CN108023086A - The method that carbon dioxide catalysis prepares iron-based polyanion-high porosity biomass carbon composite material with multidimensional hierarchy - Google Patents
The method that carbon dioxide catalysis prepares iron-based polyanion-high porosity biomass carbon composite material with multidimensional hierarchy Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 124
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 98
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 74
- 239000002028 Biomass Substances 0.000 title claims abstract description 62
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 49
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 22
- 229920000447 polyanionic polymer Polymers 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001994 activation Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 239000007800 oxidant agent Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 241000512259 Ascophyllum nodosum Species 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 230000003252 repetitive effect Effects 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 238000010306 acid treatment Methods 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 2
- 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 2
- 241000219146 Gossypium Species 0.000 claims description 2
- 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 2
- 238000004140 cleaning Methods 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims 1
- 229910052493 LiFePO4 Inorganic materials 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000002304 perfume Substances 0.000 claims 1
- 235000013599 spices Nutrition 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000010970 precious metal Substances 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 235000015165 citric acid Nutrition 0.000 description 11
- 241001474374 Blennius Species 0.000 description 8
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical class [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 description 5
- 150000002823 nitrates Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical class [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical class [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000011091 sodium acetates Nutrition 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
-
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The method that carbon dioxide catalysis prepares the iron-based polyanion high porosity biomass carbon composite material with multidimensional hierarchy.The present invention relates to field of electrochemical energy storage materials, particularly a kind of method of iron-based polyanion high porosity biomass carbon composite material.The present invention is energy crisis caused by order to solve existing Precious Metals Resources scarcity, and biomass is discarded the problem of cannot efficiently using.Using carbon dioxide as the high hole biomass carbon of catalyst preparation, and using it as iron-based polyanion composite material of the matrix Fast back-projection algorithm with multidimensional hierarchy.
Description
Technical field
The present invention relates to field of electrochemical energy storage materials, particularly a kind of iron-based polyanion-high porosity biomass carbon
The method of composite material.
Background technology
The sustainable development of energy and environment is one of matter of utmost importance that the current world is faced.With mobile communication, electricity
The fast development of motor-car, aerospace, renewable energy utilization (such as solar energy and wind energy) field, stores up high performance energy
Deposit and rapidly increase with the demand of conversion equipment, greatly promoted the research and development in the field.The hair of high performance electrode material
Exhibition is to restrict the principal element that energy storage device (such as battery, capacitor) performance improves.Exploitation design is inexpensive, safety, environment friend
The good, electrochemical material higher than energy, is the key for promoting energy storage device development, and the emphasis studied at present.Existing
In electrode material, polyanionic compound is a kind of important positive electrode.It is with polyanion group (XOn) it is core knot
Structure, has a stable three-dimensional frame structure, good stability and security, be electrochemical energy storage field primary study object it
One.In polyanionic material, iron-based polyanionic material has cheap advantage, becomes current research hotspot.But
It is that relatively low electron conduction have impact on the performance of iron-based polyanionic material.Although traditional carbon doping method of modifying can be with
The electric conductivity of raising material, but common chemical synthesis carbon source (such as graphene (Graphene), carbon nanotubes (CNT), activity
Charcoal (AC)) etc., it is necessary to largely have the strong oxidizer (such as concentrated sulfuric acid, potassium permanganate) of pollution and chemical reagent just can be with to environment
Synthesis.Therefore, it is imperative that green, environmentally friendly, low cost new synthesis mode and method of modifying are found.Biomass is by abundant
Carboxyl, hydroxyl isopolarity group are formed, it is internal with substantial amounts of ventilation (water) duct, can pass through appropriate treatment technology
Prepare loose structure carbon source.Waste resource not only is reused moreover, preparing porous carbon as matrix using abandoned biomass, is also had
Beneficial to the protection of environment.But current treatment technology can not make full use of the structure of biomass, prepared biomass carbon
Porosity is low, the performance of composite material is affected.It is then desired to research and develop more effective preparation method, the profit of biology is improved
With efficiency, improve the structure of biomass carbon, so as to improve the performance of composite material.
The content of the invention
The present invention is energy crisis caused by order to solve existing Precious Metals Resources scarcity, and biomass is discarded cannot be effective
The problem of utilization, and provide carbon dioxide catalysis and prepare the iron-based polyanion with multidimensional hierarchy-high porosity life
The method of material carbon composite.
Carbon dioxide catalysis prepares iron-based polyanion-high porosity biomass carbon composite wood with multidimensional hierarchy
What the method for material specifically carried out according to the following steps：
First, biomass is subjected to removing surface, acid treatment and activation process successively, adopts and be washed with distilled water to neutrality,
Temperature is dried under conditions of being 60 DEG C~80 DEG C, product after being activated；
2nd, product after activation is placed in vacuum airtight container, carbon dioxide gas is then filled with into vacuum airtight container
Body, vacuumizes, and is filled with carbon dioxide again, and repetitive operation three times, then preserves 24h under carbon dioxide atmosphere, obtains
Material after processing；
3rd, processed material is subjected to carbonization treatment under inert gas shielding, obtains high hole biomass carbon；
4th, the chemical formula according to iron-based material to be composite, in various elements ratio weigh it is corresponding prepare material, and weigh
The Oxidizing and Reducing Agents of respective amount；By weigh prepare material, Oxidizing and Reducing Agents is dissolved in water, add step 3 obtain
High hole biomass carbon, temperature be 80~100 DEG C under conditions of be evaporated, obtain precursor powder；The iron-based to be composite
The molar ratio of ferro element and oxidant is 1 in material:(0.5~2)；The molar ratio of the Oxidizing and Reducing Agents is 1:1；
5th, precursor powder is put into high temperature furnace and calcines 3min~5min under conditions of temperature is 600~800 DEG C,
Obtain the iron-based polyanion-high porosity biomass carbon composite material with multidimensional hierarchy.
Iron-based polyanion with multidimensional hierarchy prepared by the present invention-high porosity biomass carbon composite material is used
In energy storage field, such as electrochmical power source (including lithium ion battery, sodium-ion battery), ultracapacitor.
Beneficial effects of the present invention：
The present invention is using carbon dioxide as the high hole biomass carbon of catalyst preparation, and using it as matrix Fast back-projection algorithm (3
Minute in) have multidimensional hierarchy iron-based polyanion composite material method.Your gold is this method both can effectively alleviate
Belong to the energy crisis caused by scarcity of resources, and abandoned biomass can be made to be utilized effectively, solve existing high-performance material
Expect developing major issue, be conducive to the protection of environment and the sustainable development of resource.It is made by catalyst of carbon dioxide
Product of the standby biomass carbon prepared by than no catalyst, its porosity improve more than 30%.The height prepared in this way
The iron base composite material that porosity biomass carbon is made of matrix, its heavy-current discharge performance significantly improve.In 30 hour rates
Its lower discharge capacity improves more than 40% than contrast sample (i.e. the iron-based material of inanimate object matter carbon base body), realizes the material
The 72% of theoretical capacity.
Brief description of the drawings
Fig. 1 is that iron-based polyanion-high porosity biomass carbon with multidimensional hierarchy that embodiment one obtains is answered
The scanning electron microscope (SEM) photograph of condensation material；
Fig. 2 is the scanning electron microscope (SEM) photograph of the iron-based polyanionic material of inanimate object carbon base body；
Fig. 3 is that iron-based polyanion-high porosity biomass carbon with multidimensional hierarchy that embodiment one obtains is answered
The charging and discharging curve of condensation material；
Fig. 4 is the charging and discharging curve of the iron-based polyanionic material of inanimate object carbon base body；
Fig. 5 is that iron-based polyanion-high porosity biomass carbon with multidimensional hierarchy that example IV obtains is answered
The transmission electron microscope picture of condensation material；
Fig. 6 is that iron-based polyanion-high porosity biomass carbon with multidimensional hierarchy that example IV obtains is answered
The cycle performance curve of condensation material.
Embodiment
Embodiment one：The carbon dioxide catalysis of present embodiment prepares the iron-based with multidimensional hierarchy and gathers the moon
What the method for ion-high porosity biomass carbon composite material specifically carried out according to the following steps：
First, after biomass being carried out removing surface, acid treatment and activation process successively, in the bar that temperature is 60 DEG C~80 DEG C
It is dried under part, product after being activated；
2nd, product after activation is placed in vacuum airtight container, carbon dioxide gas is then filled with into vacuum airtight container
Body, vacuumizes, and is filled with carbon dioxide again, and repetitive operation three times, then preserves 24h under carbon dioxide atmosphere, obtains
Material after processing；
3rd, processed material is subjected to carbonization treatment under inert gas shielding, obtains high hole biomass carbon；
4th, the chemical formula according to iron-based material to be composite, in various elements ratio weigh it is corresponding prepare material, and weigh
The Oxidizing and Reducing Agents of respective amount；By weigh prepare material, Oxidizing and Reducing Agents is dissolved in water, add step 3 obtain
High hole biomass carbon, temperature be 80~100 DEG C under conditions of be evaporated, obtain precursor powder；The iron-based to be composite
The molar ratio of ferro element and oxidant is 1 in material:(0.5~2)；The molar ratio of the Oxidizing and Reducing Agents is 1:1；
5th, precursor powder is put into high temperature furnace and calcines 3min~5min under conditions of temperature is 600~800 DEG C,
Obtain the iron-based polyanion-high porosity biomass carbon composite material with multidimensional hierarchy.
Embodiment two：The present embodiment is different from the first embodiment in that：Biomass described in step 1
For kelp, cotton, rice shell or banana skin.Other steps and parameter are identical with embodiment one.
Embodiment three：The present embodiment is different from the first and the second embodiment in that：Table described in step 1
Face cleaning be biomass is put into clean 5~10 times in clear water after immersion 24h~48h.Other steps and parameter and specific implementation
Mode one or two is identical.
Embodiment four：Unlike one of present embodiment and embodiment one to three：Institute in step 1
It is that the hydrochloric acid for using concentration as 0.5mol/L cleans the biomass after surface clean to state acid treatment, and using distillation washing
Wash to neutrality.Other steps and parameter are identical with one of embodiment one to three.
Embodiment five：Unlike one of present embodiment and embodiment one to four：Institute in step 1
State activation process be activation process 10h under conditions of the highly basic for using concentration as 0.5~2mol/L is 80~150 DEG C in temperature~
50h, and adopt and be washed with distilled water to neutrality；The highly basic is sodium hydroxide or potassium hydroxide.Other steps and parameter with it is specific
One of embodiment one to four is identical.
Embodiment six：Unlike one of present embodiment and embodiment one to five：Institute in step 3
It is nitrogen or argon gas to state inert gas.Other steps and parameter are identical with one of embodiment one to five.
Embodiment seven：Unlike one of present embodiment and embodiment one to six：Institute in step 3
It is the 2h~4h that is carbonized under conditions of temperature is 900 DEG C to state carbonization treatment.Other steps and parameter and embodiment one to
One of six is identical.
Embodiment eight：Unlike one of present embodiment and embodiment one to seven：Institute in step 5
It is LiFePO to state iron-based material to be composite4、FePO4、Na3.12Fe2.44(P2O7)2Or Li2-xFeP2O7.Other steps and parameter and tool
One of body embodiment one to seven is identical.
Embodiment nine：Unlike one of present embodiment and embodiment one to eight：Institute in step 5
It is nitric acid to state oxidant.Other steps and parameter are identical with one of embodiment one to eight.
Embodiment ten：Unlike one of present embodiment and embodiment one to nine：Institute in step 5
It is tartaric acid or citric acid to state reducing agent.Other steps and parameter are identical with one of embodiment one to nine.
Beneficial effects of the present invention are verified by following embodiments
Embodiment one：Carbon dioxide catalysis prepares the iron-based polyanion with multidimensional hierarchy-high porosity biology
What the method for matter carbon composite specifically carried out according to the following steps：
The first, commercially available kelp 500g is put into immersion 24h~48h after being cleaned 5~10 times in clear water；Then use concentration for
The hydrochloric acid of 0.5mol/L cleans the commercially available kelp after surface clean, and adopts and be washed with distilled water to neutrality；Continue to use
Activation process 10h~50h under conditions of the sodium hydroxide that concentration is 0.5~1mol/L is 80~150 DEG C in temperature, and use
Water washing is distilled to neutrality；It is dried under conditions of being finally 80 DEG C in temperature, product after being activated；
2nd, product after activation is placed in vacuum airtight container, carbon dioxide gas is then filled with into vacuum airtight container
Body, vacuumizes, and is filled with carbon dioxide again, and repetitive operation three times, then preserves 24h under carbon dioxide atmosphere, obtains
Material after processing；
3rd, by processed material under the protection of nitrogen or argon gas temperature be 900 DEG C under conditions of be carbonized 2h~4h,
Obtain the multiple-biological carbon using kelp as template；
4th, 13.2g lithium acetates, 24.19g ferric nitrates, 23g ammonium dihydrogen phosphates, 19.2g citric acids and nitric acid are dissolved in
Water, adds multiple-biological carbon of the 5g using kelp as template, is evaporated under conditions of being 80 DEG C in temperature, obtains precursor powder；Institute
The molar ratio for stating nitric acid and citric acid is 1:1；
5th, precursor powder is put into high temperature furnace and calcines 3min under conditions of temperature is 650 DEG C, obtained with multidimensional
The iron-based polyanion of hierarchy-high porosity biomass carbon composite material.
Embodiment two：Carbon dioxide catalysis prepares the iron-based polyanion with multidimensional hierarchy-high porosity biology
What the method for matter carbon composite specifically carried out according to the following steps：
The first, rice shell 300g is put into immersion 24h~48h after being cleaned 5~10 times in clear water；Then use concentration for
The hydrochloric acid of 0.5mol/L cleans the rice shell after surface clean, and adopts and be washed with distilled water to neutrality；Continue using dense
Activation process 10h~50h under conditions of the sodium hydroxide for 2 mol/L is 80~150 DEG C in temperature is spent, and using distillation washing
Wash to neutrality；It is dried under conditions of being finally 80 DEG C in temperature, product after being activated；
2nd, product after activation is placed in vacuum airtight container, carbon dioxide gas is then filled with into vacuum airtight container
Body, vacuumizes, and is filled with carbon dioxide again, and repetitive operation three times, then preserves 24h under carbon dioxide atmosphere, obtains
Material after processing；
3rd, by processed material under the protection of nitrogen or argon gas temperature be 900 DEG C under conditions of be carbonized 2h~4h,
Obtain the multiple-biological carbon using rice shell as template；
4th, 9.9g lithium acetates, 24.19g ferric nitrates, 23g ammonium dihydrogen phosphates, 19.2g citric acids and nitric acid are dissolved in water,
Multiple-biological carbon of the 5g using kelp as template is added, is evaporated under conditions of being 80 DEG C in temperature, obtains precursor powder；The nitre
The molar ratio of acid and citric acid is 1:1；
5th, precursor powder is put into high temperature furnace and calcines 3min under conditions of temperature is 650 DEG C, obtained with multidimensional
The iron-based polyanion of hierarchy-high porosity biomass carbon composite material.
Embodiment three：Carbon dioxide catalysis prepares the iron-based polyanion with multidimensional hierarchy-high porosity biology
What the method for matter carbon composite specifically carried out according to the following steps：
The first, commercially available kelp 500g is put into immersion 24h~48h after being cleaned 5~10 times in clear water；Then use concentration for
The hydrochloric acid of 0.5mol/L cleans the commercially available kelp after surface clean, and adopts and be washed with distilled water to neutrality；Continue to use
Activation process 10h~50h under conditions of the sodium hydroxide that concentration is 0.5~1mol/L is 80~150 DEG C in temperature, and use
Water washing is distilled to neutrality；It is dried under conditions of being finally 80 DEG C in temperature, product after being activated；
2nd, product after activation is placed in vacuum airtight container, carbon dioxide gas is then filled with into vacuum airtight container
Body, vacuumizes, and is filled with carbon dioxide again, and repetitive operation three times, then preserves 24h under carbon dioxide atmosphere, obtains
Material after processing；
3rd, by processed material under the protection of nitrogen or argon gas temperature be 900 DEG C under conditions of be carbonized 2h~4h,
Obtain the multiple-biological carbon using kelp as template；
4th, 20.6g sodium acetates, 59g ferric nitrates, 46g ammonium dihydrogen phosphates, 38.4g citric acids and nitric acid are dissolved in water, added
Enter multiple-biological carbon of the 10g using kelp as template, be evaporated under conditions of being 80 DEG C in temperature, obtain precursor powder；The nitre
The molar ratio of acid and citric acid is 1:1；
5th, precursor powder is put into high temperature furnace and calcines 3min under conditions of temperature is 650 DEG C, obtained with multidimensional
The iron-based polyanion of hierarchy-high porosity biomass carbon composite material.
Example IV：Carbon dioxide catalysis prepares the iron-based polyanion with multidimensional hierarchy-high porosity biology
What the method for matter carbon composite specifically carried out according to the following steps：
The first, seaweed 500g is put into immersion 24h~48h after being cleaned 5~10 times in clear water；Then use concentration for
The hydrochloric acid of 0.5mol/L cleans the seaweed after surface clean, and adopts and be washed with distilled water to neutrality；Continue to use concentration
Activation process 10h~50h under conditions of sodium hydroxide for 0.5~1mol/L is 80~150 DEG C in temperature, and using distillation
Water washing is to neutrality；It is dried under conditions of being finally 80 DEG C in temperature, product after being activated；
2nd, product after activation is placed in vacuum airtight container, carbon dioxide gas is then filled with into vacuum airtight container
Body, vacuumizes, and is filled with carbon dioxide again, and repetitive operation three times, then preserves 24h under carbon dioxide atmosphere, obtains
Material after processing；
3rd, by processed material under the protection of nitrogen or argon gas temperature be 900 DEG C under conditions of be carbonized 2h~4h,
Obtain the multiple-biological carbon using seaweed as template；
4th, 20.6g sodium acetates, 59g ferric nitrates, 46g ammonium dihydrogen phosphates, 38.4g citric acids and nitric acid are dissolved in water, added
Enter multiple-biological carbon of the 10g using seaweed as template, be evaporated under conditions of being 80 DEG C in temperature, obtain precursor powder；The nitre
The molar ratio of acid and citric acid is 1:1；
5th, precursor powder is put into high temperature furnace and calcines 3min under conditions of temperature is 650 DEG C, obtained with multidimensional
The iron-based polyanion of hierarchy-high porosity biomass carbon composite material.
Embodiment five：Carbon dioxide catalysis prepares the iron-based polyanion with multidimensional hierarchy-high porosity biology
What the method for matter carbon composite specifically carried out according to the following steps：
The first, seaweed 300g is put into immersion 24h~48h after being cleaned 5~10 times in clear water；Then use concentration for
The hydrochloric acid of 0.5mol/L cleans the seaweed after surface clean, and adopts and be washed with distilled water to neutrality；Continue to use concentration
Activation process 10h~50h under conditions of sodium hydroxide for 2mol/L is 80~150 DEG C in temperature, and adopt and be washed with distilled water
To neutrality；It is dried under conditions of being finally 80 DEG C in temperature, product after being activated；
2nd, product after activation is placed in vacuum airtight container, carbon dioxide gas is then filled with into vacuum airtight container
Body, vacuumizes, and is filled with carbon dioxide again, and repetitive operation three times, then preserves 24h under carbon dioxide atmosphere, obtains
Material after processing；
3rd, by processed material under the protection of nitrogen or argon gas temperature be 900 DEG C under conditions of be carbonized 2h~4h,
Obtain the multiple-biological carbon using seaweed as template；
4th, 4.95g lithium acetates, 24.19g ferric nitrates, 11.5g ammonium dihydrogen phosphates, 9.6g citric acids and nitric acid are dissolved in
Water, adds multiple-biological carbon of the 10g using seaweed as template, is evaporated under conditions of being 80 DEG C in temperature, obtains precursor powder；Institute
The molar ratio for stating nitric acid and citric acid is 1:1；
5th, precursor powder is put into high temperature furnace and calcines 3min under conditions of temperature is 650 DEG C, obtained with multidimensional
The iron-based polyanion of hierarchy-high porosity biomass carbon composite material.
Fig. 1 is that iron-based polyanion-high porosity biomass carbon with multidimensional hierarchy that embodiment one obtains is answered
The scanning electron microscope (SEM) photograph of condensation material；Fig. 2 is the scanning electron microscope (SEM) photograph of the iron-based polyanionic material of inanimate object carbon base body；By Fig. 1 and Fig. 2
As can be seen that there is the prepared iron-based material using material bio-based carbon as matrix micrometer/nanometer to be classified compound microstructure
And high porosity, the structure are conducive to the charge-discharge performance of material；There is very big particle without adulterating biomass carbon material
Degree and very low porosity, are unfavorable for the charge-discharge performance of material.Fig. 3 be embodiment one obtain there is multidimensional hierarchy
The charging and discharging curve of iron-based polyanion-high porosity biomass carbon composite material；Fig. 4 is that the iron-based of inanimate object carbon base body gathers the moon
The charging and discharging curve of ionic material；By Fig. 3 and Fig. 4 can see multidimensional composite material than the iron-based of inanimate object carbon base body gather it is cloudy from
Sub- material has more preferable charge-discharge performance, this is because it is with good multidimensional hierarchy.
Fig. 5 is that iron-based polyanion-high porosity biomass carbon with multidimensional hierarchy that example IV obtains is answered
The transmission electron microscope picture of condensation material；By Fig. 5, it can be seen that, which has the high pore structure of nanoscale, which is conducive to material
Chemical property.Fig. 6 is iron-based polyanion-high porosity biomass with multidimensional hierarchy that example IV obtains
The cycle performance curve of carbon composite；Material has excellent cyclical stability as seen from Figure 6, its point with material
Level composite construction is related.
Claims (10)
1. carbon dioxide catalysis prepares iron-based polyanion-high porosity biomass carbon composite material with multidimensional hierarchy
Method, it is characterised in that carbon dioxide catalysis prepares the iron-based polyanion-high porosity biology with multidimensional hierarchy
What the method for matter carbon composite specifically carried out according to the following steps：
First, after biomass being carried out removing surface, acid treatment and activation process successively, under conditions of temperature is 60 DEG C~80 DEG C
It is dried, product after being activated；
2nd, product after activation is placed in vacuum airtight container, carbon dioxide is then filled with into vacuum airtight container, taken out
Vacuum, is filled with carbon dioxide again, and repetitive operation three times, then preserves 24h, after obtaining processing under carbon dioxide atmosphere
Material；
3rd, processed material is subjected to carbonization treatment under inert gas shielding, obtains high hole biomass carbon；
4th, the chemical formula according to iron-based material to be composite, in various elements ratio weigh it is corresponding prepare material, and weigh corresponding
The Oxidizing and Reducing Agents of amount；By weigh prepare material, Oxidizing and Reducing Agents is dissolved in water, add the obtained height of step 3
Hole biomass carbon, is evaporated under conditions of being 80~100 DEG C in temperature, obtains precursor powder；The iron-based material to be composite
The molar ratio of middle ferro element and oxidant is 1:(0.5~2)；The molar ratio of the Oxidizing and Reducing Agents is 1:1；
5th, precursor powder is put into high temperature furnace and calcines 3min~5min under conditions of temperature is 600~800 DEG C, obtained
Iron-based polyanion with multidimensional hierarchy-high porosity biomass carbon composite material.
2. carbon dioxide catalysis according to claim 1 prepares iron-based polyanion-high hole with multidimensional hierarchy
The method of porosity biomass carbon composite material, it is characterised in that biomass described in step 1 is kelp, cotton, rice shell or perfume (or spice)
Any of several broadleaf plants skin.
3. carbon dioxide catalysis according to claim 1 prepares iron-based polyanion-high hole with multidimensional hierarchy
The method of porosity biomass carbon composite material, it is characterised in that removing surface described in step 1 is that biomass is put into clear water
24h~48h is soaked after cleaning 5~10 times.
4. carbon dioxide catalysis according to claim 1 prepares iron-based polyanion-high hole with multidimensional hierarchy
The method of porosity biomass carbon composite material, it is characterised in that acid treatment described in step 1 uses concentration as 0.5mol/L
Hydrochloric acid cleans the biomass after surface clean, and adopts and be washed with distilled water to neutrality.
5. carbon dioxide catalysis according to claim 1 prepares iron-based polyanion-high hole with multidimensional hierarchy
The method of porosity biomass carbon composite material, it is characterised in that activation process described in step 1 be use concentration for 0.5~
Activation process 10h~50h under conditions of the highly basic of 2mol/L is 80~150 DEG C in temperature, and adopt and be washed with distilled water to neutrality；
The highly basic is sodium hydroxide or potassium hydroxide.
6. carbon dioxide catalysis according to claim 1 prepares iron-based polyanion-high hole with multidimensional hierarchy
The method of porosity biomass carbon composite material, it is characterised in that inert gas described in step 3 is nitrogen or argon gas.
7. carbon dioxide catalysis according to claim 1 prepares iron-based polyanion-high hole with multidimensional hierarchy
The method of porosity biomass carbon composite material, it is characterised in that carbonization treatment described in step 3 is in the bar that temperature is 900 DEG C
Be carbonized 2h~4h under part.
8. carbon dioxide catalysis according to claim 1 prepares iron-based polyanion-high hole with multidimensional hierarchy
The method of porosity biomass carbon composite material, it is characterised in that iron-based material to be composite described in step 5 is LiFePO4、
FePO4、Na3.12Fe2.44(P2O7)2Or Li2-xFeP2O7。
9. carbon dioxide catalysis according to claim 1 prepares iron-based polyanion-high hole with multidimensional hierarchy
The method of porosity biomass carbon composite material, it is characterised in that oxidant described in step 5 is nitric acid.
10. carbon dioxide catalysis according to claim 1 prepares iron-based polyanion-high hole with multidimensional hierarchy
The method of porosity biomass carbon composite material, it is characterised in that reducing agent described in step 5 is tartaric acid or citric acid.
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| CN104701498A (en) * | 2015-03-27 | 2015-06-10 | 陕西科技大学 | Method for preparing biochar/ammonium vanadate lithium ion cell cathode material |
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| CN104701498A (en) * | 2015-03-27 | 2015-06-10 | 陕西科技大学 | Method for preparing biochar/ammonium vanadate lithium ion cell cathode material |
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