CN105540585A - Method for preparing electrode material of supercapacitor from mimosa pudica - Google Patents
Method for preparing electrode material of supercapacitor from mimosa pudica Download PDFInfo
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- CN105540585A CN105540585A CN201610023346.2A CN201610023346A CN105540585A CN 105540585 A CN105540585 A CN 105540585A CN 201610023346 A CN201610023346 A CN 201610023346A CN 105540585 A CN105540585 A CN 105540585A
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- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
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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 relates to a method for preparing an electrode material of a supercapacitor from mimosa pudica. The method mainly includes the steps that mimosa pudica is freeze-dried in vacuum, carbonized at the low temperature of 200 DEG C-400 DEG C and then carbonized at the low temperature of 600 DEG C-800 DEG C in a tube type resistance furnace, biochar and analytically pure potassium hydroxide are mixed uniformly by the mass ratio of 1:0.5-4 and carbonized for 0.5-3 h at the constant temperature ranging from 600 DEG C to 900 DEG C in a box-type atmosphere furnace, and an activated product is subjected to acid treatment, centrifugally washed to be neutral and dried to obtain the electrode material of the supercapacitor. The method is simple in synthesis step, relative moderate in reaction condition, high in repeatability, high in yield and easy to industrialize on a large scale; the specific surface area of the prepared electrode material of the supercapacitor reaches up to 1307 m<2>/g, the measured capacitance reaches up to 250 F/g under the current density of 1A/g in a 6M KOH solution, cycling stability is good, and the electrode material of the supercapacitor is relatively ideal.
Description
Technical field
The invention belongs to electrochemical field, particularly a kind of preparation method of electrode material for super capacitor.
Background technology
As everyone knows, energy problem is related to Economic development and the social stability in the world.Science and technology is maked rapid progress, and portable electric appts, mixed power electric car, science and techniques of defence, aerospace obtain develop rapidly, make market day by day urgent to the demand of large power energy storage element.Scientists is new electric energy storage unit---the ultracapacitor solving energy problem and excavate rapidly, also known as electrochemical capacitor.The advantages such as ultracapacitor has that power density is high, charge-discharge velocity is fast, have extended cycle life, safety and environmental protection, it is the brand-new type energy storage device of one between a kind of rapid charge and discharge between traditional capacitor and the Large Copacity of store battery, meet the widespread demand of new millennium to stored energy, development prospect is wide.
But, the difficult problem of pendulum in face of numerous scientific research personnel is that most electrical condenser is in energy density or can not compare favourably with chemical cell, and the key factor affecting ultracapacitor performance is selecting of electrode materials, thus study high-energy-density, stable performance electrode materials extremely urgent.In all electrode material for super capacitor, research the earliest and the most ripe be carbon material.Carbon-based material is due to its good chemical stability, high thermal conductivity, high conductivity, improve the status of carbon material in electrode material for super capacitor further.Current different sorts, the various types of materials with different structure have been widely studied and have tested.JianhuaHou etc. are raw material at " Scientificreports " with rice bran, and prepared the three-dimensional porous absorbent charcoal material of high-specific surface area by high temperature cabonization and KOH chemical activation method, obtained active carbon material specific surface area is up to 1067m
2g
-1, mean pore size is 0.76nm, in three-electrode system, in 6MKOH solution, and 1Ag
-1under current density, record electric capacity up to 313Fg
-1.The research such as JiandongXu find by the pre-carbonization of first for happy shell low temperature (270 DEG C) again high temperature (750 DEG C) carbonization obtain biological carbon materials (C-SPN), with hydrofluoric acid dips washing removing silica impurity, finally with KOH admixture activation in varing proportions with it, the two-dimensional layer sheet structure of thickness close to 200nm can be obtained, and to study in reactivation process activator add-on to the impact of absorbent charcoal material performance.The two raw material is all taken agriculture byproduct and food industry wastes and is achieved and turn waste into wealth, and has larger economic worth and interests.Be not difficult to find, the quality of the final performance of gac not only with its preparation method, the template type selected is closely related, and the selection of carbon matrix precursor is also vital.Whether the carbon matrix precursor selected wants to be applied to energy storage device better, depends on that it is as the intrinsic physicochemical property of presoma, cost, source, containing as these hybridized atoms of N, P, B etc.
As far back as 18th century, scientist has just found electricity in electric eel, thus creates bioelectric concept.Except people self with bioelectricity, a lot of plant of occurring in nature also all belongs to charged plant, such as: Touch-me-notAction Plant (minosapudica), Venus's-flytrap, candle grass, Sunflower Receptacle etc.When finger touches Touch-me-notAction Plant, its blade of just " bowing and bow one's head " is closely sealed, and Venus's-flytrap is subject to insect stimulation and closes delicately leaf folder, and these are all bioelectric embodiments.Scientists has progressively opened the Mysterious Veil of these plant phenomenons.For Touch-me-notAction Plant, why " shy " it be because blade is when experiencing stimulation, can generation current immediately.Electric current imports the coccoid organ in blade into along petiole, cause the activity of coccoid organ.The activity of the latter is with again rotor blade movable, and blade is closed.And the moment transmission of the quick generation of these potential differences and current potential is the quick flowing by cells in vivo liquid, investigation finds that the multi-pore channel structure that Touch-me-notAction Plant branches and leaves have general not charged plant and do not have, the structure as far as possible retained after the charing of its internal structure are conducive to the transfer of electrolytic solution intermediate ion in inside and transport.Touch-me-notAction Plant strong adaptability in addition, planting technology is easy, and rapidly, cost is low in growth.Research and utilization Touch-me-notAction Plant branches and leaves of the present invention prepare electrode material for super capacitor.There is no the relevant report utilizing Touch-me-notAction Plant branches and leaves to prepare the active carbon material of ultracapacitor both at home and abroad at present.
Summary of the invention
The object of this invention is to provide a kind of technique Touch-me-notAction Plant that utilizes that is simple, reproducible, that be easy to realize industrialization and prepare the method for electrode material for super capacitor.The present invention mainly with charged plant Touch-me-notAction Plant branches and leaves for raw material, analytical pure potassium hydroxide is the method that electrode material for super capacitor prepared by activator.
Technical scheme of the present invention comprises the following steps.
(1) Touch-me-notAction Plant pre-treatment: the Touch-me-notAction Plant branches and leaves dehydrated alcohol of cutting, deionized water are washed 3 times respectively, puts into vacuum freeze drier afterwards at vacuum tightness 4.0Pa, frozen dried 24h under the condition of-103 DEG C, takes out stand-by.
(2) preparation of Touch-me-notAction Plant biological carbon (C-MP): the Touch-me-notAction Plant of step (1) is placed in quartz boat and puts into tube type resistance furnace; under argon shield; with 5 DEG C/min temperature rise rate; first be warming up to 200 ~ 400 DEG C; carbonization at low temperature 1 ~ 3 hour; be warming up to 600 ~ 800 DEG C again; high temperature cabonization 1 ~ 3 hour, treats that it is cooled to room temperature, takes out carbonized product; grind into powder; with absolute ethanol washing 3 ~ 6 times, finally carbonized product is placed in baking oven, 60 ~ 80 DEG C; dry 7 ~ 10h, obtains Touch-me-notAction Plant biological carbon (C-MP).
(3) KOH activation: the Touch-me-notAction Plant biological carbon of step (2) and analytical pure KOH are mixed 1:0.5 ~ 4 in mass ratio; be placed in box atmosphere furnace; under argon shield; with 5 DEG C/min temperature rise rate; be warming up to 600 ~ 900 DEG C; constant temperature carbonization 0.5 ~ 3 hour, treats that it is cooled to room temperature at this temperature, takes out activation products.
(4) activation products acid treatment: the activation products of step (3) are placed in concentrated acid and soak 3 ~ 10h, supersound process 0.5 ~ 2 hour afterwards, ultrasonic power is 60W, use dehydrated alcohol, deionized water wash to neutral successively, finally product is placed in baking oven, 60 ~ 80 DEG C, dry 7 ~ 10h, obtained electrode material for super capacitor.
Described concentrated acid is concentrated hydrochloric acid (massfraction is 36% ~ 38%) or concentrated nitric acid (massfraction is 65% ~ 68%).
The present invention compared with prior art tool has the following advantages:
1, select charged plant Touch-me-notAction Plant, make full use of it and be beneficial to the bioelectric self structure of storage.
2, adopt Vacuum Freezing & Drying Technology, high temperature cabonization after the first carbonization at low temperature of carbonization process, adequately protect its primary formation.
3, synthesis step is simple, and reaction conditions is relatively gentle, and aftertreatment technology is simple, reproducible, and the biomass undergoes adaptation selected is strong, growth is rapid, is easy to realize industrialization.
4, gac (AC-PT) electrode material for super capacitor of preparation, specific surface area is up to 1307m
2g
-1, in 6MKOH solution, 1Ag
-1under current density, record electric capacity up to 250Fg
-1, and good cycling stability.
Accompanying drawing explanation
Fig. 1 is the C-MP scanning electron microscope diagram of the non-activation treatment that the embodiment of the present invention 4 obtains.
Fig. 2 is the scanning electron microscope diagram of the AC-MP of the activated process that the embodiment of the present invention 4 obtains, and wherein, a is activation products AC-MP surface pore structure pattern, and b is activation products AC-MP surface folding pattern.
Fig. 3 is the XRD spectra of absorbent charcoal material prepared by the embodiment of the present invention 4.
Fig. 4 is the constant current charge-discharge test pattern of absorbent charcoal material prepared by the embodiment of the present invention 4.
Fig. 5 is the cyclical stability test pattern of the absorbent charcoal material that the embodiment of the present invention 4 obtains.
Embodiment
Embodiment 1
By fresh for the 15g of cutting Touch-me-notAction Plant dehydrated alcohol and deionized water wash 3 times, put into vacuum freeze drier afterwards at vacuum tightness 4.0Pa, frozen dried 24h under the condition of-103 DEG C.Touch-me-notAction Plant is placed in quartz boat and puts into tube furnace; under argon shield, be first warming up to 200 DEG C with the temperature rise rate of 5 DEG C/min, carbonization at low temperature 1h; be warming up to 800 DEG C again; high temperature cabonization 3 hours, treats that it is cooled to room temperature, takes out carbonized product; grind into powder; with absolute ethanol washing 3 times, be placed in 60 DEG C of dry 10h of baking oven, obtain Touch-me-notAction Plant biological carbon (C-MP).
By even for the ratio mixed grinding of Touch-me-notAction Plant biological carbon and analytically pure potassium hydroxide solid 1:0.5 in mass ratio, be placed in box atmosphere furnace, under argon shield; to be warming up to 600 DEG C under the temperature rise rate of 5 DEG C/min; continuous activation 3h, treats that it is cooled to room temperature, takes out activation products.
Activation products concentrated nitric acid is soaked 3h, ultrasonic 0.5 hour, ultrasonic power was 60W, mixture was added the dilution of 200ml deionized water and used dehydrated alcohol, deionized water wash to neutral more successively, then vacuum-drying 10h at 60 DEG C, obtained electrode material for super capacitor (AC-MP).
Embodiment 2
By fresh for the 15g of cutting Touch-me-notAction Plant dehydrated alcohol and deionized water wash 3 times, put into vacuum freeze drier afterwards at vacuum tightness 4.0Pa, frozen dried 24h under the condition of-103 DEG C.Touch-me-notAction Plant is placed in quartz boat and puts into tube furnace; under argon shield, be first warming up to 300 DEG C with the temperature rise rate of 5 DEG C/min, carbonization at low temperature 3h; be warming up to 600 DEG C again; high temperature cabonization 2 hours, treats that it is cooled to room temperature, takes out carbonized product; grind into powder; with absolute ethanol washing 6 times, finally carbonized product is placed in 80 DEG C of dry 7h of baking oven, obtains Touch-me-notAction Plant biological carbon.
By even for the ratio mixed grinding of Touch-me-notAction Plant biological carbon and analytically pure potassium hydroxide solid 1:4 in mass ratio, be placed in box atmosphere furnace, under argon shield; to be warming up to 900 DEG C under the temperature rise rate of 5 DEG C/min; continuous activation 0.5h, treats that it is cooled to room temperature, takes out activation products.
Activation products concentrated hydrochloric acid is soaked 3h, ultrasonic 2 hours, ultrasonic power was 60W, mixture was added the dilution of 200ml deionized water and used dehydrated alcohol, deionized water wash to neutral more successively, then vacuum-drying 7h at 80 DEG C, obtained electrode material for super capacitor.
Embodiment 3
By fresh for the 15g of cutting Touch-me-notAction Plant dehydrated alcohol and deionized water wash 3 times, put into vacuum freeze drier afterwards at vacuum tightness 4.0Pa, frozen dried 24h under the condition of-103 DEG C.Touch-me-notAction Plant is placed in quartz boat and puts into tube furnace; under argon shield, be first warming up to 400 DEG C with the temperature rise rate of 5 DEG C/min, carbonization at low temperature 2h; be warming up to 750 DEG C again; high temperature cabonization 2 hours, treats that it is cooled to room temperature, takes out carbonized product; grind into powder; with absolute ethanol washing 4 times, be placed in 70 DEG C of dry 10h of baking oven, obtain Touch-me-notAction Plant biological carbon (C-MP).
By even for the ratio mixed grinding of Touch-me-notAction Plant biological carbon and analytically pure potassium hydroxide solid 1:2 in mass ratio, be placed in box atmosphere furnace, under argon shield; to be warming up to 750 DEG C under the temperature rise rate of 5 DEG C/min; continuous activation 2h, treats that it is cooled to room temperature, takes out activation products.
Activation products concentrated hydrochloric acid is soaked 6h; Ultrasonic 0.5 hour, ultrasonic power was 60W, used dehydrated alcohol, deionized water wash to neutral more successively, then vacuum-drying 10h at 70 DEG C, obtained electrode material for super capacitor after mixture being added the dilution of 200ml deionized water.
Embodiment 4
By fresh for the 15g of cutting Touch-me-notAction Plant dehydrated alcohol and deionized water wash 3 times, put into vacuum freeze drier afterwards at vacuum tightness 4.0Pa, frozen dried 24h under the condition of-103 DEG C.Touch-me-notAction Plant is placed in quartz boat and puts into tube furnace; under argon shield, be first warming up to 400 DEG C with the temperature rise rate of 5 DEG C/min, carbonization at low temperature 1h; be warming up to 800 DEG C again; high temperature cabonization 1 hour, treats that it is cooled to room temperature, takes out carbonized product; grind into powder; with absolute ethanol washing 4 times, be placed in 70 DEG C of dry 10h of baking oven, obtain Touch-me-notAction Plant biological carbon (C-MP).
By even for the ratio mixed grinding of Touch-me-notAction Plant biological carbon and analytically pure potassium hydroxide solid 1:3 in mass ratio, be placed in box atmosphere furnace, under argon shield; to be warming up to 900 DEG C under the temperature rise rate of 5 DEG C/min; continuous activation 1h, treats that it is cooled to room temperature, takes out activation products.
Activation products concentrated nitric acid is soaked 10h, ultrasonic 2 hours, ultrasonic power was 60W, mixture was added the dilution of 200ml deionized water and used dehydrated alcohol, deionized water wash to neutral more successively, then vacuum-drying 10h at 70 DEG C, obtained electrode material for super capacitor.
As shown in Figure 1, through vacuum freezing process, after carbonization at low temperature and high temperature cabonization, the multi-pore channel structure of primordial matter keeps complete, but reduces on certain size.
As shown in Figure 2, after activation biological carbon surface occur fold (figure b) and a large amount of pore-creating (figure a), find that macropore inwall has the pore structure interpenetrated not of uniform size, be conducive to the increase of pore volume and specific surface area, thus be conducive to the capacitive property improving material.
As shown in Figure 3, the absorbent charcoal material that the present invention obtains is in 2 θ=24 ° with 43 °, neighbouring appearance 2 graphite features peaks, corresponding with (002) and (100) face of carbon material respectively, and be the broad peak of disperse, belong to typical agraphitic carbon, illustrate that the absorbent charcoal material graphite microcrystal of preparation is undeveloped.
As shown in Figure 4, the charging and discharging curve that the absorbent charcoal material that obtains of the present invention is corresponding under different current density.The discharge and recharge time be corresponding in turn to from long to short current density be 1,2,5,10Ag
-1, curve trilateral all symmetrically.Illustrate that, under constant current charge-discharge state, voltage changes in time obvious linear relationship, mainly owing to there occurs electrostatic double layer charge transfer reaction, the symmetry of curve also show electrostatic double layer charge transfer and has good reversibility.
As shown in Figure 5, the absorbent charcoal material that obtains of the present invention is at 10Ag
-1cyclical stability test under current density.Capacity retention is high, and the minimum capacitance conservation rate is still more than 97%.
Claims (2)
1. utilize Touch-me-notAction Plant to prepare a method for electrode material for super capacitor, it is characterized in that: it comprises the following steps:
(1) Touch-me-notAction Plant pre-treatment: the Touch-me-notAction Plant branches and leaves dehydrated alcohol of cutting and deionized water are washed 3 times respectively, puts into vacuum freeze drier at vacuum tightness 4.0Pa, frozen dried 24h under the condition of-103 DEG C, takes out stand-by;
(2) Touch-me-notAction Plant of step (1) is placed in quartz boat and puts into tube type resistance furnace, under argon shield, with 5 DEG C/min temperature rise rate, first be warming up to 200 ~ 400 DEG C, carbonization at low temperature 1 ~ 3 hour, then be warming up to 600 ~ 800 DEG C, high temperature cabonization 1 ~ 3 hour, treats that it is cooled to room temperature, takes out carbonized product, grind into powder, with absolute ethanol washing 3 ~ 6 times, finally product is placed in baking oven, 60 ~ 80 DEG C, dry 7 ~ 10h, obtains Touch-me-notAction Plant biological carbon;
(3) the Touch-me-notAction Plant biological carbon of step (2) and analytical pure KOH are mixed 1:0.5 ~ 4 in mass ratio, be placed in box atmosphere furnace, under gas shield, with 5 DEG C/min temperature rise rate, be warming up to 600 ~ 900 DEG C, constant temperature carbonization 0.5 ~ 3 hour, treats that it is cooled to room temperature at this temperature, takes out activation products;
(4) activation products of step (3) are placed in concentrated acid and soak 3 ~ 10h, supersound process 0.5 ~ 2 hour afterwards, ultrasonic power is 60W, use dehydrated alcohol, deionized water wash to neutral successively, finally product is placed in baking oven, 60 ~ 80 DEG C, dry 7 ~ 10h, obtained electrode material for super capacitor.
2. the method utilizing Touch-me-notAction Plant to prepare electrode material for super capacitor according to claim 1, is characterized in that: described concentrated acid to be massfraction be 36% ~ 38% concentrated hydrochloric acid or massfraction be 65% ~ 68% concentrated nitric acid.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106207179A (en) * | 2016-07-07 | 2016-12-07 | 陕西科技大学 | The method that a kind of KOH activation pomelo peel prepares sodium-ion battery negative material |
| CN106517182A (en) * | 2016-11-08 | 2017-03-22 | 南昌航空大学 | Preparation method of biomass carbon adopting layered structure |
| CN106587053A (en) * | 2016-11-29 | 2017-04-26 | 东至县森茂炭业有限公司 | Preparation process of special activated carbon for desulfurization |
| CN107055530A (en) * | 2017-05-05 | 2017-08-18 | 商洛学院 | Pumpkin derives stratiform carbon as the preparation method of electrode material for super capacitor |
| CN108622896A (en) * | 2018-05-21 | 2018-10-09 | 桂林电子科技大学 | A kind of egg white based cellular structures carbon material and its preparation method and application |
| CN110063224A (en) * | 2019-05-30 | 2019-07-30 | 湖南省作物研究所 | A kind of In Cadmium Polluted Area spring open country watermelon-autumn corn safety in production rotation system |
| CN110182805A (en) * | 2019-06-22 | 2019-08-30 | 合肥煜创碳业有限公司 | A kind of preparation method of active carbon |
| CN111285688A (en) * | 2020-02-10 | 2020-06-16 | 北方民族大学 | Biomass carbon film and preparation method and application thereof |
| CN112374485A (en) * | 2020-11-12 | 2021-02-19 | 滁州学院 | Preparation method of nitrogen-phosphorus double-doped foamy carbon for zinc ion hybrid capacitor |
| CN114988405A (en) * | 2022-05-23 | 2022-09-02 | 海南师范大学 | Preparation method and application of broadleaf holly leaf biological porous carbon material |
| CN115425229A (en) * | 2022-11-04 | 2022-12-02 | 中科南京绿色制造产业创新研究院 | Positive electrode additive and preparation method and application thereof |
| CN115974074A (en) * | 2019-05-30 | 2023-04-18 | 贵州大学 | Method for preparing nitrogen-containing porous carbon material by utilizing cockroaches |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106207179A (en) * | 2016-07-07 | 2016-12-07 | 陕西科技大学 | The method that a kind of KOH activation pomelo peel prepares sodium-ion battery negative material |
| CN106517182A (en) * | 2016-11-08 | 2017-03-22 | 南昌航空大学 | Preparation method of biomass carbon adopting layered structure |
| CN106587053A (en) * | 2016-11-29 | 2017-04-26 | 东至县森茂炭业有限公司 | Preparation process of special activated carbon for desulfurization |
| CN107055530A (en) * | 2017-05-05 | 2017-08-18 | 商洛学院 | Pumpkin derives stratiform carbon as the preparation method of electrode material for super capacitor |
| CN108622896A (en) * | 2018-05-21 | 2018-10-09 | 桂林电子科技大学 | A kind of egg white based cellular structures carbon material and its preparation method and application |
| CN110063224B (en) * | 2019-05-30 | 2021-07-09 | 湖南省作物研究所 | Safe production rotation mode for watermelons and autumn sweet corns in spring open field in cadmium-polluted area |
| CN110063224A (en) * | 2019-05-30 | 2019-07-30 | 湖南省作物研究所 | A kind of In Cadmium Polluted Area spring open country watermelon-autumn corn safety in production rotation system |
| CN115974074A (en) * | 2019-05-30 | 2023-04-18 | 贵州大学 | Method for preparing nitrogen-containing porous carbon material by utilizing cockroaches |
| CN110182805A (en) * | 2019-06-22 | 2019-08-30 | 合肥煜创碳业有限公司 | A kind of preparation method of active carbon |
| CN111285688A (en) * | 2020-02-10 | 2020-06-16 | 北方民族大学 | Biomass carbon film and preparation method and application thereof |
| CN112374485A (en) * | 2020-11-12 | 2021-02-19 | 滁州学院 | Preparation method of nitrogen-phosphorus double-doped foamy carbon for zinc ion hybrid capacitor |
| CN114988405A (en) * | 2022-05-23 | 2022-09-02 | 海南师范大学 | Preparation method and application of broadleaf holly leaf biological porous carbon material |
| CN114988405B (en) * | 2022-05-23 | 2023-12-29 | 海南师范大学 | Preparation method and application of kuding tea biological porous carbon material |
| CN115425229A (en) * | 2022-11-04 | 2022-12-02 | 中科南京绿色制造产业创新研究院 | Positive electrode additive and preparation method and application thereof |
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| CN105540585B (en) | 2017-11-24 |
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