CN110723736A - Biomass porous activated carbon material and preparation method and application thereof - Google Patents
Biomass porous activated carbon material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 239000000463 material Substances 0.000 title claims abstract description 67
- 239000002028 Biomass Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000003990 capacitor Substances 0.000 claims abstract description 7
- 235000020238 sunflower seed Nutrition 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 23
- 230000003213 activating effect Effects 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 230000004913 activation Effects 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000012190 activator Substances 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000010000 carbonizing Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 5
- 229920005610 lignin Polymers 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 18
- 239000012535 impurity Substances 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000011232 storage material Substances 0.000 abstract description 3
- 230000019635 sulfation Effects 0.000 abstract description 3
- 238000005670 sulfation reaction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001816 cooling Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000003513 alkali Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
- Y02E60/10—Energy storage using batteries
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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
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention relates to the technical field of energy storage materials, and provides a biomass porous activated carbon material, a preparation method and application thereof, aiming at solving the problems of high impurity content and uncontrollable pore structure of the traditional biomass activated carbon material. The biomass porous activated carbon material has large specific surface area and adjustable pore size, meets the requirements of a super capacitor and a lead-carbon battery, and can remarkably improve the sulfation of a negative electrode and prolong the cycle life of the battery when being used as a negative electrode additive of the lead-carbon battery; the preparation method has the advantages of easily available raw materials, abundant sources, low cost, simple steps and convenience for industrial production.
Description
Technical Field
The invention relates to the technical field of energy storage materials, in particular to a biomass porous activated carbon material and a preparation method and application thereof.
Background
The activated carbon is classified into biomass activated carbon, coal-based activated carbon, petroleum-based activated carbon and the like according to the difference of raw materials, and is applied to various fields of national economy due to the characteristics of large specific surface area, developed pores, low price and the like. The activated carbon is mainly activated by chemical activation or physical activation. The chemical activation method is to mix various carbon sources and medicines uniformly and then to perform the processes of carbonization, activation, rinsing, drying and the like at a certain temperature. The general activating medicines are strong alkali or sulfuric acid, phosphoric acid and the like, the energy consumption is low, but the pollution of chemical agents is serious, and the process takes a long time. The physical activation method is a process of mixing carbonized raw materials with steam, nitrogen, carbon dioxide and the like at high temperature and then carrying out activation reaction, and has the advantages of relatively simple process, high specific surface area of products, developed pore structure, long process time, high energy consumption and certain component pollution.
The application of the active carbon as an energy storage material has good application prospect, and is mainly applied to double electric layer capacitors and lead carbon batteries. The activated carbon is added into the negative electrode of the lead-carbon battery, so that the salinization of the sodium sulfate of the negative electrode is mainly inhibited, the cycle life of the battery is prolonged, the performance requirement on the activated carbon is high, the specific surface area is high, the pore volume and the pore diameter structure can be regulated, and the impurity content is in a specified range. The biomass-based activated carbon has rich sources, low cost and simple and controllable preparation process, and has good research and application values.
At present, the bio-based activated carbon is widely applied to lead carbon batteries and is based on rice hulls and coconut shells, and the specific surface area of the bio-based activated carbon can reach 2000m2The Chinese patent literature discloses a preparation method of biomass-based activated carbon, and the application publication number is CN109179410A, the specific surface area of the rice hull-based activated carbon prepared by the invention is up to 2094.15m2And the surface of the activated carbon has rich pore-size structures. The rice hull-based activated carbon is used for adsorbing and removing benzene series substances, and the removal rate is as high as 80.2%. However, the biomass-based activated carbon prepared by the method has the defects of more impurities, uncontrollable pore structure, relatively complex preparation process and higher production cost.
Disclosure of Invention
The invention provides a biomass porous activated carbon material with low impurity content and directionally controllable pore structure, aiming at overcoming the problems of high impurity content and uncontrollable pore structure of the traditional biomass activated carbon material.
The invention also provides a preparation method of the biomass porous activated carbon material, and the method has the advantages of easily available raw materials, abundant sources, low cost, simple process steps and convenience for industrial production.
The invention also provides application of the biomass activated carbon material in lead carbon batteries and super capacitors.
In order to achieve the purpose, the invention adopts the following technical scheme:
a biomass porous activated carbon material is prepared by taking sunflower seed shells as a raw material, cleaning, drying, carbonizing, crushing, activating, cleaning and drying.
The biomass porous activated carbon material adopts sunflower seed shells as a carbon source, the sunflower seed shells are difficult to be economically utilized, the raw material source is rich, the cost is low, and compared with coal-based and petroleum-based activated carbon, the biomass porous activated carbon material has low impurity content and low cost.
A preparation method of a biomass porous activated carbon material comprises the following steps:
(1) cleaning sunflower seed shells in deionized water, and drying; the drying temperature is 30-80 ℃, and the drying time is 10-48 h;
(2) carbonizing the sunflower seed shells treated in the step (1);
(3) grinding the sunflower seed shells treated in the step (2) to obtain sunflower seed shell powder;
(4) adding an activating agent into the sunflower seed shell powder, carrying out activating treatment in inert gas, and then washing and drying by deionized water to obtain the biomass porous activated carbon material. Before drying, the activated carbon needs to be washed and filtered to be neutral.
Preferably, in the step (2), the carbonization treatment temperature is 200-500 ℃, and the carbonization treatment time is 1-4 h. The capacitance of the subsequent material can be affected by the carbonization temperature, and the capacitance value is too small due to too low carbonization temperature.
Preferably, in the step (3), the particle size of the sunflower seed hull powder is 40-60 meshes.
Preferably, in step (4), the activator is a basic activator or an acidic activator; the temperature of the activation treatment is 600-1300 ℃, and the activation time is 0.5-2 h. The different activation temperatures can generate activated carbon materials with different specific surface areas, and the higher the activation temperature is, the larger the specific surface area is.
Preferably, the addition amount of the alkaline activator is 1: (1-20); the alkaline activator is selected from one or more of potassium hydroxide, sodium hydroxide, ammonia water, potassium carbonate and sodium carbonate. The alkali-carbon mass ratio refers to the mass ratio of the alkaline activator to the sunflower seed hull powder.
Preferably, the acidic activator is selected from one or more of sulfuric acid, phosphoric acid, polyphosphoric acid and boric acid; the concentration of the acidic activator is 2-50 wt%.
Preferably, in the step (4), the inert gas is one selected from nitrogen, argon and helium.
Preferably, in the step (4), before the activation treatment, deionized water is added for soaking treatment; when the activating agent is an alkaline activating agent, the soaking time is 0.5-4 h; when the activating agent is an acidic activating agent, the soaking time is 1-12 h.
Before the activation treatment, the soaking effect enables the activating agent and the carbonized material to be fully mixed together, and the soaking time can influence the pore volume and the pore diameter of the subsequent material. The long soaking time may result in a large pore size.
Preferably, in the step (4), the temperature rise rate of the activation treatment is controlled to be 3 to 5 ℃/min, preferably 4 ℃/min. The temperature rise rate determines the pore structure of the final product, and the ordered pore structure is favorably formed in the temperature rise rate range, so that the directional regulation and control of the pore structure of the product are realized.
An application of a biomass porous activated carbon material in a lead carbon battery and a super capacitor.
The invention takes sunflower seed shells as raw materials, the specific surface area and the pore diameter of the prepared biomass porous activated carbon material are adjustable, and the requirements of a super capacitor and a lead-carbon battery can be met.
Preferably, the biomass porous activated carbon material is prepared into a lead-carbon battery by performing paste, plate coating and solidification according to the following formula: 1000 parts of lead powder, 1.1 parts of short fibers, 1.5-6 parts of carbon black, 2-60 parts of activated carbon, 5-30 parts of barium sulfate, 1-10 parts of lignin, 55-60 parts of sulfuric acid and 140-160 parts of pure water.
The biomass porous activated carbon material is used as a lead-carbon battery cathode additive, and can remarkably improve cathode sulfation and prolong the cycle life of the battery according to the formula proportion.
Therefore, the invention has the following beneficial effects:
(1) the carbon source adopted is sunflower seed shells which are difficult to be economically utilized, the raw material source is rich, the cost is low, and the impurity content is low;
(2) the biomass porous activated carbon material has large specific surface area and adjustable pore size, meets the requirements of a super capacitor and a lead-carbon battery, and can remarkably improve the sulfation of a negative electrode and prolong the cycle life of the battery when being used as a negative electrode additive of the lead-carbon battery;
(3) the preparation method has the advantages of easily available raw materials, abundant sources, low cost, simple steps and convenience for industrial production.
Drawings
FIG. 1 is an SEM image of a biomass porous activated carbon material prepared in example 1.
FIG. 2 is an SEM image of a biomass porous activated carbon material prepared in example 2.
FIG. 3 is XRD spectra of biomass porous activated carbon materials prepared in example 1(a) and example 2 (b).
Fig. 4 is a CV curve of the lead-carbon battery prepared in example 1 at a scan rate of 10 mv/s.
Fig. 5 is a battery cycle life curve of lead carbon batteries manufactured in example 1(a) and comparative example 5 (b).
Fig. 6 is an isothermal adsorption and desorption curve of the biomass porous activated carbon material prepared in example 1.
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
(1) Washing sunflower seed shell with deionized water for 3 times, filtering, and drying at 40 deg.C for 12 hr;
(2) putting the dried sample in a high-temperature furnace, carbonizing for 2h at 300 ℃, and taking out after cooling;
(3) grinding a sample to obtain sunflower seed shell powder with the granularity of 50 meshes;
(4) weighing 20g of sunflower seed shell powder, and mixing the following raw materials according to carbon: the mass ratio of alkali is 1: adding 60g of potassium hydroxide, adding 500g of deionized water, soaking for 2h, placing in a high-temperature furnace in a nitrogen atmosphere, heating to 950 ℃ at a heating rate of 4 ℃/min, preserving heat for 1h, naturally cooling to room temperature, washing for 2 times by using deionized water, and placing in a drying oven for drying at 4 ℃ for 12h to obtain the biomass porous activated carbon material, wherein an SEM picture of the biomass porous activated carbon material is shown in figure 1, and the prepared biomass porous activated carbon material is in an irregular blocky structure; the XRD spectrum of the material is shown as a curve a in figure 3, and the prepared material is an activated carbon material.
The biomass porous activated carbon material prepared in the example 1 is used in a negative electrode formula of a lead-carbon battery, and the preparation of an experimental battery is carried out by performing paste, plate coating and solidification according to the following formula, wherein 1000g of lead powder, 1.1g of short fiber, 1.5g of carbon black, 20g of activated carbon, 5g of barium sulfate, 3g of lignin, 55 g of sulfuric acid and 140g of pure water; the amount of the used paste acid was 1.4 g/ml.
Fig. 4 is a CV curve of the lead-carbon battery prepared in this example at a scan rate of 10mv/s, which is a result of a test in a three-electrode system, and it can be seen that the electrode material has excellent capacitance characteristics.
Fig. 5, curve a, is the battery cycle life curve of the lead-carbon battery prepared in this example, and fig. 5, curve b, is the battery cycle life curve of the comparative example 5, which is prepared by the existing production formulation without adding the biomass porous activated carbon material prepared by the present invention, it can be seen from the graph that the charging voltage of the lead-carbon battery is less than that of the comparative example 5, which shows that the charging acceptance of the lead-carbon battery is good, and from the discharge voltage, after dozens of cycles, the discharge voltage of the common battery is less than 1.75V, which is out of service, while the discharge voltage curve of the lead-carbon battery with the biomass porous activated carbon material prepared by the present invention is relatively stable and is maintained above 1.9V. The battery cycling test was performed at 30% -80% DOD (after the battery was fully charged, the first step was to discharge 20% and the second 50% and the third step was to repeat the second step again and again with the same amount of charge charged according to the amount of charge discharged in the second step.)
As can be seen from the isothermal adsorption and desorption curves of fig. 6: the adsorption curve of the prepared activated carbon is in I type at the beginning; the gas adsorption quantity is not obviously increased at the low-pressure end, which indicates that micropores exist a little. The gas adsorption capacity in the middle-high pressure section is increased sharply, and an obvious desorption hysteresis loop appears, which indicates that the activated carbon has a large amount of 80% mesopores (2-50 nm) and micropores and macropores account for 20%. The specific surface area of the activated carbon thus calculated was 1222m2/g。
Example 2
Example 2 differs from example 1 in that potassium hydroxide is added in an amount of carbon: the mass ratio of alkali is 1: 4, the activation temperature is 900 ℃, the heat preservation time is 0.5h, and the rest processes are completely the same. An SEM image of the biomass porous activated carbon material prepared in the embodiment is shown in FIG. 2, and it can be seen that the prepared biomass porous activated carbon material is in an irregular blocky structure; the XRD spectrogram is shown as a curve b in figure 3, and the prepared material is an activated carbon material;
the biomass porous activated carbon material prepared in the example 2 is used in a lead-carbon battery cathode formula, and an experimental battery is prepared by performing paste, plate coating and solidification according to the following formula: 1000g of lead powder, 1.1g of short fibers, 2g of carbon black, 15g of active carbon, 65g of barium sulfate, 4g of lignin, 55 g of sulfuric acid and 150g of pure water; the adopted paste acid is 1.4 g/ml;
the obtained activated carbon sample is used in a lead-carbon battery cathode formula and the performance of the activated carbon sample is tested, and the specific surface area of the activated carbon material is 852m2And/g, the cycle life of the prepared lead-carbon battery under 30-80% DOD can reach 1020 times (failure is determined when the number of times is continuously less than 3 times).
Example 3
Example 3 differs from example 1 in that the activator in step (4) is an acidic activator: weighing 30g of sunflower seed shell powder, soaking the sunflower seed shell powder in 30% phosphoric acid by mass for 3h, then placing the sunflower seed shell powder in a high-temperature furnace in nitrogen atmosphere, heating to 950 ℃ at a speed of 4 ℃/min, preserving heat for 1h, naturally cooling to room temperature, then cleaning for 2 times by using deionized water, and then placing the sunflower seed shell powder in a drying oven for drying for 12h at a temperature of 4 ℃ to obtain the biomass porous activated carbon material. The specific surface area was determined to be 1324m2/g。
Example 4
(1) Washing sunflower seed shell with deionized water for 3 times, filtering, and drying at 30 deg.C for 48 hr;
(2) putting the dried sample in a high-temperature furnace, carbonizing for 1h at 500 ℃, and taking out after cooling;
(3) grinding a sample to obtain sunflower seed shell powder with the granularity of 60 meshes;
(4) weighing 20g of sunflower seed shell powder, and mixing the following raw materials according to carbon: the mass ratio of alkali is 1: 20, adding 200g of potassium carbonate and 200g of sodium hydroxide, then adding 500g of deionized water, soaking for 4h, then placing in a high-temperature furnace in an argon atmosphere, heating to 1300 ℃ at a heating rate of 3 ℃/min, preserving heat for 0.5h, naturally cooling to room temperature, then cleaning for 2 times by using deionized water, and then placing in a drying oven for drying for 10h at 5 ℃ to obtain the biomass porous activated carbon material. The specific surface area was determined to be 1430m2/g。
Example 5
(1) Washing sunflower seed shell with deionized water for 3 times, filtering, and drying at 80 deg.C for 10 hr;
(2) putting the dried sample in a high-temperature furnace, carbonizing for 4h at 200 ℃, and taking out after cooling;
(3) grinding a sample to obtain sunflower seed shell powder with the granularity of 40 meshes;
(4) weighing 20g of sunflower seed shell powder, and mixing the following raw materials according to carbon: the mass ratio of alkali is 1: 1, adding 20g of sodium carbonate, adding 500g of deionized water, soaking for 0.5h, placing in a high-temperature furnace in a nitrogen atmosphere, heating to 600 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, naturally cooling to room temperature, cleaning for 2 times by using deionized water, and placing in a drying oven for drying at 4 ℃ for 12h to obtain the biomass porous activated carbon material. The specific surface area was measured to be 530m2/g。
Comparative example 1
Comparative example 1 is different from example 1 in that the temperature increase rate of the activation treatment in step (4) is 8 ℃/min, and the rest of the processes are completely the same. The mesopore proportion of the obtained biomass porous activated carbon material is only 40 percent, and the rest 60 percent is micropores or macropores.
Comparative example 2
The comparative example 2 is different from the example 1 in that the carbonization temperature is 180 ℃ in the step (2), and the rest of the process is completely the same. The prepared activated carbon has a capacitance value of 20F/g, and the capacitance value is reduced due to low temperature.
Comparative example 3 (without addition of Biomass porous activated carbon Material)
Carrying out paste, plate coating and curing according to the following formula to prepare an experimental battery, wherein 1000g of lead powder, 1.1g of short fiber, 1.5g of carbon black, 5g of barium sulfate, 3g of lignin, 55 g of sulfuric acid and 140g of pure water; the amount of the used paste acid was 1.4 g/ml.
The biomass porous activated carbon materials of examples 1-5 were used in the lead carbon battery negative electrode formulations and tested for performance, and the cycle life of the lead carbon batteries prepared in example 3 was tested at 30% -80% DOD and reported in Table 1.
The performance of the biomass porous activated carbon materials and the experimental batteries prepared in the examples 1 to 5 and the comparative examples 1 to 3 was tested, and the results are shown in table 1:
TABLE 1 test results
As can be seen from Table 1, the cycle life of the batteries of comparative examples 1 to 5 and comparative example 3 is 10 to 20 times that of the battery after adding the biomass porous activated carbon material prepared by the invention; the battery without the biomass porous activated carbon material prepared by the method has cycle life of only dozens of times under the condition of 30-80% DOD, and the cycle performance of the battery is poor. Comparing examples 1-5 with comparative example 2, it can be seen that the capacitance value of the biomass porous activated carbon material is greatly influenced by the carbonization temperature, and the capacitance value is too small due to the too low carbonization temperature (lower than 200 ℃); comparing examples 1-5 with comparative example 1, it can be seen that the temperature increase rate of the activation treatment determines the pore structure of the final product, and when the temperature increase rate is out of the range of the present invention, the mesopore ratio in the obtained biomass porous activated carbon material is obviously reduced (less than 50%).
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. The biomass porous activated carbon material is characterized in that the biomass porous activated carbon material is prepared by taking sunflower seed shells as a raw material, cleaning, drying, carbonizing, crushing, activating, cleaning and drying.
2. The preparation method of the biomass porous activated carbon material as claimed in claim 1, characterized by comprising the following steps:
(1) cleaning sunflower seed shells in deionized water, and drying;
(2) carbonizing the sunflower seed shells treated in the step (1);
(3) grinding the sunflower seed shells treated in the step (2) to obtain sunflower seed shell powder;
(4) adding an activating agent into the sunflower seed shell powder, carrying out activating treatment in inert gas, and then washing and drying by deionized water to obtain the biomass porous activated carbon material.
3. The preparation method of the biomass porous activated carbon material according to claim 2, wherein in the step (2), the carbonization treatment temperature is 200-500 ℃, and the carbonization treatment time is 1-4 h.
4. The preparation method of the biomass porous activated carbon material as claimed in claim 2, wherein in the step (3), the particle size of the sunflower seed hull powder is 40-60 meshes.
5. The method for preparing the biomass porous activated carbon material according to claim 2, wherein in the step (4), the activating agent is an alkaline activating agent or an acidic activating agent; the temperature of the activation treatment is 600-1300 ℃, and the activation time is 0.5-2 h; the temperature rise rate of the activation treatment is controlled to be 3-5 ℃/min.
6. The preparation method of the biomass porous activated carbon material according to claim 5, wherein the addition amount of the alkaline activator is 1: (1-20); the alkaline activator is selected from one or more of potassium hydroxide, sodium hydroxide, ammonia water, potassium carbonate and sodium carbonate.
7. The preparation method of the biomass porous activated carbon material as claimed in claim 5, wherein the acidic activator is one or more selected from sulfuric acid, phosphoric acid, polyphosphoric acid and boric acid; the concentration of the acidic activator is 2-50 wt%.
8. The method for preparing the biomass porous activated carbon material according to claim 2, wherein in the step (4), the inert gas is selected from one of nitrogen, argon and helium.
9. The preparation method of the biomass porous activated carbon material according to claim 2, wherein in the step (4), deionized water is added for soaking treatment before activating treatment is carried out by adding an activating agent; when the activating agent is an alkaline activating agent, the soaking time is 0.5-4 h; when the activating agent is an acidic activating agent, the soaking time is 1-12 h.
10. The application of the biomass porous activated carbon material in the lead-carbon battery and the super capacitor as claimed in claim 1, wherein the biomass porous activated carbon material is prepared into the lead-carbon battery by the following formula through pasting, coating and curing: 1000 parts of lead powder, 1.1 parts of short fibers, 1.5-6 parts of carbon black, 2-60 parts of activated carbon, 5-30 parts of barium sulfate, 1-10 parts of lignin, 55-60 parts of sulfuric acid and 140-160 parts of pure water.
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