CN112010283A - Preparation method of high-performance biomass-based carbonaceous electrode material - Google Patents
Preparation method of high-performance biomass-based carbonaceous electrode material Download PDFInfo
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- CN112010283A CN112010283A CN202010891791.7A CN202010891791A CN112010283A CN 112010283 A CN112010283 A CN 112010283A CN 202010891791 A CN202010891791 A CN 202010891791A CN 112010283 A CN112010283 A CN 112010283A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 136
- 239000007772 electrode material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000835 fiber Substances 0.000 claims abstract description 77
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000007864 aqueous solution Substances 0.000 claims abstract description 55
- 239000000843 powder Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000002791 soaking Methods 0.000 claims abstract description 32
- 239000004744 fabric Substances 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 29
- 239000002019 doping agent Substances 0.000 claims abstract description 20
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 20
- 230000008961 swelling Effects 0.000 claims abstract description 18
- -1 transition metal salt Chemical class 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000007710 freezing Methods 0.000 claims abstract description 14
- 230000008014 freezing Effects 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000012190 activator Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 150000003681 vanadium Chemical class 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- 238000007654 immersion Methods 0.000 abstract description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 33
- 235000017491 Bambusa tulda Nutrition 0.000 description 33
- 241001330002 Bambuseae Species 0.000 description 33
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 33
- 239000011425 bamboo Substances 0.000 description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 13
- 229920002678 cellulose Polymers 0.000 description 12
- 239000001913 cellulose Substances 0.000 description 12
- 229910052573 porcelain Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 241000609240 Ambelania acida Species 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000010905 bagasse Substances 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 10
- 238000003763 carbonization Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000009777 vacuum freeze-drying Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 6
- 229940078494 nickel acetate Drugs 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 244000025254 Cannabis sativa Species 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 235000014676 Phragmites communis Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 235000009120 camo Nutrition 0.000 description 2
- 235000005607 chanvre indien Nutrition 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000011487 hemp Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- 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
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a preparation method of a high-performance biomass-based carbonaceous electrode material. The preparation method sequentially comprises the following steps: firstly, soaking swelling biomass powder, biomass fiber paper or cloth in N-methylmorpholine-N-oxide aqueous solution; secondly, freezing the biomass powder, the biomass fiber paper or the cloth to freeze water contained in the biomass powder and the biomass fiber paper or the cloth to form ice crystals; thirdly, drying in a frozen state; fourthly, sintering at high temperature after drying; fifthly, cooling the sintered product; and sixthly, preparing the high-performance biomass-based carbonaceous electrode material. The aqueous solution of N-methylmorpholine-N-oxide used for the immersion preferably further contains at least one of a water-soluble transition metal salt, an activator and a dopant. And soaking in water solution of water soluble transition metal salt, activator and dopant between the third and fourth steps. The preparation method is simple and easy to implement, and the prepared electrode material has excellent electrochemical performance.
Description
Technical Field
The invention relates to a preparation method of an electrode material, in particular to a preparation method of a high-performance biomass-based carbon electrode material, and belongs to the field of electrodes for super capacitors and batteries.
Background
Carbon materials have the advantages of stability and long life as electrodes for supercapacitors and batteries, but graphene and carbon nanotubes are expensive. The carbon electrode material for the super capacitor and the battery with high performance is obtained by adopting a low-cost way, and becomes a hotspot of research and development. The biomass has the advantages of low price, environmental friendliness, reproducibility and the like, and can be obtained in a large scale at a low cost, so that the biomass-based carbon-based electrode material has a wide application prospect. However, the preparation process of obtaining carbon-based electrode materials by carbonizing biomass is complicated at present, and particularly, the electrochemical performance is not ideal. How to obtain a high-performance biomass-based carbonaceous electrode material with excellent electrochemical performance by a simple method is still a problem at present.
Disclosure of Invention
The purpose of the present invention is to provide a simple method for producing a high-performance biomass-based carbonaceous electrode material having excellent electrochemical properties.
The technical solution for realizing the purpose of the invention is as follows: a preparation method of a high-performance biomass-based carbonaceous electrode material sequentially comprises the following steps:
firstly, soaking swelling biomass powder in an N-methylmorpholine-N-oxide aqueous solution;
secondly, freezing the biomass powder swelled with the N-methylmorpholine-N-oxide aqueous solution to freeze water contained therein to form ice crystals;
thirdly, drying the frozen biomass powder in a frozen state;
fourthly, sintering the dried biomass powder at a high temperature;
fifthly, cooling the sintered product;
and sixthly, preparing the high-performance biomass-based carbonaceous electrode material.
The preparation method of the high-performance biomass-based carbonaceous electrode material can also sequentially comprise the following steps of:
soaking swelling biomass fibers in an N-methylmorpholine-N-oxide aqueous solution, and preparing the biomass fibers swelled with the N-methylmorpholine-N-oxide aqueous solution into paper; or the biomass fiber is adopted to prepare paper, and the swelling biomass fiber paper is soaked in the N-methylmorpholine-N-oxide aqueous solution; or soaking the swelling biomass fiber cloth by adopting an N-methylmorpholine-N-oxide aqueous solution;
secondly, freezing the biomass fiber paper or cloth swelled with the N-methylmorpholine-N-oxide aqueous solution to freeze water contained therein to form ice crystals;
thirdly, drying the frozen biomass fiber paper or cloth in a frozen state;
fourthly, sintering the dried biomass fiber paper or cloth at high temperature;
fifthly, cooling the sintered product;
and sixthly, preparing the high-performance biomass-based carbonaceous electrode material.
In the preparation method of the high-performance biomass-based carbonaceous electrode material, the mass concentration of N-methylmorpholine-N-oxide in the N-methylmorpholine-N-oxide aqueous solution adopted in the first step of soaking is preferably below 30%.
In the preparation method of the high-performance biomass-based carbonaceous electrode material of the invention, the first step to the third step can be repeated.
In the preparation method of the high-performance biomass-based carbonaceous electrode material, the fourth step of high-temperature sintering process comprises the following sintering conditions: sintering for 1-4 hours at 600-1100 ℃ under inert atmosphere.
In the preparation method of the high-performance biomass-based carbonaceous electrode material, the sintered product can be soaked by acid between the fifth step and the sixth step.
In the preparation method of the high-performance biomass-based carbonaceous electrode material, the N-methylmorpholine-N-oxide aqueous solution adopted in the first-step soaking can also contain at least one of water-soluble transition metal salt, water-soluble activating agent and water-soluble doping agent.
In the preparation method of the high-performance biomass-based carbonaceous electrode material, between the third step and the fourth step, the biomass powder, the biomass fiber paper or cloth can be soaked in the aqueous solution containing at least one of the water-soluble transition metal salt, the water-soluble activator and the water-soluble dopant and then dried. The aqueous solution used for the immersion preferably contains N-methylmorpholine-N-oxide.
In the preparation method of the high-performance biomass-based carbonaceous electrode material, the water-soluble transition metal salt can be at least one of nickel salt, cobalt salt, manganese salt, copper salt, zinc salt or vanadium salt, the water-soluble activator can be at least one of zinc chloride, sodium hydroxide or potassium hydroxide, and the water-soluble dopant can be at least one of urea, melamine, thiourea or phosphoric acid.
The preparation method of the high-performance biomass-based carbonaceous electrode material has the following remarkable advantages: (1) cheap and commercialized cellulose biomass is used as a raw material to prepare a high-performance electrode material; (2) the cellulose biomass is soaked in the N-methylmorpholine-N-oxide aqueous solution, and the N-methylmorpholine-N-oxide can well swell the cellulose biomass, so that the cellulose biomass is frozen to form more ice crystals, and finally the carbonaceous material obtains more micropores and mesopores, has larger specific surface area and excellent electrochemical performance; (3) the preparation method is flexible and changeable, and water-soluble transition metal salt, water-soluble activator and water-soluble dopant can be added into the N-methylmorpholine-N-oxide aqueous solution for soaking, or the (N-methylmorpholine-N-oxide) aqueous solution of the water-soluble transition metal salt, the water-soluble activator and the water-soluble dopant is subsequently soaked, so that the specific surface area and the surface hydrophilicity of the final carbonaceous material are further improved, and more excellent electrochemical performance is obtained; (4) the N-methylmorpholine N-oxide adopted by the invention is environment-friendly and can not cause environmental pollution.
Detailed Description
The preparation method of the high-performance biomass-based carbonaceous electrode material comprises the following steps in sequence:
firstly, soaking swelling biomass powder in an N-methylmorpholine-N-oxide aqueous solution;
secondly, freezing the biomass powder swelled with the N-methylmorpholine-N-oxide aqueous solution to freeze water contained therein to form ice crystals;
thirdly, drying the frozen biomass powder in a frozen state;
fourthly, sintering the dried biomass powder at a high temperature;
fifthly, cooling the sintered product;
and sixthly, preparing the high-performance biomass-based carbonaceous electrode material.
The preparation method of the high-performance biomass-based carbonaceous electrode material provided by the invention also can comprise the following steps in sequence:
soaking swelling biomass fibers in an N-methylmorpholine-N-oxide aqueous solution, and preparing the biomass fibers swelled with the N-methylmorpholine-N-oxide aqueous solution into paper; or the biomass fiber is adopted to prepare paper, and the swelling biomass fiber paper is soaked in the N-methylmorpholine-N-oxide aqueous solution; or soaking the swelling biomass fiber cloth by adopting an N-methylmorpholine-N-oxide aqueous solution;
secondly, freezing the biomass fiber paper or cloth swelled with the N-methylmorpholine-N-oxide aqueous solution to freeze water contained therein to form ice crystals;
thirdly, drying the frozen biomass fiber paper or cloth in a frozen state;
fourthly, sintering the dried biomass fiber paper or cloth at high temperature;
fifthly, cooling the sintered product;
and sixthly, preparing the high-performance biomass-based carbonaceous electrode material.
The biomass powder adopted by the invention can be various plant straws and plant shells mainly containing cellulose, such as rice hull powder, peanut hull powder, bagasse powder, wood powder, bamboo powder, cotton pollen, grass powder, reed powder, hemp powder and the like. The biomass fiber can be at least one of cellulose-based plant fibers such as wood, bamboo, sugarcane, cotton, grass, reed and hemp. The biomass fiber cloth used may be cloth of various fibers of cellulose type (including non-woven cloth and woven cloth), such as cloth formed of at least one fiber of cotton fiber, bamboo fiber, viscose fiber, Lyocell fiber, and the like. The biomass powder or biomass fiber used herein may be biomass powder or biomass fiber from which non-cellulose impurities have been removed by alkali treatment or the like.
The invention adopts N-methylmorpholine N-oxide aqueous solution with a certain concentration to soak swelling biomass powder or fiber to swell the powder or fiber, then the swelling powder or fiber is frozen to freeze water contained therein to form ice crystals, the ice crystals are dried in a freezing state to obtain a large number of holes left by the ice crystals, then the biomass fiber containing the holes left by the ice crystals is sintered, and simultaneously the N-methylmorpholine N-oxide is decomposed into gas to run away in the sintering process, and finally a large number of microporous and mesoporous carbonaceous materials are obtained, thus showing excellent electrochemical performance.
In the preparation method of the high-performance biomass-based carbonaceous electrode material, the mass concentration of N-methylmorpholine-N-oxide in the N-methylmorpholine-N-oxide aqueous solution adopted for soaking is not higher than 50%. The effect of freezing pore-forming is rather low, preferably 30% or less, due to the excessively high mass concentration of N-methylmorpholine-N-oxide.
In the preparation method of the high-performance biomass-based carbonaceous electrode material of the invention, the first step to the third step may be repeated one or more times.
In the preparation method of the high-performance biomass-based carbonaceous electrode material, the third step of drying the frozen biomass powder in a frozen state can be freeze-drying in a vacuum freeze-drying machine.
In the preparation method of the high-performance biomass-based carbonaceous electrode material, the fourth step of high-temperature sintering process comprises the following sintering conditions: sintering for 1-4 hours at 600-1100 ℃ under inert atmosphere.
In the preparation method of the high-performance biomass-based carbonaceous electrode material, the sintered product can be soaked by acid between the fifth step and the sixth step. The acid soaking sintered product can eliminate impurity from carbon electrode material and raise electrochemical stability.
In the preparation method of the high-performance biomass-based carbonaceous electrode material, the N-methylmorpholine-N-oxide aqueous solution adopted in the first-step soaking can also contain at least one of water-soluble transition metal salt, water-soluble activating agent and water-soluble doping agent. If the N-methylmorpholine-N-oxide aqueous solution used for soaking also contains water-soluble transition metal salt, more pores can be formed in the final carbon material, and pseudo capacitance is given. The water-soluble transition metal salt may be at least one of a nickel salt, a cobalt salt, a manganese salt, a copper salt, a zinc salt or a vanadium salt. The transition metal salt used may be a transition metal organic salt such as an acetate; transition metal inorganic salts such as sulfates, nitrates, and the like are also possible. For the carbon material used as the electrode, an activator may be used in order to increase the porosity, and a dopant may be used in order to dope the carbon. If the N-methylmorpholine-N-oxide aqueous solution used for soaking also contains a water-soluble activating agent, such as alkali, zinc chloride, calcium chloride and potassium ferrite, wherein the alkali can be sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like, pore-forming can be activated during high-temperature sintering, so that the final carbonaceous material can obtain more micropores and mesopores and a larger specific surface area, and better electrochemical performance can be obtained. For the carbon material used as an electrode, the dopant is to dope carbon with nitrogen, sulfur and phosphorus elements, to improve the hydrophilicity of the carbon material to improve the electrochemical performance, to realize carbon-doped nitrogen water-soluble dopants such as urea and melamine, to realize carbon-doped sulfur water-soluble dopants such as thiourea, and to realize carbon-doped phosphorus water-soluble dopants such as phosphoric acid. The water solution of N-methylmorpholine-N-oxide adopted for soaking contains water-soluble transition metal salt, water-soluble activating agent and/or water-soluble doping agent, so that the N-methylmorpholine-N-oxide can be better swelled into the biomass cellulose, the swelling amount of the N-methylmorpholine-N-oxide in the biomass cellulose is improved, and carbon pore-forming and/or carbon doping higher than that of pure water is realized.
In the preparation method of the high-performance biomass-based carbonaceous electrode material, between the third step and the fourth step, the biomass powder, the biomass fiber paper or the cloth can be soaked in the aqueous solution containing one or more of the water-soluble transition metal salt, the water-soluble activating agent and the water-soluble doping agent, and then dried. The water-soluble transition metal salt, water-soluble activator, and water-soluble dopant are as described herein. The water solution adopted by the soaking preferably contains N-methylmorpholine-N-oxide, so that the swelling amount of the N-methylmorpholine-N-oxide in the biomass cellulose can be increased, and better pore-forming and doping effects can be realized.
In the preparation method of the high-performance biomass-based carbonaceous electrode material, the N-methylmorpholine-N-oxide aqueous solution used for soaking can also contain an organic solvent which can be mixed and dissolved with water, so that ice crystals with better morphology can be obtained, the final carbonaceous material can obtain a more ideal micropore mesoporous structure and a larger specific surface area, and better electrochemical performance can be obtained. The water-miscible organic solvent used herein may be, for example, ethanol, acetone or dimethylformamide, and may be one or more of them.
When electrochemical performance tests (including constant current charge and discharge tests and cyclic charge and discharge tests) are carried out, a standard three-electrode test system is adopted, and carbonaceous electrode material powder to be tested, acetylene black and poly-tetra-ethyl acetate are adoptedMixing the fluoroethylene emulsion (the solid mass ratio of the three is 8: 1) into paste, coating the paste on foamed nickel to be used as a working electrode, taking an Hg/HgO electrode as a reference electrode, taking a platinum sheet as a counter electrode, and obtaining 6mol L of the foamed nickel, the Hg/HgO electrode and the Pt/Hg electrode-1The KOH solution of (3) as an electrolyte. Electrochemical tests were performed using the AUTO electrochemical workstation (vancoun PGSTAT302N, switzerland). According to the discharge curve of the constant current charge-discharge test, according to CmCalculating the mass specific capacitance C by the formula I delta t/(m delta V)m(F g-1) In the formula, I is a test current (A), delta t is a discharge time(s), m is the mass (g) of the carbonaceous electrode material powder to be tested on the working electrode, and delta V is a discharge potential difference (V).
Example 1
Dispersing 0.5g of bamboo pulp fiber for papermaking in 80mL of 10% by mass N-methylmorpholine N-oxide aqueous solution to obtain N-methylmorpholine N-oxide suspension solution of the bamboo pulp fiber, soaking the bamboo pulp fiber for 6 hours at 70 ℃, and then filtering and removing redundant N-methylmorpholine N-oxide aqueous solution in the suspension solution to obtain the bamboo pulp fiber containing the N-methylmorpholine N-oxide aqueous solution. And then, fully freezing the bamboo pulp fiber containing the N-methylmorpholine N-oxide aqueous solution at the temperature of-16 ℃, and putting the frozen bamboo pulp fiber into a vacuum freeze dryer for vacuum freeze drying for 48 hours to obtain the freeze-dried bamboo fiber. And (3) putting the freeze-dried bamboo fiber into a porcelain square boat, and putting the porcelain square boat into a horizontal tube furnace for sintering and carbonizing in a nitrogen atmosphere. The carbonization process is carried out at 2 deg.C for min-1The temperature rising rate of (1) is increased from room temperature to 400 ℃ for 2 hours, and then the temperature is increased for 5 min-1Heating to 900 deg.C, sintering for 2 hr, and cooling to 5 deg.C for min-1And cooling to room temperature to obtain the high-performance biomass-based carbonaceous electrode material. The high-performance biomass-based carbon electrode material is 1A g-1The mass specific capacitance reaches 216F g under the current density-1At 1A g-1The mass specific capacitance of the capacitor still reaches 203F g after 8000 times of cyclic charge and discharge tests-1And the cycle life is excellent.
Comparative example 1
Drying 0.4g of bamboo pulp fiber for papermaking at 70 ℃, putting the dried bamboo pulp fiber block into a porcelain ark, and putting the porcelain ark into a horizontal tube furnaceSintering and carbonizing under nitrogen atmosphere. The carbonization process is carried out at 2 deg.C for min-1The temperature rising rate of (1) is increased from room temperature to 400 ℃ for 2 hours, and then the temperature is increased for 5 min-1The temperature rising rate is increased to 900 ℃, the sintering is carried out for 2 hours in a heat preservation way, and finally, the temperature is increased for 5 min-1And cooling to room temperature to obtain the comparative biomass-based carbonaceous electrode material. Comparative example biomass-based carbonaceous electrode material at 1A g-1Current density of only 103F g mass specific capacitance-1。
Comparative example 2
0.4g of bamboo pulp fiber for papermaking is dispersed in 80ml of deionized water to obtain a water suspension of the bamboo pulp fiber, and after the bamboo pulp fiber is soaked for 6 hours at 70 ℃, the excessive water in the suspension is filtered and removed to obtain the water-containing bamboo pulp fiber. Fully freezing the bamboo pulp fiber containing water at the temperature of minus 16 ℃, and putting the frozen bamboo pulp fiber into a vacuum freeze dryer for vacuum freeze drying for 48 hours to obtain the freeze-dried bamboo fiber. And (3) putting the freeze-dried bamboo fiber into a porcelain ark, and putting the porcelain ark into a horizontal tube furnace to be sintered and carbonized in a nitrogen atmosphere. The carbonization process is carried out at 2 deg.C for min-1The temperature rising rate of (1) is increased from room temperature to 400 ℃ for 2 hours, and then the temperature is increased for 5 min-1The temperature rising rate is increased to 900 ℃, the sintering is carried out for 2 hours in a heat preservation way, and finally, the temperature is increased for 5 min-1And cooling to room temperature to obtain the comparative biomass-based carbonaceous electrode material. Comparative example biomass-based carbonaceous electrode material, at 1A g-1Current density of only 150F g mass specific capacitance-1。
Example 2
Soaking 0.5g of bamboo pulp fiber paper in 80mL of N-methylmorpholine N-oxide aqueous solution (prepared by adding zinc chloride and ethanol into 15 mass percent of N-methylmorpholine N-oxide aqueous solution) containing 12g of zinc chloride and 3g of ethanol at 70 ℃ for 6 hours, taking out the bamboo pulp fiber paper, fully freezing the bamboo pulp fiber paper by using liquid nitrogen, and putting the frozen bamboo pulp fiber paper into a vacuum freeze dryer for vacuum freeze drying for 48 hours to obtain the freeze-dried bamboo pulp fiber paper. And (3) putting the freeze-dried bamboo pulp fiber paper into a porcelain square boat, and putting the porcelain square boat into a horizontal tube furnace for sintering and carbonization in nitrogen atmosphere. The carbonization process is carried out at 2 deg.C for min-1The heating rate is increased from room temperature to 900 ℃ and the sintering is carried out for 2 hoursFinally at 5 ℃ for min-1And cooling to room temperature to obtain the high-performance biomass-based carbonaceous electrode material. The high-performance biomass-based carbon electrode material is 1A g-1The mass specific capacitance reaches 265F g under the current density-1At 1A g-1The mass specific capacitance still reaches 223F g after 8000 times of cyclic charge and discharge tests-1And the cycle life is excellent.
Example 3
Soaking 0.5g of commercially available bamboo fiber cloth in 80mL of N-methylmorpholine N-oxide aqueous solution containing 8g of nickel acetate (prepared by dissolving nickel acetate in 13 mass percent of N-methylmorpholine N-oxide aqueous solution) at 70 ℃ for 6 hours, taking out the bamboo fiber cloth containing the nickel acetate and the N-methylmorpholine N-oxide aqueous solution, fully freezing the bamboo fiber cloth by using liquid nitrogen, and putting the frozen bamboo fiber cloth into a vacuum freeze dryer for vacuum freeze drying for 48 hours to obtain the freeze-dried bamboo fiber cloth. And (3) putting the freeze-dried bamboo fiber cloth into a porcelain square boat, and putting the porcelain square boat into a horizontal tube furnace for sintering and carbonization in nitrogen atmosphere. The carbonization process is carried out at 2 deg.C for min-1The temperature rising rate is increased from room temperature to 800 ℃, the sintering is carried out for 2 hours in a heat preservation way, and finally, the temperature is increased for 5 min-1And cooling to room temperature to obtain the high-performance biomass-based carbonaceous electrode material. The high-performance biomass-based carbon electrode material is 1A g-1The mass specific capacitance reaches 248F g-1 under the current density and is 1A g-1The mass specific capacitance still reaches 211F g after 8000 times of cyclic charge and discharge tests-1And the cycle life is excellent.
Example 4
Dispersing 0.5g of bagasse powder in 80mL of N-methylmorpholine N-oxide aqueous solution with the mass concentration of 20% to obtain N-methylmorpholine N-oxide suspension of the bagasse powder, soaking at 70 ℃ for 6 hours, then filtering and removing the redundant N-methylmorpholine N-oxide aqueous solution in the suspension to obtain bagasse powder containing the N-methylmorpholine N-oxide aqueous solution, fully freezing the bagasse powder by using liquid nitrogen, and putting the frozen bagasse powder into a vacuum freeze-drying machine for vacuum freeze-drying for 48 hours to obtain freeze-dried bagasse powder. Then, 80mL of N-methylmorpholine N-oxide containing 4g of urea and 8g of nickel acetate was usedSoaking the freeze-dried bagasse powder in an aqueous solution of a compound (prepared by dissolving urea and nickel acetate in an aqueous solution of N-methylmorpholine N-oxide with the mass concentration of 8%) at 70 ℃ for 6 hours to obtain freeze-dried bagasse powder soaked with urea and nickel acetate, and then drying. And putting the dried bagasse powder into a porcelain ark, and putting the porcelain ark into a horizontal tube furnace to be sintered and carbonized in a nitrogen atmosphere. The carbonization process is carried out at 2 deg.C for min-1The heating rate is increased from room temperature to 900 ℃, the sintering is carried out for 2 hours, and finally, the temperature is increased for 5 min-1Cooling to room temperature. And then, soaking the carbonized product for 6 hours at room temperature by using 1M hydrochloric acid, filtering, and repeatedly washing the carbonized product to be neutral by using deionized water to obtain the high-performance biomass-based carbonaceous electrode material. The high-performance biomass-based carbon electrode material is 1A g-1The mass specific capacitance reaches 283F g under the current density-1At 1A g-1The mass specific capacitance still reaches 223F g after 8000 times of cyclic charge and discharge tests-1And the cycle life is excellent.
Sintering is carried out at other temperatures of 600-900 ℃ under inert atmosphere, the sintering time is changed within 1-4 hours, the high-performance biomass-based carbonaceous electrode material is prepared according to the embodiment method, and compared with the corresponding comparative example, the high-performance biomass-based carbonaceous electrode material has the remarkable invention effect similar to that of the embodiment. The other biomass powder, biomass fiber paper or biomass fiber cloth with cellulose as the main component is adopted to prepare the corresponding high-performance biomass-based carbonaceous electrode material according to the embodiment method, and compared with the corresponding comparative example, the invention has the remarkable invention effect similar to the previous embodiment. The corresponding high-performance biomass-based carbonaceous electrode material of the invention was prepared according to the examples using other water-soluble transition metal salts, water-soluble activators and water-soluble dopants, and compared to the corresponding comparative examples, the invention exhibited significant inventive effects similar to those of the foregoing examples. With the implementation method of repeating the first to third steps, the present invention exhibits more excellent and significant inventive effects than the corresponding comparative examples. The corresponding high-performance biomass-based carbonaceous electrode material of the invention is prepared according to the method of the embodiment by adopting N-methylmorpholine N-oxide aqueous solution with other concentration as the swelling agent, and compared with the corresponding comparative example, the invention has the similar remarkable invention effect with the previous embodiment.
In the invention, a proper amount of carbon nanotubes and/or graphene (such as 1-20% of the amount of biomass powder or fibrous solid) can be added into the biomass powder or the pulp during the preparation of the biomass fiber paper, or a high-content carbon nanotube and/or graphene layer is formed in the middle of the paper during the preparation of the biomass fiber paper, so that the final high-performance biomass-based carbonaceous electrode material has better conductivity, and a current collector is not additionally adopted during the preparation of a solid battery or a supercapacitor. Which still fall within the scope of protection of the present invention.
Claims (10)
1. A preparation method of a high-performance biomass-based carbonaceous electrode material is characterized by comprising the following steps: the method sequentially comprises the following steps:
firstly, soaking swelling biomass powder in an N-methylmorpholine-N-oxide aqueous solution;
secondly, freezing the biomass powder swelled with the N-methylmorpholine-N-oxide aqueous solution to freeze water contained therein to form ice crystals;
thirdly, drying the frozen biomass powder in a frozen state;
fourthly, sintering the dried biomass powder at a high temperature;
fifthly, cooling the sintered product;
and sixthly, preparing the high-performance biomass-based carbonaceous electrode material.
2. A preparation method of a high-performance biomass-based carbonaceous electrode material is characterized by comprising the following steps: the method sequentially comprises the following steps:
soaking swelling biomass fibers in an N-methylmorpholine-N-oxide aqueous solution, and preparing the biomass fibers swelled with the N-methylmorpholine-N-oxide aqueous solution into paper; or the biomass fiber is adopted to prepare paper, and the swelling biomass fiber paper is soaked in the N-methylmorpholine-N-oxide aqueous solution; or soaking the swelling biomass fiber cloth by adopting an N-methylmorpholine-N-oxide aqueous solution;
secondly, freezing the biomass fiber paper or cloth swelled with the N-methylmorpholine-N-oxide aqueous solution to freeze water contained therein to form ice crystals;
thirdly, drying the frozen biomass fiber paper or cloth in a frozen state;
fourthly, sintering the dried biomass fiber paper or cloth at high temperature;
fifthly, cooling the sintered product;
and sixthly, preparing the high-performance biomass-based carbonaceous electrode material.
3. The method for producing a high-performance biomass-based carbonaceous electrode material according to claim 1 or 2, characterized in that: the mass concentration of the N-methylmorpholine-N-oxide in the N-methylmorpholine-N-oxide aqueous solution adopted in the first-step soaking is not higher than 30%.
4. The method for producing a high-performance biomass-based carbonaceous electrode material according to claim 1 or 2, characterized in that: repeating the first step to the third step.
5. The method for producing a high-performance biomass-based carbonaceous electrode material according to claim 1 or 2, characterized in that: the fourth step of high-temperature sintering process comprises the following sintering conditions: sintering for 1-4 hours at 600-1100 ℃ under inert atmosphere.
6. The method for producing a high-performance biomass-based carbonaceous electrode material according to claim 1 or 2, characterized in that: and between the fifth step and the sixth step, soaking the sintered product by acid.
7. The method for preparing the high-performance biomass-based carbonaceous electrode material according to any one of claims 1 to 6, characterized in that: the first step soaking adopts N-methylmorpholine-N-oxide water solution also containing at least one of water soluble transition metal salt, water soluble activator and water soluble dopant.
8. The method for preparing the high-performance biomass-based carbonaceous electrode material according to any one of claims 1 to 7, characterized in that: and between the third step and the fourth step, soaking the biomass powder, the biomass fiber paper or cloth by using an aqueous solution containing at least one of water-soluble transition metal salt, water-soluble activating agent and water-soluble doping agent, and then drying.
9. The method for preparing a high-performance biomass-based carbonaceous electrode material according to claim 8, characterized in that: the aqueous solution used for soaking contains N-methylmorpholine-N-oxide.
10. The method for producing a high-performance biomass-based carbonaceous electrode material according to claim 7 or 8, characterized in that: the water-soluble transition metal salt is at least one of nickel salt, cobalt salt, manganese salt, copper salt, zinc salt or vanadium salt; the water-soluble activator is at least one of zinc chloride, sodium hydroxide or potassium hydroxide; the water-soluble dopant is at least one of urea, melamine, thiourea or phosphoric acid.
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