CN105314622A - Method for preparing hetero-atom doped porous carbon material through carbonation of biomass under assistance of molten salt - Google Patents

Method for preparing hetero-atom doped porous carbon material through carbonation of biomass under assistance of molten salt Download PDF

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Publication number
CN105314622A
CN105314622A CN201510783477.6A CN201510783477A CN105314622A CN 105314622 A CN105314622 A CN 105314622A CN 201510783477 A CN201510783477 A CN 201510783477A CN 105314622 A CN105314622 A CN 105314622A
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China
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porous carbon
biomass
molten salt
melting salt
hetero
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CN201510783477.6A
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Chinese (zh)
Inventor
程魁
曹殿学
欧阳田
江杰涛
叶克
王贵领
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哈尔滨工程大学
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Priority to CN201510783477.6A priority Critical patent/CN105314622A/en
Publication of CN105314622A publication Critical patent/CN105314622A/en

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Abstract

The invention provides a method for preparing a hetero-atom doped porous carbon material through carbonation of biomass under the assistance of molten salt. The method comprises the following steps: uniformly mixing biomass powder, the molten salt and a hetero-atom doped compound to obtain a product A, wherein the molten salt contains LiCl and KCl, the mass of LiCl accounts for 59 percent of that of the molten salt, and the mass of KCl accounts for 59 percent of that of the molten salt; putting the product A in a pipe furnace; carrying out high-temperature calcination; cleaning with distilled water to remove the molten salt and obtain the final product, namely the hetero-atom doped porous carbon material. The method has the advantages that the biomass is taken as a raw material, and the molten salt containing hetero-atoms is taken as a carbonization medium, so that the hetero-atoms can be introduced into the skeleton of the carbon material during the pyrolysis and carbonization process of the biomass synchronously and controllably, and the hetero-atom in-situ doped porous carbon material is obtained finally. Compared with the conventional doping method, the method provided by the invention have the advantages that the steps are simple; the cost is low; the operation is easy; the reactant purity is high; the application prospect is relatively good.

Description

Melting salt assists carbonize biomass to prepare the method for Heteroatom doping porous carbon materials
Technical field
That the present invention relates to is a kind of preparation method of porous carbon materials, and a kind of melting salt assists carbonize biomass to prepare the method for Heteroatom doping porous carbon materials specifically.
Background technology
Ultracapacitor is a kind of Novel energy storage apparatus between traditional capacitor and rechargeable battery, due to its have that specific power is large, operating temperature range is wide, long service life, good reliability and the plurality of advantages such as non-maintaining, thus cause and pay close attention to widely.But compared with lithium ion battery, its energy density is relatively low, cannot meet at present for the requirement of chemical power source high-energy-density, therefore need further to be improved.Ultracapacitor comprises two kinds of different storage electric charge mechanism: one is electric double layer capacitance, mechanism is the rapid aggregation process of positive and negative charge on electrode and solution interface, because in charge and discharge process, electrode interface place Charger transfer does not occur, the therefore fast and stable in properties of speed.Traditional double layer capacitor material mainly carbon material.Another kind is the fake capacitance of the quick Faradaic processes based on material interface, be by electrode surface or body mutually in electroactive substance and the faradaic current that produce of the redox reaction of underpotential deposition, chemical adsorption desorption or high reversible that occurs of electrolytic solution carry out the electrical condenser of storage power, owing to creating faraday's reaction in electrode, so the phase transformation of electrode active material generally can be attended by, therefore the cycle life of Faraday pseudo-capacitance and high rate performance poor.
The mechanical property of pore texture, huge specific surface area, good chemical stability and excellence that porous carbon materials enriches because of it, as commercial electrode material for super capacitor.And utilize biomass-making to become for ultracapacitor carbon material the direction that people pay close attention to gradually.In general, desirable super capacitor carbon electrode material should have high specific surface area, high mesoporosity, reasonably pore size distribution, less internal resistance, high bulk specific gravity, high conductivity, high purity and high performance-price ratio, good electrolytic solution wetting property and have special microscopic appearance structure, but, the gac of high-specific surface area mostly is microporous carbon, and the mesopore of prosperity will certainly sacrifice certain specific surface area, simultaneously flourishing pore texture also constrains the bulk specific gravity of carbon material, reduces the specific conductivity of material.In addition Heteroatom doping is carried out to carbon material and also can significantly improve its ratio capacitance.The people such as Raymundo-Pinero (Adv.Mater., 2006,18,1877) take biopolymer as presoma, have prepared high performance carbon back double layer capacitor by single stage method.Result shows, the specific surface area of sample is smaller, but its electrochemical performance, and major cause is that the sample surfaces oxygen-containing functional group of preparation shows fake capacitance performance.The people such as Guo (Mater.Chem.Phys., 2003,80,704) are starting material with rice bran, utilize the method for chemical activation to prepare porous carbon materials.Result shows, and the specific storage and its specific surface area that obtain sample are not linear, and ratio capacitance is not increase along with the increase of surface-area, affected to a greater extent by its pore structure and surface functional group.The people such as Rufford (J.PowerSources, 2010,195,912) are that biomass carbon material prepared by starting material with discarded coffee berry, and result shows, and using it as electrode of super capacitor, specific storage is up to 368Fg -1.The chemical property of sample excellence is the oxygen-containing functional group on its porousness and its surface and nitrogen-containing functional group mainly.
But Problems existing is that direct carbonization-later stage activation method needs to complete at a higher temperature usually at present, therefore production energy consumption is the major issue of its development of restriction, and the chemical reagent of use produces heavy corrosion to production unit when carrying out chemical activation, if simultaneously due to the waste water that produces in production process and waste gas, to deal with environmental pollution improperly larger.Template step is superfluous tired, and matrix is combined with template and the step length consuming time such as the removing of template.Wherein the removal of template is also learned and is wanted a large amount of solvent, acid or alkali as hydrofluoric acid, sodium hydroxide etc.Therefore, the method for simple and fast in of developing is prepared porous carbon tool and is of great significance.
Summary of the invention
A kind of can obtaining is the object of the present invention is to provide to have larger specific surface area, good electroconductibility, still have the melting salt of the greying porous carbon of strong stored energy and releasability to assist carbonize biomass to prepare the method for Heteroatom doping porous carbon materials at higher current densities.
The object of the present invention is achieved like this:
The compound of powdered biomass, melting salt and Heteroatom doping is even, and obtain product A, described melting salt is the mass ratio of LiCl and KCl is the melting salt of 59/41;
Product A is inserted in tube furnace, high-temperature calcination, remove melting salt with distilled water cleaning, obtain final product Heteroatom doping porous carbon materials.
The present invention can also comprise:
1, described powdered biomass is one in stalk, bean curd powder, rice hulls, marine alga or wood chip or mixture.
2, the compound of described Heteroatom doping is the mixture of one or more in nitrate, phosphoric acid salt, borate, carbonate, sulfide or fluorochemical.
3, the compound of Heteroatom doping and the mass ratio of powdered biomass are 0.01 ~ 0.5:1, and the mass ratio of powdered biomass and melting salt is 1:1 ~ 10.
4, described high-temperature calcination is calcining 10 ~ 180 minutes under vacuum or inert atmosphere, and calcining temperature is 600 ~ 1100 DEG C.
Heteroatom doping in Heteroatom doping porous carbon materials of the present invention be N, F, S, P, B etc. wherein one or more.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention adopts biomass to be raw material, method one step of being assisted by melting salt obtains the porous graphite carbon of Heteroatom doping, compared with conventional high temperature carbonization, melting salt is adopted to assist carbonization synchronously can realize activating the object of perforate in carbonization process, thus obtained greying porous carbon has larger specific surface area, good electroconductibility, therefore still has strong stored energy and releasability at higher current densities.
(2) this project utilizes containing heteroatomic melting salt as carbonization medium, realize introducing hetero-atoms in carbon material skeleton synchronously controlled in biomass pyrolytic carbonization process, finally obtain the carbon-based material that heteroatoms is in-situ doped, compared with conventional adulterating method, step of the present invention is simple, and cost is low, easily operates, reactant purity is high, has good application prospect.
Gained porous carbon materials is applied to ultracapacitor, lithium ion battery, fuel cell etc.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the porous carbon materials that embodiment 1 obtains.
Fig. 2 a-Fig. 2 d is the ultimate analysis figure of N doped porous carbon material.
Fig. 3 is the nitrogen adsorption desorption curve of the porous carbon materials that embodiment 1 obtains.
Fig. 4 is that embodiment 1 obtains the capacitance of porous carbon materials under different discharge current density.
Embodiment
By enforcement of the present invention, finally obtain specific surface area at 780 ~ 1800m 2g -1active carbon material, its ultracapacitor performance test show, 1Ag -1under discharge current density, specific storage is for can reach about 200Fg -1, 50Ag -1time electric capacity still can reach about 100Fg -1.Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
Embodiment 1
The preparation of N doped porous carbon material
Take the bean curd powder (the bean curd lyophilize grinding bought by market obtains) of 1g, with the melting salt (mass ratio of LiCl and KCl is 59/41) of the LiCl/KCl of 5g and the KNO of 0.1g 3after mixing, insert in tube furnace, under Ar atmosphere, with 5 DEG C of min -1temperature rise rate rise to 750 DEG C, constant temperature 60min, after cooling with distilled water cleaning remove fused salt, centrifugal drying is for subsequent use.
Utilize scanning electronic microscope, the analysis of nitrogen adsorption desorption and elemental analyser to carry out physico-chemical property sign to prepared porous carbon materials, the results are shown in Figure 1, Fig. 2 and Fig. 3, ultracapacitor test is carried out to prepared porous carbon materials, the results are shown in Figure 4.
Fig. 1 shows, and prepared porous carbon materials is cellular, and Fig. 3 shows the nitrogen adsorption desorption curve of gained carbon material, and its specific surface area is 1570m 2g -1, Fig. 2 a-Fig. 2 d display element analytical results is carbon 89.2%, oxygen 6.3%, nitrogen 4.5%.Gained carbon material Fig. 4 shows, and carries out the charge-discharge test under different discharge current density, 0.5Ag to it -1under discharge current density, specific storage is 363Fg -1, 50Ag -1time electric capacity still remain 140Fg -1.
Embodiment 2
The preparation of S doped porous carbon material
Take the powdered biomass (being obtained by grinding after wood chip high temperature drying) of 1g, after mixing with the salt (mass ratio of LiCl and KCl is 59/41) of the LiCl/KCl of 5g and the NaS of 0.1g, insert in tube furnace, under Ar atmosphere, with 5 DEG C of min -1temperature rise rate rise to 750 DEG C, constant temperature 60min, after cooling with distilled water cleaning remove fused salt, centrifugal drying is for subsequent use.
The specific surface area of the S doping carbon material prepared by the analysis of nitrogen adsorption desorption is 1310m 2g -1, results of elemental analyses is carbon 90.4%, oxygen 6.5%, sulphur 3.1%.Ultracapacitor performance test shows, 1Ag -1under discharge current density, specific storage is 285Fg -1, 50Ag -1time electric capacity still remain 120Fg -1.
Embodiment 3
The preparation of N and S doped porous carbon material
Take the biomass powder (ground by green marine alga drying and dehydrating and obtain) of 1g, after mixing with the salt (mass ratio of LiCl and KCl is 59/41) of the LiCl/KCl of 5g and the thiocarbamide of 0.1g, insert in tube furnace, under Ar atmosphere, with 5 DEG C of min -1temperature rise rate rise to 750 DEG C, constant temperature 60min, after cooling with distilled water cleaning remove fused salt, centrifugal drying is for subsequent use.
The specific surface area of N and the S codoped carbon material prepared by the analysis of nitrogen adsorption desorption is 1800m 2g -1, results of elemental analyses is carbon 88.6%, oxygen 5.5%, nitrogen 3.5%, sulphur 2.4%.Ultracapacitor performance test shows, 1Ag -1under discharge current density, specific storage is 350Fg -1, 50Ag -1time electric capacity still remain 180Fg -1.
Embodiment 4
The preparation of F doped porous carbon material
Take the powdered biomass of 1g, after mixing with the salt (mass ratio of LiCl and KCl is 59/41) of the LiCl/KCl of 5g and the NaF of 0.1g, insert in tube furnace, under Ar atmosphere, with 5 DEG C of min -1temperature rise rate rise to 750 DEG C, constant temperature 60min, after cooling with distilled water cleaning remove fused salt, centrifugal drying is for subsequent use.
Prepared by the analysis of nitrogen adsorption desorption, the specific surface area of F doping carbon material is 780m 2g -1, results of elemental analyses is carbon 90%, oxygen 5.8%, fluorine 4.2%.Ultracapacitor performance test shows, 0.5Ag -1under discharge current density, specific storage is 255Fg -1, 50Ag -1time electric capacity still remain 120Fg -1.

Claims (5)

1. melting salt assists carbonize biomass to prepare a method for Heteroatom doping porous carbon materials, it is characterized in that:
The compound of powdered biomass, melting salt and Heteroatom doping is even, and obtain product A, described melting salt is the mass ratio of LiCl and KCl is the melting salt of 59/41;
Product A is inserted in tube furnace, high-temperature calcination, remove melting salt with distilled water cleaning, obtain final product Heteroatom doping porous carbon materials.
2. melting salt according to claim 1 assists carbonize biomass to prepare the method for Heteroatom doping porous carbon materials, it is characterized in that: described powdered biomass is one in stalk, bean curd powder, rice hulls, marine alga or wood chip or mixture.
3. melting salt according to claim 1 and 2 assists carbonize biomass to prepare the method for Heteroatom doping porous carbon materials, it is characterized in that: the compound of described Heteroatom doping is the mixture of one or more in nitrate, phosphoric acid salt, borate, carbonate, sulfide or fluorochemical.
4. melting salt according to claim 1 and 2 assists carbonize biomass to prepare the method for Heteroatom doping porous carbon materials, it is characterized in that: the compound of Heteroatom doping and the mass ratio of powdered biomass are 0.01 ~ 0.5:1, the mass ratio of powdered biomass and melting salt is 1:1 ~ 10.
5. melting salt according to claim 3 assists carbonize biomass to prepare the method for Heteroatom doping porous carbon materials, it is characterized in that: the compound of Heteroatom doping and the mass ratio of powdered biomass are 0.01 ~ 0.5:1, the mass ratio of powdered biomass and melting salt is 1:1 ~ 10.
CN201510783477.6A 2015-11-13 2015-11-13 Method for preparing hetero-atom doped porous carbon material through carbonation of biomass under assistance of molten salt CN105314622A (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105623687A (en) * 2016-03-02 2016-06-01 大连理工大学 Device and method for jointly preparing bio-oil and multihole biochar through fuse salt by spraying biomass for pyrolysis
CN106082175A (en) * 2016-08-25 2016-11-09 北京化工大学 A kind of method that melted sodium carbonate high temperature prepares carbide-derived carbon
CN106185920A (en) * 2016-06-27 2016-12-07 农业部环境保护科研监测所 A kind of porous carbon materials and its preparation method and application
CN106744951A (en) * 2017-03-21 2017-05-31 哈尔滨工程大学 A kind of quick method for preparing activated carbon
CN106938190A (en) * 2017-04-19 2017-07-11 东北农业大学 A kind of preparation method of the lamella multiporous biological charcoal with strong adsorption function
CN106955668A (en) * 2017-04-01 2017-07-18 东北农业大学 A kind of method that fuse salt assisted with high-temperature charring prepares N doping multiporous biological charcoal
CN107399730A (en) * 2017-08-22 2017-11-28 河南师范大学 The method that the carbonization of one step prepares biomass-based porous carbon materials
CN107697914A (en) * 2017-08-22 2018-02-16 河南师范大学 A kind of method for preparing nitrogen-doped porous carbon material
CN107887613A (en) * 2017-10-18 2018-04-06 温州大学 Oxygen reduction electrode and preparation method and application based on three-dimensional netted nitrogen phosphorus sulphur codope porous carbon materials
CN108622895A (en) * 2018-05-07 2018-10-09 同济大学 A method of preparing biomass-based porous carbon materials using fuse salt
CN109160514A (en) * 2018-09-21 2019-01-08 四川理工学院 A kind of bean curd expanding method and the classifying porous active carbon of preparation method and bean curd of soybean flour and preparation method thereof
CN109742384A (en) * 2019-01-07 2019-05-10 中国矿业大学 A kind of biomass porous carbon is used as the method for kalium ion battery cathode
CN109734158A (en) * 2018-12-27 2019-05-10 金川集团股份有限公司 A kind of nitrogen, sulphur codope porous carbon sheet capacitive desalination electrode material and its preparation and application
CN110451482A (en) * 2019-08-19 2019-11-15 北京理工大学 A kind of preparation method of nitrogen sulphur codope carbon nanosheet material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11121299A (en) * 1997-10-15 1999-04-30 Isuzu Advanced Engineering Center Ltd Carbon electrode for electric double-layer capacitor, and manufacture thereof
CN104495788A (en) * 2014-12-12 2015-04-08 南京工业大学 Preparation method of porous carbon

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11121299A (en) * 1997-10-15 1999-04-30 Isuzu Advanced Engineering Center Ltd Carbon electrode for electric double-layer capacitor, and manufacture thereof
CN104495788A (en) * 2014-12-12 2015-04-08 南京工业大学 Preparation method of porous carbon

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
XIAOFENG LIU ET AL.: "Molten salt activation for synthesis of porous carbon nanostructures and carbon sheets", 《CARBON》 *
ZHISHUANG MA ET AL.: "Mesoporous nitrogen-doped carbons with high nitrogen contents and ultrahigh surface areas:synthesis and applications in catalysis", 《GREEN CHEMISTRY》 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105623687B (en) * 2016-03-02 2018-01-26 大连理工大学 A kind of fuse salt spray pyrolysis biomass joint prepares bio oil and the apparatus and method of multiporous biological charcoal
CN105623687A (en) * 2016-03-02 2016-06-01 大连理工大学 Device and method for jointly preparing bio-oil and multihole biochar through fuse salt by spraying biomass for pyrolysis
CN106185920A (en) * 2016-06-27 2016-12-07 农业部环境保护科研监测所 A kind of porous carbon materials and its preparation method and application
CN106185920B (en) * 2016-06-27 2018-05-18 农业部环境保护科研监测所 A kind of porous carbon materials and its preparation method and application
CN106082175B (en) * 2016-08-25 2019-09-17 北京化工大学 A method of melting sodium carbonate high temperature prepares carbide-derived carbon
CN106082175A (en) * 2016-08-25 2016-11-09 北京化工大学 A kind of method that melted sodium carbonate high temperature prepares carbide-derived carbon
CN106744951A (en) * 2017-03-21 2017-05-31 哈尔滨工程大学 A kind of quick method for preparing activated carbon
CN106955668A (en) * 2017-04-01 2017-07-18 东北农业大学 A kind of method that fuse salt assisted with high-temperature charring prepares N doping multiporous biological charcoal
CN106938190A (en) * 2017-04-19 2017-07-11 东北农业大学 A kind of preparation method of the lamella multiporous biological charcoal with strong adsorption function
CN107399730A (en) * 2017-08-22 2017-11-28 河南师范大学 The method that the carbonization of one step prepares biomass-based porous carbon materials
CN107697914A (en) * 2017-08-22 2018-02-16 河南师范大学 A kind of method for preparing nitrogen-doped porous carbon material
CN107887613A (en) * 2017-10-18 2018-04-06 温州大学 Oxygen reduction electrode and preparation method and application based on three-dimensional netted nitrogen phosphorus sulphur codope porous carbon materials
CN107887613B (en) * 2017-10-18 2021-03-26 温州大学 Oxygen reduction electrode based on three-dimensional net-shaped nitrogen, phosphorus and sulfur co-doped porous carbon material, and preparation method and application thereof
CN108622895A (en) * 2018-05-07 2018-10-09 同济大学 A method of preparing biomass-based porous carbon materials using fuse salt
CN109160514A (en) * 2018-09-21 2019-01-08 四川理工学院 A kind of bean curd expanding method and the classifying porous active carbon of preparation method and bean curd of soybean flour and preparation method thereof
CN109734158A (en) * 2018-12-27 2019-05-10 金川集团股份有限公司 A kind of nitrogen, sulphur codope porous carbon sheet capacitive desalination electrode material and its preparation and application
CN109742384A (en) * 2019-01-07 2019-05-10 中国矿业大学 A kind of biomass porous carbon is used as the method for kalium ion battery cathode
CN110451482A (en) * 2019-08-19 2019-11-15 北京理工大学 A kind of preparation method of nitrogen sulphur codope carbon nanosheet material

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Application publication date: 20160210