excellent performance in many aspects, and the heat conductivity of such as Graphene is up to
5300W/m K, higher than diamond and CNT；Graphene is almost fully transparent, only absorbs 2.3% light, its printing opacity
Property is very good；At room temperature, the electron mobility of Graphene is up to 15000cm2/ V s, exceedes silicon crystal and CNT；Stone
The resistivity of black alkene only has 10-6Ω cm, lower than copper or silver, it is the material of resistivity minimum so far；In addition Graphene
It is also current the thinnest but hard material.Due to having these excellent physics and chemical property, Graphene is in electronics, letter
The fields such as breath, the energy, material and biomedicine have great application prospect.Particularly energy field, Graphene has height leads
Electrically, the features such as pliability is good, chemical stability is high, therefore it acts not only as the nanoparticle deposition thing of favorable dispersibility
Support, and can apply wider in lithium ion battery, fuel cell and ultracapacitor as conductive matrices.
At present, grapheme material can be prepared using multiple methods, such as mechanical stripping method, crystal epitaxy method, chemistry
Vapour deposition process, oxidation-reduction method and stripping CNT method etc..In these methods, mechanical stripping method yield is relatively low, and mistake
The more difficult control of journey；Epitaxial growth method can be used for preparing larger-size graphene film, but equally exists low yield and high cost
Problem.Although chemical vapour deposition technique can obtain the continuous graphene film of large scale, it is only applicable to micro-nano electronic device
Or transparent conductive film, but can not meet the extensive demand in energy storage material and functional composite material field.Oxidation-reduction method is led to
Be considered as often a kind of low cost, the method preparing Graphene of high yield, but the method preparation during using a large amount of
Strong acid and oxidant, destroy to graphenic surface serious, easily pollute environment, and due to carbon-coating between there is stronger Van der Waals
Power, the general lamella of the Graphene prepared is thicker, and specific surface area is less, has a strong impact on its properties, and therefore this method is also uncomfortable
Close the Graphene preparation of extensive industrialization.Additionally, the raw material that these preparation methoies use is all chemical raw material, with working as this life
The petering out and the problems such as caused environmental pollution is increasingly serious of boundary's fossil energy, the use of chemical raw material in preparation technology
Have become increasingly limited, the natural raw material beyond seeking using non-chemically raw material grinds greatly to prepare Graphene and be increasingly becoming one
Study carefully problem.
Biomass waste material is primarily referred to as the wood fibre such as the straw in addition to grain, fruit, trees during agricultural and forestry production
Element, the material such as farming industry leftover bits and pieces, agriculture and forestry organic waste material, it is mainly characterized by renewable, low stain and widely distributed.But
These discarded biomass are mostly laid in field or open incineration, not only cause the waste of biomass resource, destroy
Soil structure, make production capacity decline, also results in serious environmental pollution.Therefore, how biomass petroleum replacing, coal are utilized
The non-renewable resources such as charcoal progress into the visual field of vast researcher.
In recent years, in the face of the Graphene market of sharp increase in the world, various countries' researcher has started to explore using life
Material prepares Graphene, and patent CN 104016341 A discloses a kind of preparation method of porous graphene, makees in catalyst
With under, biomass carbon source is carried out after catalytic treatment, more just can get porous graphene through a series of isothermal holding；This method
There is the defects such as the graphene sheet layer obtaining is thicker, defect is more.Dong Han Seo et al. with Mel, sucrose, butter etc. is
Presoma, has been prepared the vertical Graphene of functionalization, but the method is higher to equipment requirements using low temperature plasma method, former
Material cost is also larger, and the yield of Graphene is relatively low (Adv.Mater., 2013,25,5638-5642).Therefore, research life
The method that material low cost produces the few layer graphene of high-quality in enormous quantities is that meaning is huge, very necessary.
Content of the invention
The technical problem to be solved in the present invention is for the deficiency in above-mentioned graphene preparation technology, provides one kind with biology
The method that matter waste material prepares Graphene for raw material, the method process is simple, easy to operate, low cost, Graphene yield are high, be easy to
Realize industrialization large-scale production, using the Graphene that the method prepares, there is the number of plies few (2-10 layer), defect few, oxygen-containing
Group is few, electrical conductivity is high, the closely spaced advantage of carbon-coating.
In order to realize foregoing invention purpose, the present invention is achieved through the following technical solutions：
A kind of method preparing Graphene for raw material with biomass waste material of the present invention, comprises the steps：
The first step：Biomass waste material pretreatment
Biomass waste material is soaked after softening, add Calx and boil, then, solid-liquid separation, obtain biomass solid residual
Slag and yellow, viscous liquid；
Second step：Biomass solid residue desiliconization is hydrolyzed
The biomass solid residue that the first step is obtained first soaks in a solution of hydrofluoric acid, then boils, obtains after filtration
Desiliconization hydrolysis residue；
3rd step：The carbonization of desiliconization hydrolysis residue
By second step gained desiliconization hydrolysis residue heating and calcining under protective atmosphere, obtain carbonized stock；
4th step：Carbonized stock decalcification remove impurity
The carbonized stock that 3rd step is obtained soaks decalcification remove impurity in acid solution, solid-liquid separation after immersion, by the filter obtaining
Pulp water wash clean, obtains biomass carbon；
5th step：High temperature graphitization
By the 4th step gained biomass carbon, under an argon atmosphere, it is heated to 2400 with the heating rate of at least 20 DEG C/min
Carry out high temperature graphitization more than DEG C, obtain the few layer graphene of biomass.
A kind of method that Graphene is prepared for raw material with biomass waste material of the present invention,
In the first step：
It is to soak 1-3 days biomass waste material with the water of 8～10 times of its quality that biomass waste material soaks softening；
The addition of Calx is the 30～35% of biomass waste material quality；
Boil temperature retention time 3～4h；
In second step：
The mass percentage concentration of hydrofluoric acid solution is 5-25%；
Hydrofluoric acid solution presses liquid-solid ratio 2-8 with biomass solid residue:1Kg/L configures, and preferred liquid-solid ratio is 3-5:1；
50-70 DEG C of soaking temperature, soak time 30-90min；
Before boiling, the liquid-solid ratio of the mixed liquor first constituting biomass solid residue with hydrofluoric acid solution is diluted to (10-
20):1 (L/Kg), preferred liquid-solid ratio is 15-20:1；Boiling time 90-150min；
In 3rd step：
Desiliconization hydrolysis residue, under atmosphere protection, rises to 400-800 DEG C with the heating rate of 1-20 DEG C/min, is incubated 1～4h；
Preferably heating rate is 5-10 DEG C/min；Holding temperature is 400-800 DEG C；
In 4th step：
The molar concentration of acid solution is 0.1-3.0mol/L, and preferred molar concentration is 1-2mol/L,
Carbonized stock presses liquid-solid ratio 1-5 with acid solution:1L/Kg configures, and preferred liquid-solid ratio is 2-3:1；
Soak time 0.5-2h,
During immersion, apply ultrasonic vibration,
It is 6-8 that filtering residue deionized water is washed till washing liquid pH；
In 5th step：
The purity of high-purity argon gas is 99.999%,
20-100 DEG C of heating rate/min, preferred heating rate is 8-100 DEG C/min,
High temperature graphitization temperature is 2400～3000 DEG C, is incubated 5-60min；Preferably high temperature graphitization temperature be 2600～
2800 DEG C, temperature retention time 30-60min.
A kind of method preparing Graphene for raw material with biomass waste material of the present invention, biomass waste material refers to that main component is
The agriculture and forestry organic waste material of cellulose, hemicellulose and lignin；Described agriculture and forestry organic waste material is straw, rice straw, corn stalk, Sorghum vulgare Pers.
One or more of stalk, rice husk, bagasse, wood flour, cotton stalk, bamboo product processing waste material.
A kind of method that Graphene is prepared for raw material with biomass waste material of the present invention,
Protective atmosphere described in 3rd step is selected from any one of nitrogen, argon, hydrogen, ammonia, the entering of protective gas
Throughput is 100～400sccm, purity >=99.999% of gas selected by protective atmosphere.
A kind of method that Graphene is prepared for raw material with biomass waste material of the present invention,
The ultrasonic power that ultrasonic vibration described in 4th step adopts is 100～200W, and frequency is 40～80KHz.
A kind of method that Graphene is prepared for raw material with biomass waste material of the present invention,
In 4th step, described acid solution is selected from hydrochloric acid, nitric acid or the mixed acid prepared by hydrochloric acid and nitric acid with arbitrary proportion.
A kind of method that Graphene is prepared for raw material with biomass waste material of the present invention,
In 5th step, described argon inlet flow is 200～500sccm, and preferred charge flow rate is 300-
500sccm.
A kind of method preparing Graphene for raw material with biomass waste material of the present invention, hydrochloric acid, nitric acid, Fluohydric acid. are analysis
Pure.
The present invention is announced, and graphene preparation method has the advantages that：
(1) raw material preparing Graphene of the present invention is biomass waste material, and this is not only the high-valued of biomass waste material
Using opening a new direction, and also reduce the pollution to environment for the biomass waste material；
(2) Graphene preparing raw material of the present invention is rich and easy to get, is that the low cost preparation of Graphene creates condition；
(3) adopt lime treatment biomass waste material, not only with low cost, but also can achieve non-fiber in biomass waste material
The efficient dissolution of plain composition, the yellow, viscous liquid of institute's dissolution is a kind of good biomass binding agent, can be used on moulded coal life
The aspects such as product；
(4) adopt hydrofluoric acid treatment further, the siliceous harmful constituent in biomass waste material not only can be removed, and,
Also further the non-cellulose components in biomass waste material can be dissolved out, further reduce the quick graphitization of subsequent high temperature
Peel off the resistance of carbon-coating；
(5) quick high-temp graphitization, on the one hand, the small molecule Quick-gasifying being retained in carbonized stock can be made, make carbonized stock
In carbon-coating quickly peel off, generate few layer graphene；On the other hand, the high-temperature process under inert gas shielding, reformable carbon-coating
In carbon arrangement, improve gained graphene conductive ability, furthermore, high temperature graphitization under argon gas, not only facilitate minimizing stone
Oxy radical in black alkene, but also impurity in Graphene can be made to enter tail gas by flashing to gaseous state with argon, so that graphite
The purity of alkene improves further.
(6) the few layer graphene of the biomass of present invention preparation has certain meso-hole structure, is particularly suitable for lithium ion
The fields such as battery, ultracapacitor.
Present invention process is simple and convenient to operate, low cost, Graphene yield high, be easily achieved industrialization large-scale production,
Using the Graphene that the method prepares, there is the number of plies few (2-10 layer), defect is few, oxy radical is few, electrical conductivity is high, carbon-coating
Closely spaced advantage.
Brief description
Accompanying drawing 1 is the scanning electron microscope (SEM) photograph of Graphene obtained by the embodiment of the present invention 1.
Accompanying drawing 2 is the x-ray photoelectron power spectrum of Graphene obtained by the embodiment of the present invention 1.
Accompanying drawing 3 is the Raman energy spectrum of Graphene obtained by the embodiment of the present invention 1.
Knowable to accompanying drawing 1, the Graphene piece for laminated structure that embodiment 1 obtains, there is transparent fold at the edge of piece.
Knowable to accompanying drawing 2, obtained by embodiment 1, the C1s peak of Graphene is very sharp, illustrates that this Graphene is substantially free of and contains
Oxygen groups and other group, and the carbon atom on Graphene is mainly with sp2Presented in hydridization, the electric conductivity of Graphene is relatively
Good.
Knowable to accompanying drawing 3, in the Raman spectrum of Graphene obtained by embodiment 1, there is D peak, G peak and 2D peak, and D peak
With G peak ratio of peak about 1:1.5 about, these show gained Graphene defect is less, electric conductivity is higher；In addition, the depositing of 2D peak
Also illustrating the prepared Graphene number of plies below 10 layers.
Specific embodiment
With reference to embodiment, the present invention will be further described in detail, but is not to be regarded as the protection to the present invention
The restriction of scope.
Embodiment 1：Graphene preparation with rice straw as raw material
1st step, the rice straw of 40-80 mesh is immersed in 3 days in the water of 8～10 times of its quality, and interpolation is equivalent to its matter afterwards
The Calx of amount 35%, stirs, and is then heated to 95～100 DEG C and filters after being incubated 3h, obtains solid residue and yellow
Viscous liquid.
2nd step, solid residue is pressed liquid-solid ratio 3:In 1 Fluohydric acid. being placed in concentration 25%, process 60min at 70 DEG C, with
Liquid-solid ratio will be diluted to 20:1, and process 90min in the case of boiling, it is filtrated to get desiliconization hydrolysis residue；
3rd step, the 2nd step gained desiliconization hydrolysis residue is carried out carbonization treatment.Under the nitrogen of 400sccm flow is protected, with 5
DEG C/heating rate of min rises to 400 DEG C, it is incubated 2h afterwards, obtain carbonized stock.
4th step, by carbonized stock in the hydrochloric acid of 1mol/L, process 1h, decalcification remove impurity at room temperature, then filters, filter cake
It is washed with deionized to be dried after 24h at being 7,80 DEG C to pH and obtain biomass carbon；
5th step, high temperature graphitization.4th step gained biomass carbon is put in high temperature graphitization stove, in 500sccm flow
High-purity argon gas protection under, be rapidly heated to after 2800 DEG C with 100 DEG C/min speed and be incubated at least 30min, obtain biomass few
Layer graphene.
Supersound process described in the present embodiment, the adopted ultrasonic power of supersound washing are 100～200W, frequency is 40～
80KHz.
The scanning electron microscope (SEM) photograph of Graphene, X-ray light obtained by accompanying drawing 1, the accompanying drawing 2 and accompanying drawing 3 respectively embodiment of the present invention 1
Electron spectrum and Raman energy spectrum.It will be apparent that gained graphene film of the present invention has laminated structure and there is transparent pleat at the edge of piece
Wrinkle, preferably, defect is less, and the Graphene number of plies is below 10 layers for the electric conductivity of Graphene.
Embodiment 2：Graphene preparation with bamboo product processing waste material as raw material
1st step, the bamboo product processing waste of 40-80 mesh is immersed in the water of 8～10 times of its quality 3 days afterwards, adds
Plus be equivalent to the Calx of its quality 35%, stir, be then heated to 95～100 DEG C and be incubated 4h obtain solid residue with
Yellow, viscous liquid.
2nd step, solid residue is pressed liquid-solid ratio 3:In 1 Fluohydric acid. being placed in concentration 25%, process 60min at 70 DEG C, with
Liquid-solid ratio will be diluted to 20:1, and process 150min in the case of boiling, it is filtrated to get desiliconization hydrolysis residue；
3rd step, the 2nd step gained desiliconization hydrolysis residue is carried out carbonization treatment.High-purity hydrogen protection in 400sccm flow
Under, rise to 600 DEG C with the heating rate of 10 DEG C/min, be incubated 4h afterwards, obtain carbonized stock.
4th step, by carbonized stock in the nitric acid of 1mol/L, process 2h, decalcification remove impurity at room temperature, then filters, filter cake
It is washed with deionized to be dried after 12h at being 7,120 DEG C to pH and obtain biomass carbon；
5th step, high temperature graphitization, the 4th step gained biomass carbon is put in high temperature graphitization stove, in 300sccm flow
High-purity argon gas protection under, be rapidly heated to after 2600 DEG C with 100 DEG C/min speed and be incubated at least 60min, obtain Graphene.
Supersound process described in the present embodiment, the adopted ultrasonic power of supersound washing are 100～200W, frequency is 40～
80KHz.
, below 10 layers, preferably, defect is less for the electric conductivity of Graphene for the number of plies of the present embodiment gained Graphene.
Claims (8)
1. a kind of method preparing Graphene for raw material with biomass waste material, comprises the steps：
The first step：Biomass waste material pretreatment
By biomass waste material soak soften after, add Calx boil, then, solid-liquid separation, obtain biomass solid residue with
Yellow, viscous liquid；
Biomass waste material refer to main component be cellulose, the agriculture and forestry organic waste material of hemicellulose and lignin；
Second step：Biomass solid residue desiliconization is hydrolyzed
The biomass solid residue that the first step is obtained first soaks in a solution of hydrofluoric acid, then boils, obtains desiliconization after filtration
Hydrolysis residue；
3rd step：The carbonization of desiliconization hydrolysis residue
Second step gained desiliconization hydrolysis residue is heated to 400-800 DEG C of calcining under protective atmosphere, obtains carbonized stock；
4th step：Carbonized stock decalcification remove impurity
The carbonized stock that 3rd step is obtained soaks decalcification remove impurity in acid solution, solid-liquid separation after immersion, by the filtering residue obtaining water
Wash clean, obtains biomass carbon；
5th step：High temperature graphitization
By the 4th step gained biomass carbon, under an argon atmosphere, with the heating rate of at least 20 DEG C/min be heated to 2400 DEG C with
On carry out high temperature graphitization, obtain the few layer graphene of biomass.
2. according to claim 1 a kind of with biomass waste material for raw material prepare Graphene method it is characterised in that：
In the first step：
It is to soak 1-3 days biomass waste material with the water of 8 ~ 10 times of its quality that biomass waste material soaks softening；
The addition of Calx is the 30 ~ 35% of biomass waste material quality；
Boil temperature retention time 3 ~ 4h；
In second step：
The mass percentage concentration of hydrofluoric acid solution is 5-25%；
Biomass solid residue presses liquid-solid ratio 2-8 with hydrofluoric acid solution:1L/Kg configures；
50-70 DEG C of soaking temperature, soak time 30-90min；
Before boiling, the liquid-solid ratio of the mixed liquor first constituting biomass solid residue with hydrofluoric acid solution is diluted to 10-20:1L/
Kg；Boiling time 90-150min；
In 3rd step：
Desiliconization hydrolysis residue, under protective atmosphere, rises to calcining heat with the heating rate of 1-20 DEG C/min, is incubated 1 ~ 4h；
In 4th step：
The molar concentration of acid solution is 0.1-3.0mol/L,
Acid solution presses liquid-solid ratio 1-5 with carbonized stock:1L/Kg configures,
Soak time 0.5-2h,
During immersion, apply ultrasonic vibration,
It is 6-8 that filtering residue deionized water is washed till washing liquid pH；
In 5th step：
20-100 DEG C of heating rate/min,
High temperature graphitization temperature is 2400 ~ 3000 DEG C, is incubated 5-60min.
3. a kind of method preparing Graphene for raw material with biomass waste material according to claim 1 and 2, its feature exists
In：Described agriculture and forestry organic waste material is straw, rice straw, corn stalk, sorghum stalk, rice husk, bagasse, wood flour, cotton stalk, bamboo product are processed
One or more of waste material.
4. a kind of method preparing Graphene for raw material with biomass waste material according to claim 1 and 2, its feature exists
In：Protective atmosphere described in 3rd step is selected from any one of nitrogen, argon, hydrogen, ammonia, the charge flow rate of protective gas
For 100 ~ 400sccm.
5. according to claim 2 a kind of with biomass waste material for raw material prepare Graphene method it is characterised in that：The
The ultrasonic power that ultrasonic vibration described in four steps adopts is 100 ~ 200W, and frequency is 40 ~ 80 KHz.
6. a kind of method preparing Graphene for raw material with biomass waste material according to claim 1 and 2, its feature exists
In：In 4th step, described acid solution is selected from hydrochloric acid, nitric acid or the mixed acid prepared by hydrochloric acid and nitric acid with arbitrary proportion.
7. a kind of method preparing Graphene for raw material with biomass waste material according to claim 1 and 2, its feature exists
In：In 5th step, described argon inlet flow is 200 ~ 500sccm.
8. according to claim 6 a kind of with biomass waste material for raw material prepare Graphene method it is characterised in that：Salt
It is pure that acid, nitric acid, Fluohydric acid. are analysis.
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| CN104724699B (en) | 2015-03-04 | 2017-04-26 | 黑龙江大学 | Method for preparing biomass graphene employing cellulose as raw material |
| CN105502365A (en) * | 2015-12-30 | 2016-04-20 | 成都新柯力化工科技有限公司 | Method for preparing graphene by controlling thickness of primary carbon source |
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| CN107879330A (en) * | 2017-12-15 | 2018-04-06 | 广州中天联合高新技术发展有限公司 | A kind of attachment means of biomass processing equipment |
| CN108298525B (en) * | 2018-03-19 | 2020-02-07 | 广西科学院 | Graphene microcrystal and preparation method thereof |
| CN111785892B (en) * | 2019-04-03 | 2021-10-08 | 中南大学 | Preparation method of lithium-sulfur battery composite diaphragm |
| CN111785912B (en) * | 2019-04-03 | 2021-12-24 | 中南大学 | Preparation method of porous carbon cathode lithium-sulfur battery |
| CN110194446B (en) * | 2019-06-10 | 2022-05-13 | 广西科学院 | Preparation method of graphene 2D powder taking 2D cellulose obtained by deeply hydrolyzing cellulose as raw material |
| CN110357077A (en) * | 2019-07-23 | 2019-10-22 | 路英军 | A kind of biomass graphene preparation method |
| CN110395720A (en) * | 2019-09-03 | 2019-11-01 | 王志朋 | The method for preparing vertical graphene film as raw material using biomass |
| CN111910285A (en) * | 2020-08-14 | 2020-11-10 | 青岛裕王智能科技床业有限公司 | Graphene biological composite fiber and preparation method and application thereof |
| CN112552941A (en) * | 2020-12-18 | 2021-03-26 | 袁新华 | Low-resistance biomass carbon material and preparation method thereof |
| CN112875685A (en) * | 2021-02-03 | 2021-06-01 | 陕西科技大学 | Graphene generated in situ based on lignin and preparation method thereof |
| CN113880078B (en) * | 2021-11-03 | 2023-05-30 | 上海爱普食品工业有限公司 | Preparation method of biomass graphene |
| CN114835108B (en) * | 2022-05-07 | 2024-08-30 | 浙江大学杭州国际科创中心 | Natural biomass-derived graphene with controllable number of layers and preparation method thereof |
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| US9249026B2 (en) * | 2013-11-12 | 2016-02-02 | Shanghai Jiaotong University | Method for preparing graphene from biomass-derived carbonaceous mesophase |
| CN104701546B (en) * | 2013-12-06 | 2019-04-09 | 北京化工大学 | A kind of porous graphene nanometer sheet, preparation method and its application as electrode material |
| CN104724699B (en) * | 2015-03-04 | 2017-04-26 | 黑龙江大学 | Method for preparing biomass graphene employing cellulose as raw material |
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