CN106952746B - Active carbon electrode material preparation method and manganese oxide/activated carbon composite electrode material preparation method - Google Patents
Active carbon electrode material preparation method and manganese oxide/activated carbon composite electrode material preparation method Download PDFInfo
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- CN106952746B CN106952746B CN201710179015.2A CN201710179015A CN106952746B CN 106952746 B CN106952746 B CN 106952746B CN 201710179015 A CN201710179015 A CN 201710179015A CN 106952746 B CN106952746 B CN 106952746B
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- electrode material
- activated carbon
- manganese oxide
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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
- 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 maize straws to make active carbon electrode material preparation method, and a kind of maize straw making manganese oxide/activated carbon composite electrode material preparation method, it can be by the way that corn straw smashing, heating to be added alkali and mix, then the processing steps such as heating, pickling, distillation produce active carbon electrode material, by the mixture of the activated carbon produced and liquor potassic permanganate and ethanol solution, manganese oxide/activated carbon composite electrode material is produced through overpickling, washing, drying process after adding sodium hydroxide solution to react.Pass through combination electrode material made from this method, effectively improve the cycle performance of transition metal oxide, improve the cyclical stability of material, enhance the high rate performance of electrode material, and solve stalk exhaust gas and burn the wasting of resources brought and problem of environmental pollution, improve the comprehensive development and utilization and its utilization rate of agricultural crop straw.
Description
Technical field
The present invention relates to electrode material preparing technical fields, specifically, being related to a kind of active carbon electrode material preparation side
Method and manganese oxide/activated carbon composite electrode material preparation method.
Background technology
Currently, the electrode material of ultracapacitor mainly uses manganese oxide/activated carbon composite electrode material, and combination electrode
The raw material of activated carbon in material has coal, timber, shell, walnut shell and stalk etc., these carbonaceous materials are placed in activation furnace,
Activated carbon is converted by pyrolysis under high temperature and certain pressure.Compared with active carbon from coal, stalk produces activated carbon
Have the shortcomings that intensity and activation grade is relatively low, conductivity is poor, while the yield of stalk production activated carbon is relatively low, most of stalk
The achievement in research of active carbon electrode material also rests on laboratory stage at present.And agricultural crop straw is widely present, crop straw burning
Atmospheric environment is seriously affected, therefore, it is necessary to solve how to improve the comprehensive utilization of agricultural crop straw and its asking for utilization rate
Topic.
Invention content
First technical problem to be solved by this invention be：One kind is provided using stalk as raw material, and specific surface area height,
The high active carbon electrode material preparation method of mesoporous.
Second technical problem to be solved by this invention be：The oxygen that a kind of cyclical stability is high, high rate performance is strong is provided
Change manganese/active carbon electrode material preparation method.
In order to solve the first technical problem mentioned above, the technical scheme is that：
Active carbon electrode material preparation method, includes the following steps：
A, corn stalk powder is broken to the stalk particle of 0.35~0.42mm of grain size, stalk particle is crossed 40 mesh sieve, and dry
Moisture to stalk particle is less than 10%；
B, the stalk particle after drying is packed into crucible, under the protection atmosphere of inert gas, according to 5~10 DEG C/min's
The rate of heat addition is heated to 500~600 DEG C in kiln, constant temperature is then kept in kiln 3~5 hours, obtains maize straw carbon
Compound material；
C, by maize straw carbonization material and activator according to mass ratio 1：1~5：1 ratio adds after mixing
Enter crucible, under the protection atmosphere of inert gas, is heated the mixture in kiln according to the rate of heat addition of 5~10 DEG C/min
700~1000 DEG C, 2 hours postcoolings of heat preservation to room temperature；
D, the mixture that will be cooled to room temperature is washed with acid solution, is then 6~7 with pure water to pH value, dry
It is crushed to the particle of 15~20 μm of grain size after processing, absorbent charcoal material is made.
Preferably, the inert gas is argon gas, nitrogen or argon gas nitrogen mixed gas.
Preferably, the activator is KOH, CaCl2Or NaOH.
To solve above-mentioned second technical problem, the technical scheme is that：
Manganese oxide/activated carbon composite electrode material preparation method, it is characterised in that：First pass through above-mentioned absorbent charcoal material electricity
Absorbent charcoal material is made in pole material preparation method, then further comprising the steps of：
E, by the liquor potassic permanganate of a concentration of 0.5~2.0mol/L, 200ml ethanol solutions and a concentration of 1.0~
The Actidose of 3.0mol/L is uniformly mixed, and is stirred 1~2 hour at normal temperatures, is obtained mixed solution, wherein the Gao Meng
The mass ratio of sour potassium solution and the Actidose is 2：1~10：1；
F, to the NaOH solution of a concentration of 1.0~1.5mol/L of the mixed solution and dripping, while it being stirred solution,
Then mixed solution is heated to 80~100 DEG C, 3~5 hours postcoolings of isothermal reaction to room temperature；
G, mixed solution is washed with hydrochloric acid solution, is then filtered with pure water, it is mixed that conductive agent is added after drying process
It closes uniformly, under inert gas protection, is heated to 400-700 DEG C, is cooled to room temperature, manganese oxide/active carbon combined electrode is made
Material.
Preferably, the conductive agent is conductive black or graphite agent.
After using above-mentioned technical proposal, the beneficial effects of the invention are as follows：
Active carbon electrode material preparation method being made with maize straw method proposes a kind of, and with maize straw system
Make manganese oxide/activated carbon composite electrode material preparation method to effectively improve by combination electrode material made from this method
The cycle performance of transition metal oxide, the distinctive porous structure of activated carbon made of this method can effectively alleviate transition gold
Belong to volume change of the oxide in charge and discharge process, improves the cyclical stability of material, meanwhile, activated carbon made of this method
The porous structure having can increase the contact area of electrolyte and electrode material, and more reactions are provided for electrochemical reaction
Point is conducive to the quick progress of electrochemical reaction, to enhance the high rate performance of electrode material.
Manganese oxide/activated carbon composite electrode material, adds conductive agent made from this method, efficiently solves stalk life
The disadvantage that intensity existing for the activated carbon of production is low, activation grade is low and conductivity is poor improves absorbent charcoal material obtained
Intensity, activation grade and conductivity.
This method is raw material using crops maize straw, produces active carbon electrode material, it is proposed that crops corn stalk
The novel processing method of stalk solves stalk exhaust gas and burns the wasting of resources brought and problem of environmental pollution, improves farming
The comprehensive development and utilization and its utilization rate of object stalk.
Specific implementation mode
With reference to specific embodiment, the present invention is further explained.
Embodiment one
Corn stalk powder is broken to the stalk particle of 0.35~0.42mm of grain size, stalk particle is crossed 40 mesh sieve, and drying is extremely
The moisture of stalk particle is less than 10%；Stalk particle after drying is packed into crucible, under the protection atmosphere of inert gas,
It is heated to 500~600 DEG C in kiln according to the rate of heat addition of 5~10 DEG C/min, constant temperature is then kept in kiln 4 hours,
Obtain maize straw carbonization material；By maize straw carbonization material and KOH according to mass ratio 1：1~5：1 ratio is uniformly mixed
After crucible is added, under the protection atmosphere of argon gas, heated the mixture in kiln according to the rate of heat addition of 5~10 DEG C/min
700~1000 DEG C, 2 hours postcoolings of heat preservation to room temperature；The mixture that will be cooled to room temperature is washed with acid solution, then with pure
Water washing to pH value is 6~7, and the particle of 15~20 μm of grain size is crushed to after drying process, and absorbent charcoal material is made.
Then by the liquor potassic permanganate of a concentration of 1.0mol/L, 200ml ethanol solutions and a concentration of 2.0mol/L
Actidose is uniformly mixed, and ethyl alcohol is generated acetic acid and manganese oxide, chemical formula are by potassium permanganate oxidation：5C2H5OH+4MnO4 -
+12H+=5CH3COOH+4Mn2 ++11H2O), then stir 1 hour at normal temperatures, obtain mixed solution, wherein potassium permanganate is molten
The mass ratio of liquid and Actidose is 2：1~10：1,；To the NaOH solution of a concentration of 1.2mol/L of mixed solution and dripping,
Acid-base neutralization reaction occurs, chemical formula is：
NaOH+CH3COOH=CH3COONa+H2O
(OH-)+(CH3COOH)=(CH3COO-)+H2O)
It is stirred solution simultaneously, mixed solution is then heated to 80~100 DEG C, 3 hours postcoolings of isothermal reaction are extremely
Room temperature；Mixed solution is washed with hydrochloric acid solution, is then filtered with pure water, it is equal that conductive black mixing is added after drying process
It is even, under inert gas protection, it is heated to 400-700 DEG C, be cooled to room temperature, manganese oxide/activated carbon composite electrode material is made.
Embodiment two
Corn stalk powder is broken to the stalk particle of 0.35~0.42mm of grain size, stalk particle is crossed 40 mesh sieve, and drying is extremely
The moisture of stalk particle is less than 10%；Stalk particle after drying is packed into crucible, under the protection atmosphere of inert gas,
It is heated to 500~600 DEG C in kiln according to the rate of heat addition of 5~10 DEG C/min, constant temperature is then kept in kiln 3 hours,
Obtain maize straw carbonization material；By maize straw carbonization material and NaOH according to mass ratio 1：1~5：1 ratio is uniformly mixed
After crucible is added, under the protection atmosphere of argon gas, heated the mixture in kiln according to the rate of heat addition of 5~10 DEG C/min
700~1000 DEG C, 2 hours postcoolings of heat preservation to room temperature；The mixture that will be cooled to room temperature is washed with acid solution, then with pure
Water washing to pH value is 6~7, and the particle of 15~20 μm of grain size is crushed to after drying process, and absorbent charcoal material is made.
Then by the liquor potassic permanganate of a concentration of 1.0mol/L, 200ml ethanol solutions and a concentration of 2.0mol/L
Actidose is uniformly mixed, and ethyl alcohol is generated acetic acid and manganese oxide, chemical formula are by potassium permanganate oxidation：5C2H5OH+4MnO4 -
+12H+=5CH3COOH+4Mn2 ++11H2O), at normal temperatures stir 2 hours, obtain mixed solution, wherein liquor potassic permanganate with
The mass ratio of Actidose is 2：1~10：1；To the NaOH solution of a concentration of 1.2mol/L of mixed solution and dripping, acid occurs
Alkali neutralization is reacted, and chemical formula is：
NaOH+CH3COOH=CH3COONa+H2O
(OH-)+(CH3COOH)=(CH3COO-)+H2O)
It is stirred solution simultaneously, mixed solution is then heated to 80~100 DEG C, 4 hours postcoolings of isothermal reaction are extremely
Room temperature；Mixed solution is washed with hydrochloric acid solution, is then filtered with pure water, graphite agent mixing is added after drying process
Uniformly, under inert gas protection, it is heated to 400-700 DEG C, is cooled to room temperature, manganese oxide/active carbon combined electrode material is made
Material.
Embodiment three
Corn stalk powder is broken to the stalk particle of 0.35~0.42mm of grain size, stalk particle is crossed 40 mesh sieve, and drying is extremely
The moisture of stalk particle is less than 10%；Stalk particle after drying is packed into crucible, under the protection atmosphere of inert gas,
It is heated to 500~600 DEG C in kiln according to the rate of heat addition of 5~10 DEG C/min, constant temperature is then kept in kiln 5 hours,
Obtain maize straw carbonization material；By maize straw carbonization material and CaCl2According to mass ratio 1：1~5：1 ratio mixing is equal
Crucible is added after even to heat mixture in kiln according to the rate of heat addition of 5~10 DEG C/min under the protection atmosphere of argon gas
To 700~1000 DEG C, 2 hours postcoolings of heat preservation to room temperature；The mixture that will be cooled to room temperature is washed with acid solution, is then used
Pure water to pH value is 6~7, and the particle of 15~20 μm of grain size is crushed to after drying process, and absorbent charcoal material is made.
Then by the liquor potassic permanganate of a concentration of 1.0mol/L, 200ml ethanol solutions and a concentration of 2.0mol/L
Actidose is uniformly mixed, and ethyl alcohol is generated acetic acid and manganese oxide, chemical formula are by potassium permanganate oxidation：5C2H5OH+4MnO4 -
+12H+=5CH3COOH+4Mn2 ++11H2O), at normal temperatures stir 1 hour, obtain mixed solution, wherein liquor potassic permanganate with
The mass ratio of Actidose is 2：1~10：1；To the NaOH solution of a concentration of 1.2mol/L of mixed solution and dripping, acid occurs
Alkali neutralization is reacted, and chemical formula is：
NaOH+CH3COOH=CH3COONa+H2O
(OH-)+(CH3COOH)=(CH3COO-)+H2O)
It is stirred solution simultaneously, mixed solution is then heated to 80~100 DEG C, 5 hours postcoolings of isothermal reaction are extremely
Room temperature；Mixed solution is washed with hydrochloric acid solution, is then filtered with pure water, it is equal that conductive black mixing is added after drying process
It is even, under inert gas protection, it is heated to 400-700 DEG C, be cooled to room temperature, manganese oxide/activated carbon composite electrode material is made.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, without departing from the spirit and scope of the present invention, this hair
Bright to will also have various changes and improvements, these changes and improvements all fall within the protetion scope of the claimed invention.The present invention claims
Protection domain is defined by the appending claims and its equivalent thereof.
Claims (4)
1. manganese oxide/activated carbon composite electrode material preparation method, it is characterised in that：Include the following steps：
A, corn stalk powder is broken to the stalk particle of 0.35~0.42mm of grain size, stalk particle is crossed 40 mesh sieve, and dry to straw
The moisture of stalk particle is less than 10%；
B, the stalk particle after drying is packed into crucible, under the protection atmosphere of inert gas, according to the heating of 5~10 DEG C/min
Rate is heated to 500~600 DEG C in kiln, constant temperature is then kept in kiln 3~5 hours, obtains maize straw carbide
Material；
C, by maize straw carbonization material and activator according to mass ratio 1：1~5：Earthenware is added in 1 ratio after mixing
Crucible heats the mixture to 700 according to the rate of heat addition of 5~10 DEG C/min under the protection atmosphere of inert gas in kiln
~1000 DEG C, 2 hours postcoolings of heat preservation to room temperature；
D, the mixture that will be cooled to room temperature is washed with acid solution, is then 6~7 with pure water to pH value, is dried
It is crushed to the particle of 15~20 μm of grain size afterwards, absorbent charcoal material is made；
E, by the liquor potassic permanganate of a concentration of 0.5~2.0mol/L, 200ml ethanol solutions and a concentration of 1.0~3.0mol/
The Actidose of L is uniformly mixed, and is stirred 1~2 hour at normal temperatures, is obtained mixed solution, wherein the liquor potassic permanganate
Mass ratio with the Actidose is 2：1~10：1；
F, to the NaOH solution of a concentration of 1.0~1.5mol/L of the mixed solution and dripping, while it being stirred solution, then
Mixed solution is heated to 80~100 DEG C, 3~5 hours postcoolings of isothermal reaction to room temperature；
G, mixed solution is washed with hydrochloric acid solution, is then filtered with pure water, it is equal that conductive agent mixing is added after drying process
It is even, under inert gas protection, it is heated to 400-700 DEG C, be cooled to room temperature, manganese oxide/activated carbon composite electrode material is made.
2. manganese oxide as described in claim 1/activated carbon composite electrode material preparation method, it is characterised in that：The inertia
Gas is argon gas, nitrogen or argon gas nitrogen mixed gas.
3. manganese oxide as claimed in claim 1 or 2/activated carbon composite electrode material preparation method, it is characterised in that：The work
Agent is KOH, CaCl2Or NaOH.
4. manganese oxide as described in claim 1/activated carbon composite electrode material preparation method, it is characterised in that：The conduction
Agent is conductive black or graphite agent.
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| CN108584956A (en) * | 2018-04-20 | 2018-09-28 | 句容市盛达环保净化材料有限公司 | A kind of production equipment producing high grade activated carbon |
| CN110518262B (en) * | 2019-08-13 | 2020-05-26 | 武汉长海电力推进和化学电源有限公司 | Microbial fuel cell anode material and preparation method thereof |
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| JP2006225231A (en) * | 2005-02-21 | 2006-08-31 | Univ Of Miyazaki | Activated carbon from chitinous matter as raw material and its manufacturing method |
| CN103072986A (en) * | 2013-01-25 | 2013-05-01 | 中国科学院新疆理化技术研究所 | Method for preparing cotton stalk based active carbon electrode material by adopting gradient constant-temperature activation method |
| CN104409225A (en) * | 2014-11-28 | 2015-03-11 | 西北师范大学 | Preparation method of manganese dioxide/ carbon microspheres composite material and application of composite material serving as supercapacitor electrode material |
| CN105513829A (en) * | 2016-02-26 | 2016-04-20 | 济南大学 | Carbon nanotube/carbon fiber composite material and carbon-base/manganese oxide composite electrode material |
| CN105731452A (en) * | 2016-01-22 | 2016-07-06 | 青岛大学 | Active carbon electrode material as well as preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006225231A (en) * | 2005-02-21 | 2006-08-31 | Univ Of Miyazaki | Activated carbon from chitinous matter as raw material and its manufacturing method |
| CN103072986A (en) * | 2013-01-25 | 2013-05-01 | 中国科学院新疆理化技术研究所 | Method for preparing cotton stalk based active carbon electrode material by adopting gradient constant-temperature activation method |
| CN104409225A (en) * | 2014-11-28 | 2015-03-11 | 西北师范大学 | Preparation method of manganese dioxide/ carbon microspheres composite material and application of composite material serving as supercapacitor electrode material |
| CN105731452A (en) * | 2016-01-22 | 2016-07-06 | 青岛大学 | Active carbon electrode material as well as preparation method and application thereof |
| CN105513829A (en) * | 2016-02-26 | 2016-04-20 | 济南大学 | Carbon nanotube/carbon fiber composite material and carbon-base/manganese oxide composite electrode material |
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Effective date of registration: 20181026 Address after: 261021 east of Tai Xiang street, east of long song Road, Weifang Economic Development Zone, Shandong. Patentee after: Weifang Huicheng New Material Technology Co., Ltd Address before: 261061 Yuqing street, Weifang high tech Zone, Shandong 169 Patentee before: Weifang Zhengyuan Powder Engineering Equipment Co.,Ltd. |