CN110395730A - A kind of preparation method of the derivative nitrogenous electrode material of porous charcoal super capacitor of discarded fish-bone - Google Patents

A kind of preparation method of the derivative nitrogenous electrode material of porous charcoal super capacitor of discarded fish-bone Download PDF

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Publication number
CN110395730A
CN110395730A CN201910680273.8A CN201910680273A CN110395730A CN 110395730 A CN110395730 A CN 110395730A CN 201910680273 A CN201910680273 A CN 201910680273A CN 110395730 A CN110395730 A CN 110395730A
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bone
fish
preparation
electrode material
powder
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牛棱渊
张小美
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Hangzhou Realistic New Materials Technology Co Ltd
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Hangzhou Realistic New Materials Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • C01B32/348—Metallic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a kind of preparation methods of the derivative nitrogenous electrode material of porous charcoal super capacitor of discarded fish-bone.This method, as presoma, the porous structure active carbon for constructing bigger serface, high specific capacitance is combined using step carbonization, activation to discard Fishbone, such as band fish-bone, grass carp bone, perch bone, butterfish bone.As carbon source, nitrogen source, auto-dope introduces nitrogen in step carbonization, activation process, while improving the content of oxygen in active carbon for collagen abundant in bone, greatly improves the chemical property of prepared active carbon.The advantages that present invention has energy-saving and emission-reduction, and low-carbon environment-friendly, preparation process is simple, is suitble to industrialized production.

Description

A kind of preparation of the derivative nitrogenous electrode material of porous charcoal super capacitor of discarded fish-bone Method
Technical field
The invention belongs to porous charcoal and electrochemical energy storage fields, and in particular to a kind of derivative nitrogenous porous charcoal of discarded fish-bone is super The preparation method of grade capacitor electrode material.
Background technique
Electrode material is the technological core of supercapacitor, researches and develops the pass of high-energy density high power density supercapacitor Key is that design prepares the electrode material of height ratio capacity, high rate capability.Carbon Materials are using most because of its good physicochemical property One of early, current most popular electrode material.In recent years due to the shortage of fossil energy, the development of Carbon Materials receives one Fixed limitation.In order to further develop Carbon Materials and cope with the challenge of energy crisis, researcher has been turned one's attention to rich in carbon member The renewable biomass resources of element.
Currently, many research workers, which have carried out using various biological materials and agricultural by-products as raw material, prepares Carbon Materials Work.For example, rice straw (CN 106587055A), wide yulan leaf (CN 106683899), sawdust (CN 107298441A), Kapok pericarp (CN 107973286A), shrimp and crab shells (CN 108002360A), garlic base (CN 108557819A) etc. are by conduct Raw material is prepared into active carbon electrode material by multi-step process such as pre-treatment, carbonization, activation, post-processings.But prepared by these raw materials The process of supercapacitor Carbon Materials, generallys use that pre- carbonization, inorganic salts activation, element doping, the multi-step process such as be carbonized again, To improve the chemical property of Carbon Materials to the maximum extent.However, due to complex process, it can not be real during direct carbonization Existing element doping, cost of manufacture are higher, it is difficult to realize the preparation of industrialization of active carbon.
China is fish culture in the world and big export country, and the yield and export volume of annual fish account for about global 50% More than, mainly domestic in the form of frozen fish, surimi product, dried fish product, fish oil etc. and outlet.In fish process In can generate a large amount of waste, account for about the 30% ~ 50% of gross mass, wherein discarded fish-bone proportion is higher.It is a large amount of useless It abandons fish-bone and does not obtain appropriate utilization, be only used as agricultural fertilizer, or directly abandon as rubbish.It not only causes in this way The waste of resource, also pollutes the environment.Therefore, how using sea leaves such as exhaust gas fish-bones, high added value material is developed The extensive concern of researcher is caused.For example, discarded fish-bone is used to prepare polypeptide and oligopeptide for raw material, but at present The complex process of separation and Extraction, Purity at high cost and preparing are lower.
Summary of the invention
In order to overcome the problems, such as existing in the prior art difficult and solve the wasting of resources, it is discarded that the present invention provides one kind The preparation method of the derivative nitrogenous electrode material of porous charcoal super capacitor of fish-bone, using fish-bone, such as band fish-bone, grass carp bone, perch Bone, butterfish bone are as presoma, and there are micropores and mesoporous in the Carbon Materials prepared using step carbonization, activation, and specific capacitance is high, It is suitable as electrode material for super capacitor, and method cleanliness without any pollution provided by the invention, at low cost, suitable scale metaplasia It produces.
To achieve the goals above, the invention provides the following technical scheme:
A kind of preparation method of the derivative nitrogenous electrode material of porous charcoal super capacitor of discarded fish-bone, specifically comprises the following steps:
(1) tallow of fish-bone head surface is washed off with ethyl alcohol, crushing obtains the powder of fish-bone material, is labeled as powder 1；
(2) solid activating agent that certain mass ratio is added is mixed with powder 1, is carried out at 500-800 DEG C under inert gas protection Carbonization, wherein the ratio of powder 1 and activating agent is 1:2 ~ 1:5；
(3), through pickling, washing, filtering, drying, nitrogenous porous carbon material will can be obtained after the cooling of above-mentioned carbonized product, it is described The abundant prosperity of active carbon electrode material pore structure, contain micropore, mesoporous, specific surface area is high, while auto-dope introducing nitrogen, Activation promotes oxygen content, the content 0 ~ 8% of nitrogen, the content 5% ~ 10% of oxygen.
Further, described in step (1) discard fish-bone be selected from band one of fish-bone, grass carp bone, perch bone, butterfish bone or It is several.
Further, the heating rate being carbonized in step (2) is 9 ~ 12 DEG C/min, soaking time 1-2h, the inertia Gas is nitrogen.
Further, concentration of hydrochloric acid 0.2-2M in step (3), drying temperature are 80 ~ 100 DEG C, drying time 10-24h.
Further, activator described in step (2) is KOH.
The beneficial effects of the present invention are:
1. raw material are discarded fish-bone, commonly it is easy to get, it is low in cost, its pollution to environment is not only effectively reduced, but also obtain High-quality Carbon Materials have been arrived, it can be achieved that " turning waste into wealth " truly, increases the Economic Value Added of discarded fish-bone；
2. have collagen abundant in bone, collagen as the feature of carbon source is that phosphorus content is high, and be rich in hydroxyl, Carboxyl, amino groups, carbonisation can auto-dope introducing nitrogens.Self-doping nitrogen atom and the oxygen content caused by activating increase Add, greatly improve the wettability of electrode material so that electrolyte ion electrode material surface can carry out quickly transmit and Migration, shows height ratio capacity and energy density；
3. being combined using step carbonization, activation and being constructed porous structure active carbon, preparation process is simple, has good application Prospect.
Specific embodiment
Technical solution of the present invention does not limit to act specific embodiment set forth below, further includes its between each specific embodiment He combines.
Embodiment 1:
(1) tallow of 100g hairtail bone surface is washed off with ethyl alcohol, crushing obtains the powder 95g of fish-bone；
(2) KOH that certain mass is added mixes (mass ratio of hairtail bone powder and activating agent is 1:3) with hairtail bone powder, In N2It is carbonized under gas shield, is warming up to 800 DEG C of target temperature from room temperature with 10 DEG C/min, and keep the temperature 1h, is carbonized Object；
(3) it will be washed after the cooling of above-mentioned carbide with 1M HCl, then washed with a large amount of deionized waters to neutrality, in 80 DEG C of baking ovens Dry 12h, obtains porous carbon material, includes mesoporous, micropore, can be used as electrode material for super capacitor.
Its specific surface area, specific volume, nitrogen oxygen content are measured, the results are shown in Table 1.
Table 1
Specific surface area (m2/ g) Specific volume (Fg-1) Oxygen content (At %) Nitrogen content (At %)
1463 154 7.6 7.9
Embodiment 2:
(1) with ethyl alcohol wash off 25g with Fishbone, 25g grass carp bone, 25g perch bone, 25g butterfish bone surface animal Rouge, crushing obtain the powder 93g of fish-bone；
(2) KOH that certain mass is added mixes (mass ratio of fish-bone powder and activating agent is 1:4) with fish-bone powder, in N2 It is carbonized under gas shield, is warming up to 700 DEG C of target temperature from room temperature with 12 DEG C/min, and keep the temperature 2h, obtains carbide；
(3) it will be washed after the cooling of above-mentioned carbide with 2M HCl, then washed with a large amount of deionized waters to neutrality, in 100 DEG C of baking ovens Middle dry 12h, obtains porous carbon material, includes mesoporous, micropore, can be used as electrode material for super capacitor.
Its specific surface area, specific volume, nitrogen oxygen content are measured, the results are shown in Table 1.
Table 2
Specific surface area (m2/ g) Specific volume (Fg-1) Oxygen content (At %) Nitrogen content (At %)
1529 186 7.2 7.5
Embodiment 3:
(1) tallow of 100g perch bone surface is washed off with ethyl alcohol, crushing obtains the powder 96g of fish-bone；
(2) KOH that certain mass is added mixes (mass ratio of perch bone powder and activating agent is 1:2) with perch bone powder, In N2It is carbonized under gas shield, is warming up to 500 DEG C of target temperature from room temperature with 9 DEG C/min, and keep the temperature 2h, is carbonized Object；
(3) it will be washed after the cooling of above-mentioned carbide with 0.5M HCl, then washed with a large amount of deionized waters to neutrality, in 80 DEG C of baking ovens Middle dry 10h, obtains porous carbon material, includes mesoporous, micropore, can be used as electrode material for super capacitor.
Its specific surface area, specific volume, nitrogen oxygen content are measured, the results are shown in Table 1.
Table 3
Specific surface area (m2/ g) Specific volume (Fg-1) Oxygen content (At %) Nitrogen content (At %)
703 201 6.0 6.3
Embodiment 4:
(1) tallow of 100g butterfish bone surface is washed off with ethyl alcohol, crushing obtains the powder 98g of fish-bone；
(2) KOH that certain mass is added mixes (mass ratio of butterfish bone powder and activating agent is 1:5) with butterfish bone powder, In N2It is carbonized under gas shield, is warming up to 600 DEG C of target temperature from room temperature with 12 DEG C/min, and keep the temperature 1h, is carbonized Object；
(3) it will be washed after the cooling of above-mentioned carbide with 2M HCl, then washed with a large amount of deionized waters to neutrality, in 80 DEG C of baking ovens Dry 18h, obtains porous carbon material, includes mesoporous, micropore, can be used as electrode material for super capacitor.
Its specific surface area, specific volume, nitrogen oxygen content are measured, the results are shown in Table 1.
Table 4
Specific surface area (m2/ g) Specific volume (Fg-1) Oxygen content (At %) Nitrogen content (At %)
1249 214 7.0 7.4
Embodiment 5:
(1) tallow of 100g perch bone, 100g hairtail bone surface is washed off with ethyl alcohol, crushing obtains the powder of fish-bone 193g；
(2) KOH that certain mass is added mixes (mass ratio of fish-bone powder and activating agent is 1:3) with fish-bone powder, in N2 It is carbonized under gas shield, is warming up to 600 DEG C of target temperature from room temperature with 11 DEG C/min, and keep the temperature 1h, obtains carbide；
(3) it will be washed after the cooling of above-mentioned carbide with 1.5M HCl, then washed with a large amount of deionized waters to neutrality, in 80 DEG C of baking ovens Middle drying for 24 hours, obtains porous carbon material, includes mesoporous, micropore, can be used as electrode material for super capacitor.
Its specific surface area, specific volume, nitrogen oxygen content are measured, the results are shown in Table 1.
Table 5
Specific surface area (m2/ g) Specific volume (Fg-1) Oxygen content (At %) Nitrogen content (At %)
1266 226 7.2 7.5
Main feature and advantages of the present invention of the invention has been shown and described in above embodiments.The above is tool of the invention Body embodiment, the present invention is not limited to the above embodiments, and the description in above embodiments and description only illustrates this hair Bright principle, rather than limit the scope of the invention in any way, without departing from the principle of the present invention, it can also do Several improvements and modifications out, these modifications and embellishments are also considered to be within the scope of the present invention.

Claims (5)

1. a kind of preparation method of the derivative nitrogenous electrode material of porous charcoal super capacitor of discarded fish-bone, it is characterised in that specific packet Include following steps:
(1) tallow of fish-bone head surface is washed off with ethyl alcohol, crushing obtains the powder of fish-bone material, is labeled as powder 1；
(2) solid activating agent that certain mass ratio is added is mixed with powder 1, is carried out at 500-800 DEG C under inert gas protection Carbonization, wherein the ratio of powder 1 and activating agent is 1:2 ~ 1:5；
(3), through pickling, washing, filtering, drying, porous carbon material, the work will can be obtained after the cooling of above-mentioned carbonized product Property the abundant prosperity of carbon electrode material pore structure, containing micropore, mesoporous, specific surface area is high, while auto-dope introduces nitrogen, activates Promote oxygen content, the content 0 ~ 8% of nitrogen, the content 5% ~ 10% of oxygen.
2. preparation method according to claim 1, which is characterized in that the discarded fish-bone is selected from band fish-bone, grass carp bone, perch One or more of fish-bone, butterfish bone.
3. preparation method according to claim 1, which is characterized in that the heating rate being carbonized in step (2) is 9 ~ 12 DEG C/ Min, soaking time 1-2h, the inert gas are high-purity nitrogen.
4. preparation method according to claim 1, which is characterized in that concentration of hydrochloric acid 0.2-2M in step (3), drying temperature It is 80 ~ 100 DEG C, drying time 10-24h.
5. preparation method according to claim 1, which is characterized in that the activator is KOH.
CN201910680273.8A 2019-07-26 2019-07-26 A kind of preparation method of the derivative nitrogenous electrode material of porous charcoal super capacitor of discarded fish-bone Pending CN110395730A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101993068A (en) * 2010-10-27 2011-03-30 北京化工大学 Preparation method of porous structured active carbon
CN102107863A (en) * 2009-12-25 2011-06-29 北京化工大学 Porous carbon material and preparation method thereof
CN103991870A (en) * 2014-05-09 2014-08-20 山东大学 Method for preparing active carbon from fish scale

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102107863A (en) * 2009-12-25 2011-06-29 北京化工大学 Porous carbon material and preparation method thereof
CN101993068A (en) * 2010-10-27 2011-03-30 北京化工大学 Preparation method of porous structured active carbon
CN103991870A (en) * 2014-05-09 2014-08-20 山东大学 Method for preparing active carbon from fish scale

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FEI AI ET AL.: "Heteroatoms-Doped Porous Carbon Deribed from Tuna Bone for High Performance Li-S Batteries", 《ELECTROCHIMICA》 *
LENGYUAN NIU ET AL.: "Waste bones derived nitrogen–doped carbon with high micropore ratio towards supercapacitor applications", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 *

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Application publication date: 20191101