CN106531476B - A kind of preparation method of metal oxide/carbon composite - Google Patents
A kind of preparation method of metal oxide/carbon composite Download PDFInfo
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- CN106531476B CN106531476B CN201611246093.1A CN201611246093A CN106531476B CN 106531476 B CN106531476 B CN 106531476B CN 201611246093 A CN201611246093 A CN 201611246093A CN 106531476 B CN106531476 B CN 106531476B
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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
A kind of entitled preparation method of metal oxide/carbon composite of the present invention.Belong to material science and electrochemistry science and technology field.It is mainly to provide a kind of metal oxide and the compound preparation method of carbon material.It is mainly characterized by：1. by immersion, centrifugal vacuum freeze-drying is mixed with metal salt solution after biomass washing, dry, crushing；It repeats 25 times, until the biomass quality after dry increases by 0.1% 15%；2. being put into solid salt in crucible, and it is continually fed into inert gas, is heated to the solid salt that 450 DEG C make to 900 DEG C in crucible and melts；3. by biomass foam nickel coated, it is immersed in and melts in solid salt, keep the temperature 0.25h 2h, be cooled to room temperature, product is taken out into washing, centrifugation, vacuum freeze drying.The technology of the present invention technological process is short, and equipment is simple, and raw material sources are extensive, at low cost, and metal oxide energy uniform load is on the carbon material in prepared metal oxide/carbon material composite material.
Description
Technical field
The invention belongs to material science and electrochemistry science and technology field, and in particular to one kind being used for electric chemical super capacitance
The preparation method of metal oxide/carbon composite of device.
Background technology
As fossil energy exhaustion and global warming make people utilize pay attention to day by day to regenerative resource, send out energetically
Opening up clean energy vehicle becomes irreversible trend.With the commercialized development of electric vehicle, hybrid vehicle etc., efficiently
Energy storage and switch technology be faced with increasing challenge.Ultracapacitor is one kind between accumulator and physical capacitors
Energy storage device between device.Because of its high-energy density, can be obtained the features such as instantaneous large-current fast charging and discharging, long circulation life
People more and more pay close attention to.
According to the difference of energy storage mechnism, ultracapacitor can be divided into two kinds：One is charge is stored in carbon electrode/electrolysis
In electric double layer at matter solution interface；Second is Faraday pseudo-capacitance or pseudo-capacitance, is in metal oxide or conducting polymer
Quick redox reaction in object surface or body phase and energy storage.The main electrode material of the first capacitor is with high-ratio surface
Long-pending carbon material, its advantage is that material is cheap and easy to get, good cycle, and Technical comparing is ripe, the disadvantage is that energy density is not high.
The main material of second of capacitor is metal oxide and conducting polymer, its advantage is that specific capacity is higher than carbon material, but gold
Belong to that oxide is of high cost, poorly conductive or toxic, conducting polymer volume in charge and discharge process can change, cause
The cycle performance of capacitor is unstable.Therefore it can pass through the double-layer electric of carbon by preparing metal oxide and carbon composite
The combination of the pseudo-capacitance of metal oxide held and be filled in carbon pores gap, plays respective advantage, obtains high performance electrode
Material.
China is large agricultural country, the stalks such as a large amount of paddy and wheat of annual output, corn, oil crop.According to investigations, China is every
Year stalk total amount is up to 800,000,000 tons or so, since stalk quantity is big, density is small, collecting and distributing storage and transportation is costly, economic value is low, people
The main waste that is considered as is abandoned or is directly burnt.Straw burning has not only influenced daily life but also has caused pole
Big problem of environmental pollution has become the public hazards of social concerns.Biomass contains a large amount of cellulose fibres, be widely present and
Renewable, manufacturing cost problem can not only have been reduced but also can solve stalk processing hardly possible and resource wave by selecting abandoned biomass as carbon source
The problem of taking.Therefore, research with abandoned biomass be carbon source have environmental protection and economic benefit double meaning.
Invention content
The purpose of the present invention is to provide a kind of preparation sides of metal oxide/carbon composite for ultracapacitor
Method.
Technical solution of the invention is：A method of preparing metal oxide/carbon composite, it is characterised in that
Include the following steps：
1. by biomass washing, dry, crushing；Biomass after crushing is mixed into immersion with metal salt solution, then from
Heart vacuum freeze drying；It repeats 2-5 times, until the biomass quality after dry increases 0.1%-15%；
2. being put into solid salt in crucible, and it is continually fed into inert gas argon gas or nitrogen, is heated to 450 DEG C to 900 DEG C
The solid salt in crucible is set to melt；
3. by the biomass foam nickel coated of processing is 1. walked through the, it is immersed in the thawing solid salt in crucible, keeps the temperature
0.25h -2h, then cool to room temperature, and product is taken out washing, centrifugation, vacuum freeze drying, metal oxide/carbon is made
Composite material.
1. the biomass described in step is that agro-ecology waste, industrial processes are discarded to technical solution of the invention the
One or more of biomass and forest abandoned biomass.
Agro-ecology waste described in technical solution of the invention is rice husk, peanut shell or stalk；Industry adds
Work abandoned biomass is bagasse, cocoanut shell, sesame-send cake or rape cake；Forest abandoned biomass is the root, stem or leaf of biomass.
Technical solution of the invention the 1. the metal salt solution described in step be Co, Ni, Mn or Fe nitrate, sulphur
The aqueous solution and/or alcoholic solution of one or more of hydrochlorate, chlorate or metallo-organic complex, a concentration of 0.3-
3mol/L。
Alcoholic solution described in technical solution of the invention is methanol solution and/or ethanol solution.
Biomass of the technical solution of the invention the 1. described in step mixes immersion with metal salt solution, and process is
Biomass after crushing is positioned in container, is vacuumized, it is 0.1-0.3Mpa to be depressurized to vacuum degree, and metal salt solution is added,
Using the porous structure of biomass, solution is set to enter inside biomass along biomass itself duct, soaking time 15min-
180min；It repeats 2-5 times, the biomass quality after drying increases 0.1%-15%.
2. the solid salt described in step is one kind in NaCl, KCl, NaOH or KOH to technical solution of the invention the
Or a variety of mixing.
The present invention impregnates abandoned biomass by metal salt solution, and metal salt is allowed to enter biomass by itself biological duct
Inside after being then freeze-dried again, obtains this product by thermal cracking in molten salt at a certain temperature.This method is by by metal
Oxide and carbon material are compound, reach the requirement for improving electric conductivity and promoting specific capacity.
The present invention has the advantage that compared with prior art：（1）The present invention selects abandoned biomass as carbon raw material, cost
It is low and derive from a wealth of sources；（2）At reduced pressure, biomass is impregnated by metal salt solution, the hole of biomass itself can be utilized
Road quickly enters inside biomass, is evenly distributed；（3）When being cracked in fused salt, the structure that biomass energy keeps its special,
Metal oxide particle can be formed in situ in metal salt, and such metal salt component is evenly distributed, and granularity is smaller, gives full play to
The synergistic effect of carbon and metal oxide；（4）It can make the metal salt in access aperture road will not be using Vacuum Freezing ＆ Drying Technology
The concentration aggregation of aperture end.
The technology of the present invention technological process is short, and equipment is simple, and raw material sources are extensive, at low cost, and prepared metal oxide/
Metal oxide energy uniform load is on the carbon material in carbon material composite material.
Specific implementation mode
The protection that preparation method of the present invention is described further with reference to specific embodiment, but is invented
Range is not limited to this.
Embodiment 1：
10g stalks are washed, 150 μm or so size particles is dried, crushed into, is put into container with foam nickel coated, it will
Container vacuum-pumping is 0.1Mpa to vacuum degree, is rapidly added the 2mol/L Ni (NO of 500ml3)2Solution, holding vacuum degree are
Biomass after immersion is taken out drying, immersion 1 time is repeated, then by biomass by 0.1Mpa or so, soaking time 30min
Vacuum freeze drying is taken out, quality is 11.24g after weighing.It is put into crucible and is placed in instead after taking 480gNaCl, 20gNaOH to mix
It answers in device, is continually fed into inert gas argon gas, heating fused salt is molten by being immersed in the good biomass of foam nickel coated to 800 DEG C
In salt, 0.5h is kept the temperature, product is taken out, cooling, centrifugation, vacuum freeze drying is to get to NiO/C composite materials.
Embodiment 2：
10g peanut shells are washed, 75 μm or so size particles is dried, crushed into, is put into container with foam nickel coated,
It is 0.3Mpa by container vacuum-pumping to vacuum degree, is rapidly added the 0.4 mol/L MnSO of 500ml4Solution, holding vacuum degree are
Biomass after immersion is taken out drying, immersion 2 times is repeated, then by biomass by 0.3Mpa or so, soaking time 60min
Vacuum freeze drying is taken out, quality is 10.58g after weighing.It is put into crucible and is placed in instead after taking 380g KCl, 120g KOH to mix
It answers in device, is continually fed into inert nitrogen gas, then heating fused salt cools to 700 DEG C to 800 DEG C, foam nickel coated will be used good
Biomass be immersed in fused salt, keep the temperature 2h, product taken out, cooling, centrifugation, vacuum freeze drying is to get compound to MnO/C
Material.
Embodiment 3：
By 10g sesame-send cakes（Residue after oil expression）Washing, is dried, crushed into 40 μm or so size particles, with nickel foam packet
It covers and is put into container, be 0.2Mpa by container vacuum-pumping to vacuum degree, be rapidly added the 3 mol/L CoCl of 500ml2Ethyl alcohol is molten
Liquid, it is 0.2Mpa or so, soaking time 90min to keep vacuum degree, and biomass after immersion is taken out drying, repeats immersion 1
Secondary, taking-up is placed on low temperature on tablet drier and dries 60min, is then freeze-dried biomass vacuum, quality is after weighing
11.37g.It is put into crucible and is placed in reactor after taking 240g KCl, 260g KOH to mix, be continually fed into inert gas argon gas,
Fused salt is heated to 800 DEG C, 570 DEG C is then cooled to, will be immersed in fused salt with the good biomass of foam nickel coated, is kept the temperature
0.25h takes out product, cooling, centrifugation, and vacuum freeze drying is to get to CoO/C composite materials.
Embodiment 4：
By the withered leaf of bamboo washings of 10g, 50 μm or so size particles are dried, crushed into, are put into container with foam nickel coated,
It is 0.1Mpa by container vacuum-pumping to vacuum degree, is rapidly added the 1 mol/L Fe (NO of 500ml3)3Solution, holding vacuum degree are
Biomass after immersion is taken out drying, immersion 4 times is repeated, then by biomass by 0.1Mpa or so, soaking time 160min
Vacuum freeze drying, quality is 10.96g after weighing.It is put into crucible after taking 245g NaCl, 255g NaOH to mix and is placed in reaction
In device, it is continually fed into inert nitrogen gas, then heating fused salt cools to 470 DEG C to 820 DEG C, will be good with foam nickel coated
Biomass is immersed in fused salt, keeps the temperature 1h, product is taken out, cooling, centrifugation, and vacuum freeze drying is to get to Fe2O3/ C is compound
Material.
Claims (5)
1. a kind of preparation method of metal oxide/carbon composite, it is characterised in that include the following steps：
1. by biomass washing, dry, crushing；Biomass after crushing is mixed into immersion with metal salt solution, is then centrifuged for true
Vacuum freecing-dry；It repeats 2-5 times, until the biomass quality after dry increases 0.1%-15%；The metal salt solution be Co,
The aqueous solution and/or alcohol of one or more of nitrate, sulfate, chlorate or the metallo-organic complex of Ni, Mn or Fe
Solution, a concentration of 0.3-3mol/L；
2. being put into solid salt in crucible, and it is continually fed into inert gas argon gas or nitrogen, being heated to 450 DEG C to 900 DEG C makes earthenware
Solid salt in crucible is melted；The solid salt is one or more mixing in NaCl, KCl, NaOH or KOH；
3. by the biomass foam nickel coated of processing is 1. walked through the, it is immersed in the thawing solid salt in crucible, keeps the temperature 0.25h
- 2h is then cooled to room temperature, and product is taken out washing, centrifugation, vacuum freeze drying, it is multiple that metal oxide/activated carbon is made
Condensation material.
2. a kind of preparation method of metal oxide/carbon composite according to claim 1, it is characterised in that：It is described
The 1. the biomass described in step be in agro-ecology waste, industrial processes abandoned biomass and forest abandoned biomass
It is one or more of.
3. a kind of preparation method of metal oxide/carbon composite according to claim 2, the agro-ecology is useless
Gurry is rice husk, peanut shell or stalk；Industrial processes abandoned biomass is bagasse, cocoanut shell, sesame-send cake or rape cake；Forest
Abandoned biomass is the root, stem or leaf of biomass.
4. a kind of preparation method of metal oxide/carbon composite according to claim 1 or 2, it is characterised in that：Institute
The alcoholic solution stated is methanol solution and/or ethanol solution.
5. a kind of preparation method of metal oxide/carbon composite according to claim 1 or 2, it is characterised in that：The
1. the biomass described in step mixes immersion with metal salt solution, process is that the biomass after crushing is positioned in container,
It vacuumizes, it is 0.1-0.3Mpa to be depressurized to vacuum degree, and metal salt solution is added keeps solution suitable using the porous structure of biomass
Biomass itself duct to enter inside biomass；Soaking time is 15min-180min；It repeats 2-5 times, after drying
Biomass quality increases 0.1%-15%.
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| CN107093529B (en) * | 2017-05-08 | 2019-04-30 | 华东理工大学 | A method of transition metal oxide/carbon composite is prepared using solar energy |
| CN109465001A (en) * | 2018-10-16 | 2019-03-15 | 江苏理工学院 | A kind of preparation method and application of carried metal carbon micron chip |
| CN110563111A (en) * | 2019-02-27 | 2019-12-13 | 湖北文理学院 | preparation method of industrial wastewater composite treating agent |
| CN110537658A (en) * | 2019-02-27 | 2019-12-06 | 湖北文理学院 | preparation method of blueberry sesame powder antioxidant additive |
| CN110104630B (en) * | 2019-05-16 | 2021-05-11 | 华南师范大学 | Porous carbon composite material for battery diaphragm and preparation method and application thereof |
| CN110416516A (en) * | 2019-07-25 | 2019-11-05 | 东北大学 | A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide |
| CN110624551B (en) * | 2019-10-10 | 2022-05-31 | 湖北文理学院 | Preparation method of lotus seedpod-based carbon-supported nickel catalyst |
| CN113249142A (en) * | 2021-05-21 | 2021-08-13 | 西北大学 | Preparation method of biomass charcoal-metal oxide composite electrode material |
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| CN104916452A (en) * | 2015-04-21 | 2015-09-16 | 中国林业科学研究院林产化学工业研究所 | Wooden active carbon composite material for super capacitor and preparing method of wooden activated carbon composite material |
| JP2016162805A (en) * | 2015-02-27 | 2016-09-05 | 国立大学法人山口大学 | Carbon fiber aggregate with layered manganese oxide carried thereon and production method thereof |
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| CN101875845A (en) * | 2010-07-08 | 2010-11-03 | 浙江工业大学 | Process for co-producing bio-oil and biological carbon by utilizing crop straws and special device |
| CN104167300A (en) * | 2014-05-30 | 2014-11-26 | 燕山大学 | Active carbon and method for preparing active carbon/zinc oxide compound electrode material |
| CN104167301A (en) * | 2014-06-04 | 2014-11-26 | 烟台大学 | Method for using carbonized Enteromorpha to prepare supercapacitor electrode material |
| JP2016162805A (en) * | 2015-02-27 | 2016-09-05 | 国立大学法人山口大学 | Carbon fiber aggregate with layered manganese oxide carried thereon and production method thereof |
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Effective date of registration: 20201028 Address after: 441000 Xiangyang City, Hubei province Xiangcheng District Long Road No. 18 Patentee after: Xiangyang University Science Park Development Co., Ltd Address before: 441053 Xiangfan City, Hubei province Xiangcheng District Long Road No. 296 Patentee before: HUBEI University OF ARTS AND SCIENCE |