CN107304048B - A kind of preparation method of polyacrylic acid grafted lignin porous charcoal - Google Patents
A kind of preparation method of polyacrylic acid grafted lignin porous charcoal Download PDFInfo
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- CN107304048B CN107304048B CN201610224202.3A CN201610224202A CN107304048B CN 107304048 B CN107304048 B CN 107304048B CN 201610224202 A CN201610224202 A CN 201610224202A CN 107304048 B CN107304048 B CN 107304048B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
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Abstract
The present invention provides a kind of preparation method of polyacrylic acid grafted lignin porous charcoal, the material preparation process is simple, the cheap preparation that can be used for electrode material for super capacitor.The purpose of the present invention is using polyacrylic acid grafted lignin as material, charing preparation low cost, high-specific surface area and internal continuous porous carbon electrode material are carried out by controlling the hole of the volume steric hindrance regulation activity charcoal of the surface functional group and lignin of presoma in polymeric gel, and to polyacrylic acid grafted lignin composite material.Porous carbon electrode material produced by the present invention specific capacity with higher and specific surface area；Diameter > 2nm pore volume accounts for 70% of total pore volume or more；Aperture is continuous and has good electric conductivity.
Description
Technical field
The present invention relates to a kind of preparations of polyacrylic acid grafted lignin porous charcoal, and the porous carbon material is by biomass-based more
Porous materials directly carbonize preparation, belong to porous carbon material production technical field.
Background technique
Problem of energy crisis is one of 21 century most important international subject under discussion.With the rapid exhausted and whole world of fossil fuel
The worsening of ecological environment, environmental pollution and the consumption of a large amount of fossil fuel, researcher have been devoted to find and can replace
For the high efficiency of fossil fuel, low cost, environmental-friendly new energy.Supercapacitor as a kind of novel energy storage apparatus,
It is big with capacity, can fast storage and release energy, leakage current is small, power density is big, standing time is long, safe and environment-friendly etc. excellent
Point.Super capacitor belongs to double layer capacitor, it is capacity maximum one in the double layer capacitor for put into the world volume production
Kind, basic principle as the double layer capacitor of other types, is formed using active carbon porous electrode and electrolyte
Double electrical layers obtain super large capacity.The electrode of the porous carbon material of supercapacitor generally want 2nm and more than sky
Between could form electric double layer, to complete effective energy storage.The commercial positive electrode majority of supercapacitor is that have height
The absorbent charcoal material of specific surface area, but the existing Carbon Materials for making supercapacitor are at high cost, account for mass customization
30% or so.Therefore, the research purpose of this project is using cheap lignin-base polymer as material, and preparation has internal hand over
The Carbon Materials of connection, low cost and high-specific surface area.
The yield of lignin in nature is only second to cellulose, is the most abundant natural aromatic polymer.Mesh
It is preceding using plant fiber as the industry of raw material, such as weaving, pulping and paper-making, wood hydrolysis, biological material, biomass energy, institute
The lignin of generation is substantially all to be discharged as waste.By taking pulping and paper-making as an example, 1 ton of slurry paper of every production then needs 1.5 tons of discharge
The black liquor solid (including carbohydrate and inorganic matter) of left and right, it is estimated that the whole world is about discharged 1.5 hundred million~1.8 hundred million tons every year
Industrial lignin, wherein the overwhelming majority is utilized as heat source.It is only used as and organises less than 1% (mainly lignosulfonates)
Resource is learned to be utilized.In addition some is discharged as environmental contaminants.Active carbon is produced by raw material of lignin, was both expanded
The big utilization ways of lignin, while there is positive effect to the new sources for opening up active carbon.The presoma of active carbon can divide
It is three kinds: graphite mould, diamond shape and amorphous.Lignin has aromatic structure, belongs to the graphite ene-type precursor of well-formed.It is wooden
Plain base charcoal is usually amorphous graphite microcrystalline structure, and the porosity of active carbon and the surface functional group of presoma and activation side
Method, therefore can be with regulation activity by the mass ratio etc. of the surface functional group and lignin of control presoma in polymeric gel
The porosity of charcoal.Meanwhile the limitation that heating equipment of the present invention to carbonization process be not stringent, it is such as commonly used in the prior art to add
Hot stove etc., preferably tube furnace, because the temperature control of tube furnace can be completed by the thermocouple of its own configuration, more just
Just.Since the degree of carbonization of porous carbon material is related with its application field, the method for the present invention can be by a certain extent
The temperature of carbonization process is controlled, the degree of carbonization of porous carbon material is easily controlled, to obtain the porous charcoal for meeting super capacitor
Material.
Summary of the invention
The present invention provides a kind of preparation method of polyacrylic acid grafted lignin porous charcoal, this method simple process, at
This is low, is not necessarily to other additives.The object of the present invention is to provide a kind of polyacrylic acid grafted lignin porous charcoal preparation side
The polyacrylic acid grafted lignin porous charcoal of method, this method preparation has the advantage that
1. porous carbon material manufactured by the present invention is a kind of simple production process, cheap can be used for supercapacitor
The Carbon Materials of electrode material.
2. porous carbon electrode material produced by the present invention specific capacity with higher and specific surface area；The hole bore dia > 2nm
The volume of diameter accounts for 70% of total pore volume or more；Aperture is continuous and has good electric conductivity.
A kind of preparation method preparing polyacrylic acid grafted lignin porous charcoal, comprising the following steps:
1. taking 3-5mL acrylic acid and ammonium persulfate, N, N '-methylene-bisacrylamide is placed in 60 DEG C~90 DEG C of water-bath
Acrylate copolymer A is obtained within reaction 5 minutes then to mix and set with polymer A by appropriate lignin dissolution in sodium hydroxide solution
Graft polymerization reacts 40~60min in the vibrator of 60 DEG C~90 DEG C water temperatures, takes out product after reaction, drying and crushing obtains
Polyacrylic acid grafted lignin particles.
2. polyacrylic acid grafted lignin particles are dispersed in reaction boat, reaction boat is placed on reaction unit
In, then under the protection of inert gas, furnace temperature is slowly warming up to 600~1000 DEG C of activation temperature from room temperature, charing 60~
It after 120 minutes, is cooled to room temperature, porous carbon material is made.
The lignin of above-mentioned polyacrylic acid grafted lignin porous charcoal can be alkali lignin, enzymolysis xylogen, sulfate
Lignin, sulfonate lignin and other modified lignin resins etc..The preparation of above-mentioned polyacrylic acid grafted lignin porous charcoal is reacted
Device can be microwave Muffle furnace, autoclave and tube type resistance furnace；It is above-mentioned to prepare polyacrylic acid grafted lignin porous charcoal
The material of reaction boat can be quartz, nickel, ceramics or corundum；It is above-mentioned prepare it is lazy needed for polyacrylic acid grafted lignin porous charcoal
Property gas can be nitrogen or argon gas.
Detailed description of the invention:
Fig. 1: cyclic voltammetric of the polyacrylic acid grafted lignin porous carbon material in 2M KOH under different scanning rates is bent
Line:
Fig. 2: polyacrylic acid grafted lignin porous carbon material is constant current charge-discharge curve in different current densities
Fig. 3: polyacrylic acid grafted lignin porous charcoal porous material is 50mAcm in current density-2When cycle life
Specific embodiment:
The content of present invention is described in detail with embodiment with reference to the accompanying drawings of the specification.
Embodiment 1:
It takes 5mL acrylic acid that the sodium hydroxide solution 30mL of 1.5mol/L is added, adds 0.2g ammonium persulfate, 0.15gN,
N '-methylene-bisacrylamide, which is placed in heat 5 minutes in 60 DEG C of water-bath, obtains acrylate copolymer A；Take 0.1g lignin molten
Then solution mixes in the vibrator for being placed on 60 DEG C of water temperatures with polymer A and gathers in the sodium hydroxide solution of the 1.5mol/L of 2mL
Reaction 60min is closed, after reaction takes out product, cooling drying, grinding obtains polyacrylic acid grafted lignin particles；Take 1g
Particulate matter be dispersed in reaction boat in, will reaction boat be placed in tube furnace, under the protection of nitrogen, by furnace temperature from room temperature with
After the heating rate of 2 DEG C/min is heated to 700 DEG C of activation temperature, charing 120 minutes, it is cooled to room temperature, porous carbon material is made.
Through surveying, the average pore size of prepared polyacrylic acid grafted lignin porous charcoal is 3.64nm, and specific surface area is
1529m2/g。
Embodiment 2:
It takes 5mL acrylic acid that the sodium hydroxide solution 30mL of 1.5mol/L is added, adds 0.2g ammonium persulfate, 0.15gN,
N '-methylene-bisacrylamide, which is placed in heat 5 minutes in 60 DEG C of water-bath, obtains acrylate copolymer A；Take 0.25g lignin molten
Then solution mixes in the vibrator for being placed on 60 DEG C of water temperatures with polymer A and gathers in the sodium hydroxide solution of the 1.5mol/L of 2mL
Reaction 60min is closed, after reaction takes out product, cooling drying, grinding obtains polyacrylic acid grafted lignin particles；Take 1g
Particulate matter be dispersed in reaction boat in, will reaction boat be placed in tube furnace, under the protection of nitrogen, by furnace temperature from room temperature with
After the heating rate of 2 DEG C/min is heated to 700 DEG C of activation temperature, charing 120 minutes, it is cooled to room temperature, porous carbon material is made.
Through surveying, the average pore size of prepared polyacrylic acid grafted lignin porous charcoal is 4.62nm, and specific surface area is
1349m2/g。
Embodiment 3:
It takes 5mL acrylic acid that the sodium hydroxide solution 30mL of 1.5mol/L is added, adds 0.2g ammonium persulfate, 0.15gN,
N '-methylene-bisacrylamide, which is placed in heat 5 minutes in 60 DEG C of water-bath, obtains acrylate copolymer A；Take 0.5g lignin molten
Then solution mixes in the vibrator for being placed on 60 DEG C of water temperatures with polymer A and gathers in the sodium hydroxide solution of the 1.5mol/L of 2mL
Reaction 60min is closed, after reaction takes out product, cooling drying, grinding obtains polyacrylic acid grafted lignin particles；Take 1g
Particulate matter be dispersed in reaction boat in, will reaction boat be placed in tube furnace, under the protection of nitrogen, by furnace temperature from room temperature with
After the heating rate of 2 DEG C/min is heated to 700 DEG C of activation temperature, charing 120 minutes, it is cooled to room temperature, porous carbon material is made.
Through surveying, the average pore size of prepared polyacrylic acid grafted lignin porous charcoal is 5.64nm, and specific surface area is
1293m2/g。
Embodiment 4:
It takes 5mL acrylic acid that the sodium hydroxide solution 30mL of 1.5mol/L is added, adds 0.2g ammonium persulfate, 0.15gN,
N '-methylene-bisacrylamide, which is placed in heat 5 minutes in 60 DEG C of water-bath, obtains acrylate copolymer A；Take 1.0g lignin molten
Then solution mixes in the vibrator for being placed on 60 DEG C of water temperatures with polymer A and gathers in the sodium hydroxide solution of the 1.5mol/L of 2mL
Reaction 60min is closed, after reaction takes out product, cooling drying, grinding obtains polyacrylic acid grafted lignin particles；Take 1g
Particulate matter be dispersed in reaction boat in, will reaction boat be placed in tube furnace, under the protection of nitrogen, by furnace temperature from room temperature with
After the heating rate of 2 DEG C/min is heated to 700 DEG C of activation temperature, charing 120 minutes, it is cooled to room temperature, porous carbon material is made.
Through surveying, the average pore size of prepared polyacrylic acid grafted lignin porous charcoal is 6.99nm, and specific surface area is
826m2/g。
Fig. 1 is the polyacrylic acid grafted lignin porous carbon material that is produced using technique described in embodiment 3 in difference
Cyclic voltammetry curve under sweep speed does not have redox peaks presence, i.e., no fake capacitance generates.When sweep speed increases
Also it is able to maintain good electric double layer capacitance.
Fig. 2 is to produce to obtain polyacrylic acid grafted lignin porous carbon material in different electricity using technique described in embodiment 3
Current density is constant current charge-discharge curve, and the corresponding electrochemical specific capacity of different current densities can be calculated from figure and is respectively
144.9F·g-l、129F·g-l、119F·g-l、159F·g-l、111F·g-l、108F·g-l.When current density is 50mA
cm-2When, it is 5mAcm that electrochemical specific capacity, which is able to maintain current density,-2When 74.5%.Therefore, prepared by the present invention porous
Carbon Materials have high specific capacity and good high-power energy.
Fig. 3 be produce to obtain polyacrylic acid grafted lignin porous carbon material using technique described in embodiment 3 it is close in electric current
Degree is 50mAcm-2When cycle life, by 2000 constant current charge-discharges, electrochemical specific capacity is able to maintain initial specific volume
The 98.1% of amount, embodying prepared porous charcoal has good cycle life.
Claims (4)
1. a kind of preparation method of polyacrylic acid grafted lignin porous charcoal, it is characterised in that: by polyacrylic acid grafted lignin
It is placed in carbonizing apparatus, under the protection of inert gas, 600~1000 DEG C is slowly warming up to from room temperature, is activated 60~120 minutes
Afterwards, it being cooled to room temperature, porous carbon material is made, the aperture of polyacrylic acid grafted lignin porous charcoal has classifying porous feature,
Control is between 2nm~100nm, and aperture has continuity, there is preferable electric conductivity；
Wherein polyacrylic acid grafted lignin the preparation method comprises the following steps: take 3-5mL acrylic acid and ammonium persulfate, N, N '-di-2-ethylhexylphosphine oxide
Acrylamide, which is placed in 60 DEG C~90 DEG C of water-bath, reacts 5 minutes to obtain acrylate copolymer A, by appropriate lignin dissolution in hydrogen-oxygen
Change in sodium solution, be then placed in polymer A mixing graft polymerization in the vibrator of 60 DEG C~90 DEG C water temperatures react 40~
60min, takes out product after reaction, and drying and crushing obtains polyacrylic acid grafted lignin particles.
2. a kind of preparation method of polyacrylic acid grafted lignin porous charcoal according to claim 1, which is characterized in that institute
It states one or two kinds of above equipment that carbonizing apparatus is microwave Muffle furnace, autoclave or tube type resistance furnace and completes charcoal jointly
Change process.
3. a kind of preparation method of polyacrylic acid grafted lignin porous charcoal according to claim 1, which is characterized in that institute
State one or two kinds of mixing that inert gas is nitrogen or argon gas.
4. a kind of preparation method of polyacrylic acid grafted lignin porous charcoal according to claim 1, which is characterized in that institute
State one kind that lignin material is alkali lignin, enzymolysis xylogen, sulfate-reducing conditions, sulfonate lignin or modified lignin resin
Or two or more mixtures.
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| CN110240142B (en) * | 2019-07-01 | 2021-05-25 | 中钢集团鞍山热能研究院有限公司 | Porous carbon electrode material with microstructure easy to regulate and control, and preparation method and application thereof |
| CN112216517B (en) * | 2020-09-03 | 2022-11-11 | 中国汽车技术研究中心有限公司 | Composite energy storage material and preparation method thereof, electrode material and energy storage device |
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| CN103145926A (en) * | 2013-01-17 | 2013-06-12 | 安徽安生生物化工科技有限责任公司 | Preparation method of wood element base polyacrylic acid microgel multiple-effect absorbing agent |
| CN103253651A (en) * | 2013-05-23 | 2013-08-21 | 广西大学 | Lignin-based porous carbon material and preparation method thereof |
| CN103964432A (en) * | 2013-02-04 | 2014-08-06 | 济南圣泉集团股份有限公司 | Method for preparing granular activated carbon from lignin |
| CN105197926A (en) * | 2015-08-18 | 2015-12-30 | 南京林业大学 | Method for preparing activated carbon with enzymatic hydrolysis lignin as raw material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145926A (en) * | 2013-01-17 | 2013-06-12 | 安徽安生生物化工科技有限责任公司 | Preparation method of wood element base polyacrylic acid microgel multiple-effect absorbing agent |
| CN103964432A (en) * | 2013-02-04 | 2014-08-06 | 济南圣泉集团股份有限公司 | Method for preparing granular activated carbon from lignin |
| CN103253651A (en) * | 2013-05-23 | 2013-08-21 | 广西大学 | Lignin-based porous carbon material and preparation method thereof |
| CN105197926A (en) * | 2015-08-18 | 2015-12-30 | 南京林业大学 | Method for preparing activated carbon with enzymatic hydrolysis lignin as raw material |
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