CN109704331B - Preparation method of activated carbon for super capacitor - Google Patents
Preparation method of activated carbon for super capacitor Download PDFInfo
- Publication number
- CN109704331B CN109704331B CN201910072871.7A CN201910072871A CN109704331B CN 109704331 B CN109704331 B CN 109704331B CN 201910072871 A CN201910072871 A CN 201910072871A CN 109704331 B CN109704331 B CN 109704331B
- Authority
- CN
- China
- Prior art keywords
- activated carbon
- radix puerariae
- organic acid
- preparation
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003990 capacitor Substances 0.000 title claims description 16
- 235000010575 Pueraria lobata Nutrition 0.000 claims abstract description 56
- 150000007524 organic acids Chemical class 0.000 claims abstract description 48
- 238000001994 activation Methods 0.000 claims abstract description 34
- 230000004913 activation Effects 0.000 claims abstract description 32
- 238000005886 esterification reaction Methods 0.000 claims abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 30
- 230000032050 esterification Effects 0.000 claims abstract description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920002472 Starch Polymers 0.000 claims abstract description 24
- 239000004202 carbamide Substances 0.000 claims abstract description 24
- 235000019698 starch Nutrition 0.000 claims abstract description 24
- 239000008107 starch Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 claims abstract description 22
- 239000012043 crude product Substances 0.000 claims abstract description 19
- 230000003213 activating effect Effects 0.000 claims abstract description 17
- 238000009826 distribution Methods 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 241000219781 Pueraria montana var. lobata Species 0.000 claims abstract 5
- 239000000203 mixture Substances 0.000 claims description 23
- 238000003763 carbonization Methods 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000007833 carbon precursor Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 235000011837 pasties Nutrition 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- 239000002243 precursor Substances 0.000 abstract description 11
- 238000005406 washing Methods 0.000 abstract description 10
- 238000010000 carbonizing Methods 0.000 abstract description 6
- 239000012445 acidic reagent Substances 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 244000046146 Pueraria lobata Species 0.000 description 51
- 229910052799 carbon Inorganic materials 0.000 description 31
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- 239000007772 electrode material Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 239000005539 carbonized material Substances 0.000 description 8
- 238000010277 constant-current charging Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 241000219780 Pueraria Species 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- KCYQMQGPYWZZNJ-BQYQJAHWSA-N hydron;2-[(e)-oct-1-enyl]butanedioate Chemical compound CCCCCC\C=C\C(C(O)=O)CC(O)=O KCYQMQGPYWZZNJ-BQYQJAHWSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 241000731396 Pueraria montana var. thomsonii Species 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 244000209700 shan ge teng Species 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 240000002234 Allium sativum Species 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 240000000716 Durio zibethinus Species 0.000 description 1
- 235000006025 Durio zibethinus Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000004611 garlic Nutrition 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of activated carbon for a supercapacitor, which comprises the steps of crushing cleaned radix puerariae, putting the crushed radix puerariae into a mixed solution of organic acid, urea and sodium trimetaphosphate, stirring and mixing, filtering, putting a semi-dry radix puerariae crude product into a reactor, and heating to complete organic acid esterification of radix puerariae starch. And carbonizing, crushing, acid washing and filtering the obtained esterified coarse material to obtain an activated carbon precursor, and finally introducing an activating agent carbon dioxide into a high-temperature furnace for physical activation to obtain the activated carbon with developed pore size and rich pore size distribution. The method can obtain the kudzu starch ester with different degrees of substitution by controlling the dosage of the esterifying agent organic acid reagent, and is easier to prepare the activated carbon with rich aperture, high specific surface area and excellent electrochemical performance in subsequent activation.
Description
Technical Field
The invention relates to the technical field of preparation of electrode materials of a super capacitor, in particular to a method for preparing active carbon of the super capacitor by esterifying pueraria starch with organic acid.
Background
The super capacitor is a novel energy storage device between a traditional capacitor and a lithium ion battery, and has the advantages of high energy density, high power density, long cycle life and the like. Besides being used as a main power source and an auxiliary power source of a power electric automobile, the power device can also be used for power devices such as photovoltaic storage batteries, power grid stabilization, radio emission and the like.
The electrode material of the capacitor is a hot spot of current research, and the electrode material used for the super capacitor is mainly activated carbon. The active carbon as a porous carbon material has important functions in the fields of environmental protection, national defense science and technology, chemical industry and the like due to the advantages of large specific surface area, rich pore structure, stable chemical performance, simple and convenient preparation process flow, low price and the like. Particularly, the market demand on the aspect of super capacitors is huge, but the yield is very small due to various reasons such as technical bottlenecks and the like in China, and most of high-quality activated carbon still needs to be imported. Due to the attention of people on environmental protection, researches on preparing activated carbon by taking regenerated plants as raw materials are more and more. The kudzu root resources in China are quite rich, and wild kudzu roots are mainly distributed in hillside grasses or shrubs in mountainous and hilly places such as Yunnan, Guizhou, Hunan, Tibet, Qinghai and Xinjiang, and are mainly distributed naturally. At present, a large amount of cultivation is carried out in Yunnan, Sichuan, Chongqing, Guangxi, Guangdong and the like.
Because the kudzu has strong growth adaptability, is favorable for warm and humid environments, is cold-resistant and drought-resistant, has low requirements on soil, and can grow in various soils and environments. The kudzu vine is easy to propagate, simple and convenient to manage, rapid to grow, strong in regeneration capacity, high in yield and extremely strong in adaptability, and is rare good economic crop suitable for mountain economic development and water and soil loss treatment. The starch in the root of kudzu vine accounts for about 40 percent of the dry weight of the root of kudzu vine and is the main component in the current application of the root of kudzu vine. The root of kudzu vine is usually ripe about 11 months each year, and the root of kudzu vine is harvested and dug in a period from autumn frost to the next spring before Qingming. The starch content of the root tuber is highest at this time. The radix puerariae starch particles are small, and the radix puerariae is used as the active carbon raw material, so that the method has the advantages of high yield, low price, convenience in activation and the like. At present, no document or patent report is found on the method for pre-activating by using organic acid esterified pueraria starch, and no document or patent report is found on the method for pre-activating by using pueraria as an active carbon initial raw material.
Through research in recent years, it is found that in addition to the pore structure and the specific surface size, which have a great influence on the electrochemical properties of the carbon material, the surface chemical properties of the carbon material also have a great influence on the capacitance properties, and a certain number of acidic, neutral oxygen-containing functional groups, such as carboxyl, carbonyl, quinonyl, lactone, phenolic hydroxyl and the like, exist on the surface of the activated carbon.
The active site groups can improve the compatibility of the material and electrolyte to a certain extent and enhance the electrochemical performance of the material. Therefore, the organic acid reagent is considered to be used as a reaction esterification reagent of the kudzuvine root to perform esterification reaction with the kudzuvine root starch and also used as a pre-activating agent for carbon activation to prepare the activated carbon with developed pore diameter and uniform pore diameter distribution. Hydroxyl contained in starch in radix puerariae and organic acid are subjected to esterification reaction under specific conditions, various organic acid groups are introduced into natural starch of radix puerariae to form the natural starch derivative of radix puerariae starch ester, and the esterified starch has better properties than the natural starch. In subsequent low-temperature carbonization and high-temperature activation, the introduced organic acids also serve as catalysts for carbon activation, and the high-specific-surface-area activated carbon with rich pore size distribution is easier to prepare.
Biomass is an important raw material for preparing activated carbon, and commonly used biomass mainly comprises crop straws, wood shells, fruit pits, rice husks and the like. Such biomass materials are inexpensive. Chinese patent (publication No. CN 102417179A) discloses that peanut shells are adopted as biomass raw materials, and the specific surface area of the obtained activated carbon material reaches 1227 m2(ii) in terms of/g. Chinese patent (publication No. CN 201710474784) discloses a method for preparing activated carbon by taking durian shell powder as a carbon source, and the specific surface area of the activated carbon is 3800 m from 1600-2The Chinese patent No. CN201710243663 discloses that the method for preparing the activated carbon by using the garlic skin as a biomass carbon source still adopts KOH alkali activation, the specific surface area of the activated carbon is as high as 2800, and the method is a typical case for changing waste into valuable. Chinese patent (with the patent number of CN104803383A) discloses a method for preparing activated carbon by taking camphor tree leaves as an initial raw material and phosphoric acid as an activating agent, but the specific surface area of the prepared activated carbon is 929-1424 m2The specific capacitance is also lower, and is 95-120F/g, and the most defect of the activated carbon prepared by the phosphoric acid activating agent is that the subsequent ash flying content is too high; by combining the methods, the reported preparation methods of various activated carbon materials have many defects, namely the utilization rate of the activating agent is low, the carbon materials fly more, the void structure of the activated carbon is difficult to adjust, the consistency of the specific surface area is poor, or the activating capacity of the activating agent activated by KOH strong base is too strong, so that the activating agent has great corrosion to equipment.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing supercapacitor active carbon by using organic acid esterified kudzuvine root starch, which comprises the steps of crushing, dipping and heat treatment, esterifying kudzuvine root and organic acid, carbonizing, and further adopting CO at high temperature2Physical activation produces activated carbon. Due to different types and different amounts of organic acids, esterificationThe substitution degree of the active carbon is different, and finally the active carbon with rich pore size distribution is formed after carbonization. The active carbon with rich pore diameters can increase the wettability, the affinity and the stability of a carbon material with electrolyte, can obviously change the specific surface area of the carbon material, and can obviously improve the specific surface area under the condition of not obviously changing the pore structure, thereby improving the electrochemical performance of the active carbon.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of activated carbon for a super capacitor is characterized by comprising the following steps:
step one, soaking with organic acid: cleaning a kudzu root raw material, crushing the kudzu root raw material by a crusher, mixing the crushed kudzu root raw material with a mixed solution of organic acid with a certain mass concentration, esterification catalyst urea and a cross-linking agent sodium trimetaphosphate, heating and stirring the mixed solution for a plurality of hours, and filtering the mixed solution to remove most of deionized water solvent;
step two, esterification: placing the kudzu root crude product after stirring and soaking with an organic acid reagent in a tubular furnace, introducing inert gas in a semi-dry state, and heating and esterifying at the esterification temperature of below 150 ℃ for 1-5 hours;
step three, carbonization: heating the esterified pasty radix Puerariae starch crude product to above 150 deg.C, carbonizing at a heating rate of 5 deg.C/min,
the carbonization temperature is 150-220 ℃;
fourthly, activation: placing the carbonized organic acid esterified radix Puerariae precursor in a high temperature box furnace, introducing CO2And heating the gas to 500-1000 ℃, wherein the heating rate is 10 ℃/min, and activating for hours to obtain the activated carbon with developed pore size distribution.
The radix Puerariae is wild radix Puerariae and planted radix Puerariae, including radix Puerariae and radix Puerariae.
The mass ratio concentration of the organic acid is 1-40%, preferably 5-20%.
The organic acid is a water-soluble aliphatic cluster organic acid R- (COOH) n (n is more than or equal to 1), R = (CH)2)n(n≥1)。
The organic acid is one or a mixture of citric acid, succinic acid, octenyl succinic acid, acrylic acid, maleic anhydride, isocyanic acid and tartaric acid.
The mass ratio concentration of the urea is 2-10%, preferably 2-4%.
The mass ratio concentration of the sodium trimetaphosphate is 0.05-0.5%, and preferably 0.1-0.2%.
The invention crushes cleaned kudzuvine root, then puts the crushed kudzuvine root into the mixed solution of organic acid, urea and sodium trimetaphosphate, stirs and mixes, after filtering, puts the semi-dry kudzuvine root crude product into a reactor, and finishes the organic acid esterification of kudzuvine root starch under heating. And carbonizing, crushing, acid washing and filtering the obtained esterified coarse material to obtain an activated carbon precursor, and finally introducing an activating agent carbon dioxide into a high-temperature furnace for physical activation to obtain activated carbon with developed pore diameter and rich pore diameter distribution. In the application, organic acid is used as an esterification reagent of the early-stage esterification reaction, the esterification reaction is completed with the radix puerariae under the action of a urea esterification catalyst, and the catalyst is used for activating carbon in subsequent low-temperature carbonization and high-temperature activation.
The invention has the following advantages:
the method adopts the kudzu root as the initial raw material of the active carbon, so that the wild kudzu root in mountainous and hilly lands is fully utilized, and the cost is zero; the starch in the kudzuvine root is fully utilized by adopting an organic acid esterification method, the process operation is simple, and the economic cost is low; the organic acid reagent is used as an esterification reagent of starch and an acidic catalytic reagent for the next step of carbon activation, so that the carbon activation process is mild and easy to control; finally, the scheme uses CO2The physical gas activation method can obtain the activated carbon with developed aperture and rich specific surface area, so that the activation process is environment-friendly and pollution-free. The method for preparing the supercapacitor active carbon from the organic acid esterified radix puerariae is low in comprehensive use cost and high in added value, can be applied to industrial production and has advancement from both environmental protection and economic cost, and the method for preparing the supercapacitor active carbon from the organic acid esterified radix puerariae is not reported in any document and patent.
Drawings
FIG. 1 is a structural formula of kudzu starch succinate prepared in example 3;
FIG. 2 is a nitrogen adsorption curve of a kudzu-based activated carbon material prepared in example 1;
FIG. 3 is a pore size distribution diagram of a kudzu-based activated carbon material prepared in example 2;
FIG. 4 is a charge and discharge curve of the kudzu-based activated carbon material prepared in example 1;
figure 5 is a cyclic voltammogram of the pueraria lobata-based activated carbon material prepared in example 8.
Detailed Description
The present invention is further illustrated by the following examples, but the present invention is not limited to the following examples, which are conventional unless otherwise specified, and the materials are commercially available from the public unless otherwise specified.
The invention discloses a method for testing the performance of organic acid esterified active carbon of kudzuvine root, which comprises the following steps:
(1) specific surface area and pore volume measurement: the specific surface area is calculated by a BET formula according to the nitrogen adsorption isotherm determination of the activated carbon under the condition of liquid nitrogen by adopting a Beijing microscopic JW-BK200C type specific surface and pore size analyzer for testing.
(2) Measurement of specific capacitance and cycle life: the blue electrochemical workstation (LAND) was used for testing.
(3) XRD diffraction data determination: the test is carried out by adopting a Nippon crystal X-ray diffractometer (XRD-700).
A preparation method of active carbon of a kudzu root organic acid esterification super capacitor comprises the following steps:
step one, soaking with organic acid: cleaning the raw material of kudzu root, crushing the cleaned raw material by a crusher, mixing the crushed raw material with a mixed solution of organic acid, urea and sodium trimetaphosphate with a certain mass concentration, stirring and mixing, and filtering to obtain a semi-dry kudzu root crude product.
Step two, esterification: and (3) putting the kudzu root crude product soaked by the organic acid reagent into a tubular furnace, and heating and esterifying the kudzu root crude product in an inert atmosphere under a semi-dry state, wherein the esterification temperature is below 150 ℃, and the esterification time is 1-5 hours.
Step three, carbonization: and (3) carbonizing, namely heating the esterified pasty kudzu root starch crude product to more than 150 ℃ for carbonization, wherein the heating rate is 5 ℃/min, the carbonization temperature is 150-220 ℃, and further carbonizing to obtain an active carbon precursor.
The fourth step, CO2Physical activation: placing carbonized radix Puerariae esterified precursor in high temperature box furnace, introducing CO2And heating the gas to 500-1000 ℃, wherein the heating rate is 10 ℃/min, and activating for hours to obtain the activated carbon with developed pore size distribution.
The raw materials in the method are wild pueraria lobata, pueraria thomsonii or planting pueraria thomsonii.
Example 1
A method for preparing activated carbon for a supercapacitor by esterifying organic acid with radix puerariae comprises the steps of dissolving a cleaned and ground radix puerariae crude product into a mixed solution of citric acid, urea and sodium trimetaphosphate, wherein the mass concentration of the citric acid is 1-40%, and preferably 5-20%; the mass concentration of the urea is 2-10%, preferably 2-4%; the mass concentration of the sodium trimetaphosphate is 0.05% -0.5%, preferably 0.1% -0.2%, and the semi-dried acidolysis radix puerariae is obtained through filtration. And (3) putting the kudzuvine root into a tube furnace, and heating under inert gas to complete esterification and low-temperature carbonization in sequence. Washing the obtained carbonized material with deionized water, centrifugally separating, putting the activated carbon precursor in a high-temperature furnace, and introducing CO2The gas is physically activated. The activation temperature is 500-1000 ℃, and the activated carbon with rich pore size distribution and high specific surface area is obtained after activation for several hours.
The prepared kudzu root-based active carbon sample AC1: polyvinylidene fluoride: the carbon black is 85: 10: 5, mixing the mixture in N-methyl-2-pyrrolidone serving as a solvent, uniformly stirring the mixture, and then coating the mixture on foamed nickel. Then dried, tabletted and weighed. And (3) placing the electrode material in KOH electrolyte, and respectively carrying out constant current charging and discharging and cyclic voltammetry tests at normal temperature in a blue and ARBIN electrochemical workstation.
Example 2
A method for preparing active carbon for supercapacitor by esterifying radix Puerariae with organic acid comprises dissolving cleaned and pulverized radix Puerariae crude product in citric acid,In the mixed solution of urea and sodium trimetaphosphate, the mass concentration of succinic acid is 1-40%, preferably 5-20%; the mass concentration of the urea is 2-10%, preferably 2-4%; the mass concentration of the sodium trimetaphosphate is 0.05-0.5%, preferably 0.1-0.2%; filtering to obtain semi-dry acidolysis radix Puerariae. The kudzu root is placed in a tube furnace, and is heated under inert gas to complete esterification and low-temperature carbonization in sequence. Washing the obtained carbonized material with deionized water, centrifugally separating, putting the activated carbon precursor in a high-temperature furnace, and introducing CO2The gas is physically activated. The activation temperature is 500-1000 ℃, and the activated carbon with rich pore size distribution and high specific surface area is obtained after activation for several hours.
The prepared kudzu root-based active carbon sample AC2: polyvinylidene fluoride: the carbon black is 85: 10: 5, mixing the mixture in N-methyl-2-pyrrolidone serving as a solvent, uniformly stirring the mixture, and then coating the mixture on foamed nickel. Then dried, tableted and weighed. And (3) placing the electrode material in KOH electrolyte, and respectively carrying out constant current charging and discharging and cyclic voltammetry tests at normal temperature in a blue and ARBIN electrochemical workstation.
Example 3
A method for preparing activated carbon for a supercapacitor by esterifying organic acid with radix puerariae comprises the steps of dissolving a cleaned and ground radix puerariae crude product into a mixed solution of octenyl succinic acid, urea and sodium trimetaphosphate, wherein the mass concentration of the octenyl succinic acid is 1-40%, and preferably 5-20%; the mass concentration of the urea is 2-10%, preferably 2-4%; the mass concentration of the sodium trimetaphosphate is 0.05-0.5%, preferably 0.1-0.2%; filtering to obtain semi-dry acidolysis radix Puerariae. And (3) putting the kudzuvine root into a tube furnace, and heating under inert gas to complete esterification and low-temperature carbonization in sequence. Washing the obtained carbonized material with deionized water, centrifugally separating, putting the activated carbon precursor in a high-temperature furnace, and introducing CO2The gas is physically activated. The activation temperature is 500-1000 ℃, and the activated carbon with rich pore size distribution and high specific surface area is obtained after activation for several hours.
The prepared kudzu root-based active carbon sample AC3: polyvinylidene fluoride: the carbon black is 85: 10: 5 mixing in solvent N-methyl-2-pyrrolidone, stirring, and coatingOn foamed nickel. Then dried, tabletted and weighed. And (3) placing the electrode material in KOH electrolyte, and respectively carrying out constant current charging and discharging and cyclic voltammetry tests at normal temperature in a blue and ARBIN electrochemical workstation.
Example 4
A method for preparing activated carbon for a supercapacitor by esterifying organic acid with radix puerariae comprises the steps of dissolving a cleaned and ground radix puerariae crude product into a mixed solution of acrylic acid, urea and sodium trimetaphosphate, wherein the mass concentration of the acrylic acid is 1-40%, and preferably 5-20%; the mass concentration of the urea is 2-10%, preferably 2-4%; the mass concentration of the sodium trimetaphosphate is 0.05-0.5%, preferably 0.1-0.2%; filtering to obtain semi-dry acidolysis radix Puerariae. The kudzu root is placed in a tube furnace, and is heated under inert gas to complete esterification and low-temperature carbonization in sequence. Washing the obtained carbonized material with deionized water, centrifugally separating, putting the activated carbon precursor in a high-temperature furnace, and introducing CO2The gas is physically activated. The activation temperature is 500-1000 ℃, and the activated carbon with rich pore size distribution and high specific surface area is obtained after activation for several hours.
The prepared kudzu root-based active carbon sample AC4: polyvinylidene fluoride: the carbon black is 85: 10: 5, mixing the mixture in N-methyl-2-pyrrolidone serving as a solvent, uniformly stirring the mixture, and then coating the mixture on foamed nickel. Then dried, tabletted and weighed. And (3) placing the electrode material in KOH electrolyte, and respectively carrying out constant current charging and discharging and cyclic voltammetry tests at normal temperature in a blue and ARBIN electrochemical workstation.
Example 5
A method for preparing activated carbon for a supercapacitor by esterifying organic acid with radix puerariae comprises the steps of dissolving a cleaned and ground radix puerariae crude product into a mixed solution of maleic anhydride, urea and sodium trimetaphosphate, wherein the mass concentration of the maleic anhydride is 1-40%, and preferably 5-20%; the mass concentration of the urea is 2-10%, preferably 2-4%; the mass concentration of the sodium trimetaphosphate is 0.05-0.5%, preferably 0.1-0.2%; filtering to obtain semi-dry acidolysis radix Puerariae. The kudzu root is placed in a tube furnace, and is heated under inert gas to complete esterification and low-temperature carbonization in sequence. Washing the obtained carbonized material with deionized water, centrifuging, and separating to obtain active carbonPlacing the body in a high temperature furnace, introducing CO2The gas is physically activated. The activation temperature is 500-1000 ℃, and the activated carbon with rich pore size distribution and high specific surface area is obtained after activation for hours.
The prepared kudzu root-based active carbon sample AC5: polyvinylidene fluoride: the carbon black is 85: 10: 5, mixing the mixture in N-methyl-2-pyrrolidone serving as a solvent, uniformly stirring the mixture, and then coating the mixture on foamed nickel. Then dried, tabletted and weighed. And (3) placing the electrode material in KOH electrolyte, and respectively carrying out constant current charging and discharging and cyclic voltammetry tests at normal temperature in a blue and ARBIN electrochemical workstation.
Example 6
A method for preparing activated carbon for a supercapacitor by esterifying organic acid with radix puerariae comprises the steps of dissolving a cleaned and ground radix puerariae crude product into a mixed solution of isocyanic acid, urea and sodium trimetaphosphate, wherein the mass concentration of the isocyanic acid is 1-40%, and preferably 5-20%; the mass concentration of the urea is 2-10%, preferably 2-4%; the mass concentration of the sodium trimetaphosphate is 0.05-0.5%, preferably 0.1-0.2%; filtering to obtain semi-dry acidolysis radix Puerariae. The kudzu root is placed in a tube furnace, and is heated under inert gas to complete esterification and low-temperature carbonization in sequence. Washing the obtained carbonized material with deionized water, centrifugally separating, putting the activated carbon precursor in a high-temperature furnace, and introducing CO2The gas is physically activated. The activation temperature is 500-1000 ℃, and the activated carbon with rich pore size distribution and high specific surface area is obtained after activation for several hours.
The prepared kudzu root-based active carbon sample AC6: polyvinylidene fluoride: the carbon black is 85: 10: 5, mixing the mixture in N-methyl-2-pyrrolidone serving as a solvent, uniformly stirring the mixture, and then coating the mixture on foamed nickel. Then dried, tabletted and weighed. And (3) placing the electrode material in KOH electrolyte, and respectively carrying out constant current charging and discharging and cyclic voltammetry tests at normal temperature in a blue and ARBIN electrochemical workstation.
Example 7
A method for preparing active carbon for supercapacitor by esterifying radix Puerariae with organic acid comprises dissolving cleaned and pulverized radix Puerariae crude product in tartaric acid, urea and sodium trimetaphosphateIn the mixed solution, the mass concentration of the tartaric acid is 1-40%, preferably 5-20%; the mass concentration of the urea is 2-10%, preferably 2-4%; the mass concentration of the sodium trimetaphosphate is 0.05-0.5%, and preferably 0.1-0.2%; filtering to obtain semi-dry acidolysis radix Puerariae. And (3) putting the kudzuvine root into a tube furnace, and heating under inert gas to complete esterification and low-temperature carbonization in sequence. Washing the obtained carbonized material with deionized water, centrifugally separating, putting the activated carbon precursor in a high-temperature furnace, and introducing CO2The gas is physically activated. The activation temperature is 500-1000 ℃, and the activated carbon with rich pore size distribution and high specific surface area is obtained after activation for several hours.
The prepared kudzu root-based active carbon sample AC7: polyvinylidene fluoride: the carbon black is 85: 10: 5, mixing the mixture in N-methyl-2-pyrrolidone serving as a solvent, uniformly stirring the mixture, and then coating the mixture on foamed nickel. Then dried, tableted and weighed. And (3) placing the electrode material in KOH electrolyte, and respectively carrying out constant current charging and discharging and cyclic voltammetry tests on a blue light electrochemical workstation and an ARBIN electrochemical workstation at normal temperature.
Example 8
A method for preparing activated carbon for a supercapacitor by esterifying organic acid with radix puerariae comprises the steps of dissolving a cleaned and ground radix puerariae crude product into a mixed solution of acrylic acid, tartaric acid, urea and sodium trimetaphosphate, wherein the mass concentration of the mixed organic acid is 1-40%, and preferably 5-20%; the mass concentration of the urea is 2-10%, preferably 2-4%; the mass concentration of the sodium trimetaphosphate is 0.05-0.5%, preferably 0.1-0.2%; filtering to obtain semi-dry acidolysis radix Puerariae. The kudzu root is placed in a tube furnace, and is heated under inert gas to complete esterification and low-temperature carbonization in sequence. Washing the obtained carbonized material with deionized water, centrifugally separating, putting the activated carbon precursor in a high-temperature furnace, and introducing CO2The gas is physically activated. The activation temperature is 500-1000 ℃, and the activated carbon with rich pore size distribution and high specific surface area is obtained after activation for several hours.
The prepared kudzu root-based active carbon sample AC8: polyvinylidene fluoride: the carbon black is 85: 10: 5, mixing the mixture in N-methyl-2-pyrrolidone serving as a solvent, uniformly stirring the mixture, and then coating the mixture on foamed nickel. Then pass throughAfter drying, the tablets were pressed and weighed. And (3) placing the electrode material in KOH electrolyte, and respectively carrying out constant current charging and discharging and cyclic voltammetry tests at normal temperature in a blue and ARBIN electrochemical workstation.
Attached table: pore size analysis data of radix puerariae-based activated carbon material
The kind of organic acid and the amount of organic acid directly affect the esterification and crosslinking degree of radix Puerariae. Different dosage, different substitution degree and different crosslinking degree, and the pore volume and the pore diameter of the activated carbon prepared by activating the pueraria starch are different, such as different specific surface area and different pore diameter. In examples 3 and 4, succinic acid and acrylic acid are used as esterifying agents to esterify the pueraria starch, the reaction activity of the pueraria starch is slightly better than that of other organic acids, and therefore the specific surface area of the prepared activated carbon is larger. In addition, the physical and chemical properties of the activated carbon are also influenced by the activation temperature, the amount of the activating agent and the reaction time.
Claims (6)
1. A preparation method of activated carbon for a super capacitor is characterized by comprising the following steps:
step one, soaking in organic acid: cleaning and crushing the raw material of kudzu root, stirring and mixing the crushed raw material and a mixed solution of organic acid, urea and sodium trimetaphosphate, and filtering to obtain a kudzu root crude product;
step two, esterification: putting the kudzu root crude product into a tubular furnace, and heating and esterifying in an inert atmosphere, wherein the esterification temperature is below 150 ℃, and the esterification time is 1-5 hours;
step three, carbonization: heating the esterified pasty kudzu root starch crude product to more than 150 ℃ for carbonization, wherein the heating rate is 5 ℃/min, the carbonization temperature is 150-220 ℃, and an active carbon precursor is obtained after carbonization;
the fourth step, CO2Physical activation: placing the active carbon precursor obtained by carbonization in a high-temperature box type furnace, and introducing CO2And heating the gas to 500-1000 ℃, wherein the heating rate is 10 ℃/min, and activating to obtain the activated carbon with developed pore size distribution.
2. The preparation method of the activated carbon for the supercapacitor according to claim 1, characterized in that: the radix Puerariae is wild radix Puerariae and planted radix Puerariae.
3. The preparation method of the activated carbon for the super capacitor according to claim 1, characterized in that: the mass concentration of the organic acid is 1% -40%.
4. The preparation method of the activated carbon for the super capacitor according to claim 1, characterized in that: the organic acid is one or a mixture of citric acid, succinic acid, acrylic acid, maleic anhydride, isocyanic acid and tartaric acid.
5. The preparation method of the activated carbon for the super capacitor according to claim 1, characterized in that: the mass concentration of the urea is 2% -10%.
6. The preparation method of the activated carbon for the super capacitor according to claim 1, characterized in that: the mass concentration of the sodium trimetaphosphate is 0.05% -0.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910072871.7A CN109704331B (en) | 2019-01-25 | 2019-01-25 | Preparation method of activated carbon for super capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910072871.7A CN109704331B (en) | 2019-01-25 | 2019-01-25 | Preparation method of activated carbon for super capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109704331A CN109704331A (en) | 2019-05-03 |
| CN109704331B true CN109704331B (en) | 2022-05-17 |
Family
ID=66262934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910072871.7A Active CN109704331B (en) | 2019-01-25 | 2019-01-25 | Preparation method of activated carbon for super capacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109704331B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110817869A (en) * | 2019-12-04 | 2020-02-21 | 山东建筑大学 | Zinc phosphate-organic acid composite activator and method for preparing activated carbon by using same |
| CN116730339B (en) * | 2023-06-28 | 2024-01-23 | 广东健态实业有限公司 | Novel wood columnar activated carbon harmless preparation equipment and process thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0931101A (en) * | 1995-07-13 | 1997-02-04 | Agency Of Ind Science & Technol | Novel water-absorbing material made of starch lees and its production |
| CN103623776A (en) * | 2013-11-22 | 2014-03-12 | 重庆工商大学 | Method for preparing iron-based magnetic activated carbon by catalytic activation of radix puerariae waste residue with compound enzyme |
| CN105948036A (en) * | 2016-04-26 | 2016-09-21 | 湘潭大学 | Preparation method and application of porous active carbon material with radix puerariae-based interconnected hierarchical aperture structure |
| CN108423676A (en) * | 2018-05-12 | 2018-08-21 | 北京化工大学 | A method of it improving biomass material and prepares activated carbon yield |
| CN109231205A (en) * | 2018-09-18 | 2019-01-18 | 中国东方电气集团有限公司 | A kind of activated carbon for super capacitors and preparation method thereof that sulfosalt surfactant is modified |
-
2019
- 2019-01-25 CN CN201910072871.7A patent/CN109704331B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0931101A (en) * | 1995-07-13 | 1997-02-04 | Agency Of Ind Science & Technol | Novel water-absorbing material made of starch lees and its production |
| CN103623776A (en) * | 2013-11-22 | 2014-03-12 | 重庆工商大学 | Method for preparing iron-based magnetic activated carbon by catalytic activation of radix puerariae waste residue with compound enzyme |
| CN105948036A (en) * | 2016-04-26 | 2016-09-21 | 湘潭大学 | Preparation method and application of porous active carbon material with radix puerariae-based interconnected hierarchical aperture structure |
| CN108423676A (en) * | 2018-05-12 | 2018-08-21 | 北京化工大学 | A method of it improving biomass material and prepares activated carbon yield |
| CN109231205A (en) * | 2018-09-18 | 2019-01-18 | 中国东方电气集团有限公司 | A kind of activated carbon for super capacitors and preparation method thereof that sulfosalt surfactant is modified |
Non-Patent Citations (1)
| Title |
|---|
| "交联酯化木薯淀粉制备条件的研究";方桂红 等;《食品与机械》;20080531;第24卷(第3期);第34页摘要和前言部分和第34-35页第1.3.1节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109704331A (en) | 2019-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108117073B (en) | Method for preparing porous carbon material by using water hyacinth and application | |
| CN107039193B (en) | A kind of garlic skin matrix activated carbon electrode material and preparation method for ultracapacitor | |
| CN110835107B (en) | Biomass porous carbon material and preparation method thereof | |
| CN108557819B (en) | Method for preparing porous carbon material from garlic-based waste and application | |
| CN107403698A (en) | A kind of application that the method for activated carbon and its activated carbon of preparation are prepared using biomass | |
| CN109081340B (en) | Pine-based biomass activated carbon, preparation method thereof and application thereof in electrochemical energy storage | |
| CN107644742A (en) | A kind of method that biogas residue activated carbon prepares ultracapacitor after dry fermentation based on biomass anaerobic | |
| CN108101051A (en) | A kind of preparation method of ultracapacitor seaweed matrix activated carbon presoma | |
| CN107601502A (en) | The preparation and the application in terms of capacitive property of a kind of nitrogen phosphorus doping porous charcoal | |
| CN106629723A (en) | Biomass-based N, S and P-containing co-doped porous carbon and application thereof | |
| CN109704331B (en) | Preparation method of activated carbon for super capacitor | |
| CN113299484B (en) | Preparation method of CCO/CoNiMn-LDH composite material and application of CCO/CoNiMn-LDH composite material in super capacitor | |
| CN109019598A (en) | A kind of mixing biomass prepares the method and manufactured three-dimensional porous carbon material and its application of the three-dimensional porous carbon material of high specific capacitance | |
| CN110697714A (en) | Radish-derived nitrogen-doped graded porous carbon and preparation method and application thereof | |
| CN108439402A (en) | A kind of ultracapacitor ginger stalk matrix activated carbon and preparation method thereof | |
| CN109939620A (en) | A kind of N doping porous cellulose based charcoal aerogel and its preparation method and application | |
| CN102683661A (en) | Method for preparing hard carbon negative electrode materials of lithium ion battery | |
| CN105236406A (en) | Supercapacitor spherical active carbon preparation method | |
| CN103964433A (en) | Preparation method of coal-based activated carbon for electrode material of supercapacitor | |
| CN113060730A (en) | Preparation method of activated carbon for supercapacitor, activated carbon and application thereof | |
| CN112624111B (en) | Preparation method of metal-catalyzed corn straw derived carbon electrode material | |
| CN111960414B (en) | Wood biomass-based porous carbon material prepared from inorganic molten salt hydrate, and preparation method and application thereof | |
| CN111968863B (en) | Preparation method of rare earth composite biomass-based capacitance carbon material | |
| CN113184848A (en) | Method for preparing biomass porous carbon for supercapacitor based on shaddock peel | |
| CN107311171A (en) | The preparation method and activated carbon of activated carbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |