CN108658056A - A kind of preparation method of the biological carbon with good electrical properties - Google Patents
A kind of preparation method of the biological carbon with good electrical properties Download PDFInfo
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- CN108658056A CN108658056A CN201810505223.1A CN201810505223A CN108658056A CN 108658056 A CN108658056 A CN 108658056A CN 201810505223 A CN201810505223 A CN 201810505223A CN 108658056 A CN108658056 A CN 108658056A
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- biological carbon
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- electrical properties
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- good electrical
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000012545 processing Methods 0.000 claims abstract description 35
- 238000003763 carbonization Methods 0.000 claims abstract description 27
- 238000007654 immersion Methods 0.000 claims abstract description 18
- 238000009835 boiling Methods 0.000 claims abstract description 17
- 238000004880 explosion Methods 0.000 claims abstract description 17
- 238000012986 modification Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000001994 activation Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 47
- 239000000843 powder Substances 0.000 claims description 45
- 239000010902 straw Substances 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000005422 blasting Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 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 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 238000010828 elution Methods 0.000 claims description 15
- KYRUBSWVBPYWEF-UHFFFAOYSA-N copper;iron;sulfane;tin Chemical compound S.S.S.S.[Fe].[Cu].[Cu].[Sn] KYRUBSWVBPYWEF-UHFFFAOYSA-N 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 12
- 229940043276 diisopropanolamine Drugs 0.000 claims description 12
- 235000002906 tartaric acid Nutrition 0.000 claims description 11
- 239000011975 tartaric acid Substances 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LRWZZZWJMFNZIK-NFJMKROFSA-N (2R)-2-chloro-3-methyloxirane Chemical compound CC1O[C@@H]1Cl LRWZZZWJMFNZIK-NFJMKROFSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 235000015393 sodium molybdate Nutrition 0.000 claims description 6
- 239000011684 sodium molybdate Substances 0.000 claims description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- -1 Oxo transition metal Chemical class 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940124274 edetate disodium Drugs 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a kind of preparation methods of the biological carbon with good electrical properties, include the following steps：（1）Boiling processing,（2）Oxidation immersion treatment,（3）Steam explosion treatment,（4）Activation process,（5）Modification,（6）Carbonization treatment.The present invention provides a kind of preparation methods of biological carbon, integrated artistic specification, it is produced convenient for batch jobs, biological carbon excellent electrical properties obtained, it has been obviously improved the capacity and cyclical stability of electric discharge, enhance its quality as lithium cell cathode material, the great market competitiveness and application value.
Description
Technical field
The invention belongs to biological carbon working process technical fields, and in particular to a kind of biological carbon with good electrical properties
Preparation method.
Background technology
Agricultural crop straw is the general name of ripe crops stem and leaf part.Be often referred to wheat, rice, corn, potato, rape,
The remainder of cotton, sugarcane and other crops after harvesting seed.The photosynthetic product of crops has more than half to deposit
It is in stalk, for stalk rich in carbon, nitrogen, phosphorus, potassium, calcium, magnesium and organic matter etc., being one kind having multiduty reproducible biology
Resource.Existing a part of agricultural crop straw is used in the making of biological carbon.
With the high speed development of social economy, the interdependency of the energy is continuously improved in human society.But the mankind's is excessive
Exploitation, has made lack of energy, severe environmental pollution.In order to solve current energy problem, people turn one's attention to renewable
Clean energy resource.However, they also have a limitation of itself, for example total amount is big, randomness, energy density are low etc. etc., these disadvantages
Cause them to be difficult with.Therefore, high-efficiency energy-storage technology becomes research hotspot.
Chargeable battery system based on lead-acid battery, nickel-cadmium cell and lithium ion battery is the electrochemical energy storage of large capacity
The important member of technology, and the lead-acid battery and nickel-cadmium cell of low, the serious pollution environment of energy density will gradually exit history
Stage.In contrast, as the outstanding person in novel energy-storing technology, lithium ion battery have open-circuit voltage from, it is higher than energy,
Security performance is superior and advantages of environment protection, superior performance will also make it substitute plumbic acid, nickel-cadmium cell.Except this it
Outside, lithium ion battery is cheap, and security performance is high, is a kind of very promising green battery.In recent years, lithium ion battery
It is widely used in electric vehicle etc..
Negative material is one of core of lithium ion battery, the most commonly used lithium ion battery negative material studied at present
It is carbon based negative electrodes material, such as graphite mainly to have two major classes, one kind；One kind is non-carbon based negative electrodes material, such as tin base cathode material and
Oxo transition metal（Sulphur）Compound.Biological carbon belongs to carbon based negative electrodes material, and in recent years, the research of biological carbon material has started energy storage material
The another stock upsurge in material field.Biological carbon is because of its own unique physicochemical property for having, its is resourceful in addition, and price is low
It is honest and clean, it is renewable and environmentally protective many advantages, such as, become extremely potential up-and-coming youngster in non-graphitized carbon material,
And cause the extensive interest of researcher.But that mostly there is electrical properties is bad for biological carbon material made from the prior art, no
The problems such as stablizing, there is an urgent need for be improved.
Invention content
The purpose of the present invention is for existing problem, provide a kind of preparation side of the biological carbon with good electrical properties
Method.
The present invention is achieved by the following technical solutions：
A kind of preparation method of the biological carbon with good electrical properties, includes the following steps：
（1）Boiling is handled：
Agricultural crop straw is put into sodium hydroxide solution and is heated to boiling, is then boiled crops after boiling 20 ~ 30min of processing
Stalk takes out spare；
（2）Aoxidize immersion treatment：
By step（1）Immersion treatment 4 in the hydrogen peroxide solution that agricultural crop straw is put into volume fraction that treated is 20 ~ 25% ~
6h, it is spare after being washed with deionized to neutrality after taking-up；
（3）Steam explosion treatment：
By step（2）Treated, and agricultural crop straw is put into progress Steam explosion treatment in steam blasting tank, takes out after the completion,
It is spare to obtain agricultural residues powder for 100 mesh excessively after drying and crushing；
（4）Activation process：
By step（3）The agricultural residues powder of gained is put into tartaric acid solution and is taken out after 5 ~ 7min of immersion treatment, spend from
Drying for standby after sub- water washing to neutrality；
（5）Modification：
A. argon gas is passed through into reaction kettle, then by methyltriethoxysilane and diisopropanolamine (DIPA) according to weight ratio 1:2~2.4
It is mixed, it is 118 ~ 124 DEG C that then heating, which keeps the temperature in reaction kettle, is stirred to react after 5 ~ 7h of processing and is filtered, subtracted
Pressure, distillation processing, it is spare to obtain mixture A after the completion；Using in the chlorine atom and diisopropanolamine (DIPA) in methyltriethoxysilane
Amino react, mixture A obtained is a kind of silane of modification；
B. it is passed through argon gas into reaction kettle, then will operate mixture A and absolute methanol, R- epoxychloropropane, second two made from a
Amine tetraacethyl disodium, sodium cellulosate, sodium molybdate, stannite powder are according to weight ratio 6 ~ 8:65~70:5~7:0.15~0.25：0.2~
0.5: 2~4：7 ~ 9 are mixed, and it is 44 ~ 50 DEG C that then heating, which keeps the temperature in reaction kettle, is taken after being stirred to react 2 ~ 3h of processing
Go out mixture B is spare；Mixture A and R- epoxychloropropane ingredient occurs quaternization reaction and generates quaternary ammonium salt, later again in second
With on sodium cellulosate, the compound surface for grafting on stannite powder of sodium molybdate under the action of edetate disodium, yellow tin is improved
The surface group type and content of miberal powder, enhance to Li+Insertion fixed effect；
C. it is spare to obtain material C after mixture B made from operation b being carried out rotary evaporation, elution processing, is dried in vacuo；
D. material C and dispersant, deionized water obtained by c will be operated according to weight ratio 10 ~ 14:3~6:90 ~ 100 are mixed,
Then by step（4）Treated, and agricultural residues powder is immersed in this solution, by agricultural residues powder after 2 ~ 3h of supersound process
It filters out spare；
E. the agricultural residues powder obtained by operation d is put into drying box spare after being dried；
（6）Carbonization treatment：
By step（5）Treated, and agricultural residues powder puts into that carbonization treatment is carried out in carbonizing apparatus, is during which to protect with nitrogen
Retaining ring border, the temperature for controlling carbonization are 520 ~ 580 DEG C, are taken out after 2 ~ 2.5h of heat preservation carbonization treatment.After modification again into
Row carbonization treatment, being fixed on modified stable components in biological carbon, optimize its interlayer structure, and if after carbonization treatment
The electrical property quality of biological carbon own face can be influenced by being modified processing again, compromise whole stability.
Further, step（1）Described in sodium hydroxide solution in sodium hydroxide mass fraction be 8 ~ 12%.
Further, step（3）Described in Steam explosion treatment operation be specifically into steam blasting tank to be passed through temperature
For 103 ~ 108 DEG C of vapor, while the pressure in steam blasting tank is increased into 0.5 ~ 0.6MPa, heat-insulation pressure keeping processing 20 ~
After 24min, steam blasting tank is unloaded to normal temperature and pressure in 2min, finally takes out agricultural crop straw.
Further, step（4）Described in tartaric acid solution mesotartaric acid mass fraction be 3 ~ 5%.
Further, step（5）The grain diameter for operating the stannite powder described in b is 0.1 ~ 1 μm.
Further, step（5）The elution processing operated described in c is to carry out elution processing using anhydrous ether.
Further, step（5）It is low molecule wax class dispersant, the supersound process to operate the dispersant described in d
When ultrasonic wave frequency be 300 ~ 350kHz.
Further, step（5）Temperature when operating the drying process described in e in control drying box is 75 ~ 80 DEG C.
Present invention improves the preparation methods of biological carbon, and crop straw refuse, biology obtained are utilized well
Carbon has good electrical property, can be used as the negative material of lithium battery.In preparation process, lye boiling and oxidation have first been carried out
Immersion treatment eliminates the ingredient for being unfavorable for carbonization in stalk, is conducive to promote carbonation rate and material utilization, then be steamed
Vapour explosion treatment, the effective loose institutional framework of agricultural crop straw, improves fibre gap and specific surface area, is subsequent
Processing is laid a good foundation, and tartaric acid solution immersion treatment has then been carried out, and tissue space is further expanded using acid solution, is promoted
The further refinements of fiber fines, improves specific surface area, has activated surface characteristic；Modification then has been carried out again, to
Composite parts-the object based on stannite powder particles secured by specially treated is penetrated into agricultural residues powder fiber
Expect C, on the one hand can promote the specific surface area of biological carbon entirety, enhance the exchange adsorption ability of subsequent bio carbon, another party
Face can expand the spacing of biological carbon interlayer, be conducive to more Li+Insertion, while its same energy of a large amount of active groups for containing
It is enough to be promoted to Li+Embedded fixed and release, improve discharge capacity and cyclical stability jointly, enhance the electrical of biological carbon
Energy；Carbonization treatment is finally carried out, effectively mentioned component is stabilized in biological carbon, improves whole stability in use and product
Matter.
The present invention has the following advantages compared with prior art：
The present invention provides a kind of preparation method of biological carbon, integrated artistic specification produces, biology obtained convenient for batch jobs
Carbon excellent electrical properties, hence it is evident that the capacity and cyclical stability for improving electric discharge enhance it as lithium cell cathode material
Quality, the great market competitiveness and application value.
Specific implementation mode
Embodiment 1
A kind of preparation method of the biological carbon with good electrical properties, includes the following steps：
（1）Boiling is handled：
Agricultural crop straw is put into sodium hydroxide solution and is heated to boiling, is then boiled crops straw after boiling processing 20min
Stalk takes out spare；
（2）Aoxidize immersion treatment：
By step（1）Treated, and agricultural crop straw is put into immersion treatment 4h in the hydrogen peroxide solution that volume fraction is 20%, takes
It is spare after being washed with deionized to neutrality after going out；
（3）Steam explosion treatment：
By step（2）Treated, and agricultural crop straw is put into progress Steam explosion treatment in steam blasting tank, takes out after the completion,
It is spare to obtain agricultural residues powder for 100 mesh excessively after drying and crushing；
（4）Activation process：
By step（3）The agricultural residues powder of gained is put into tartaric acid solution and is taken out after immersion treatment 5min, and deionization is used
Drying for standby after water washing to neutrality；
（5）Modification：
A. argon gas is passed through into reaction kettle, then by methyltriethoxysilane and diisopropanolamine (DIPA) according to weight ratio 1:2 carry out
Mixing, it is 118 DEG C that then heating, which keeps the temperature in reaction kettle, is stirred to react after handling 5h and is filtered, depressurized, at distillation
It is spare to obtain mixture A after the completion for reason；
B. it is passed through argon gas into reaction kettle, then will operate mixture A and absolute methanol, R- epoxychloropropane, second two made from a
Amine tetraacethyl disodium, sodium cellulosate, sodium molybdate, stannite powder are according to weight ratio 6:65:5:0.15：0.2: 2：7 are mixed,
Then heating keep reaction kettle in temperature be 44 DEG C, be stirred to react processing 2h after take out mixture B is spare；
C. it is spare to obtain material C after mixture B made from operation b being carried out rotary evaporation, elution processing, is dried in vacuo；
D. material C and dispersant, deionized water obtained by c will be operated according to weight ratio 10:3:90 are mixed, then by step
（4）Treated, and agricultural residues powder is immersed in this solution, is filtered out agricultural residues powder after supersound process 2h spare；
E. the agricultural residues powder obtained by operation d is put into drying box spare after being dried；
（6）Carbonization treatment：
By step（5）Treated, and agricultural residues powder puts into that carbonization treatment is carried out in carbonizing apparatus, is during which to protect with nitrogen
Retaining ring border, the temperature for controlling carbonization are 520 DEG C, are taken out after heat preservation carbonization treatment 2h.
Further, step（1）Described in sodium hydroxide solution in sodium hydroxide mass fraction be 8%.
Further, step（3）Described in Steam explosion treatment operation be specifically into steam blasting tank to be passed through temperature
For 103 DEG C of vapor, while the pressure in steam blasting tank is increased into 0.5MPa, after heat-insulation pressure keeping handles 20min, then at
Steam blasting tank is unloaded to normal temperature and pressure in 2min, finally takes out agricultural crop straw.
Further, step（4）Described in tartaric acid solution mesotartaric acid mass fraction be 3%.
Further, step（5）The grain diameter for operating the stannite powder described in b is 0.1 ~ 1 μm.
Further, step（5）The elution processing operated described in c is to carry out elution processing using anhydrous ether.
Further, step（5）It is low molecule wax class dispersant, the supersound process to operate the dispersant described in d
When ultrasonic wave frequency be 300kHz.
Further, step（5）Temperature when operating the drying process described in e in control drying box is 75 DEG C.
Embodiment 2
A kind of preparation method of the biological carbon with good electrical properties, includes the following steps：
（1）Boiling is handled：
Agricultural crop straw is put into sodium hydroxide solution and is heated to boiling, is then boiled crops straw after boiling processing 25min
Stalk takes out spare；
（2）Aoxidize immersion treatment：
By step（1）Treated, and agricultural crop straw is put into immersion treatment 5h in the hydrogen peroxide solution that volume fraction is 23%, takes
It is spare after being washed with deionized to neutrality after going out；
（3）Steam explosion treatment：
By step（2）Treated, and agricultural crop straw is put into progress Steam explosion treatment in steam blasting tank, takes out after the completion,
It is spare to obtain agricultural residues powder for 100 mesh excessively after drying and crushing；
（4）Activation process：
By step（3）The agricultural residues powder of gained is put into tartaric acid solution and is taken out after immersion treatment 6min, and deionization is used
Drying for standby after water washing to neutrality；
（5）Modification：
A. argon gas is passed through into reaction kettle, then by methyltriethoxysilane and diisopropanolamine (DIPA) according to weight ratio 1:2.2 into
It goes and mixes, it is 120 DEG C that then heating, which keeps the temperature in reaction kettle, is stirred to react after handling 6h and is filtered, depressurized, at distillation
It is spare to obtain mixture A after the completion for reason；
B. it is passed through argon gas into reaction kettle, then will operate mixture A and absolute methanol, R- epoxychloropropane, second two made from a
Amine tetraacethyl disodium, sodium cellulosate, sodium molybdate, stannite powder are according to weight ratio 7:68:6:0.2：0.4: 3：8 are mixed, so
Afterwards heating keep reaction kettle in temperature be 46 DEG C, be stirred to react processing 2.5h after take out mixture B is spare；
C. it is spare to obtain material C after mixture B made from operation b being carried out rotary evaporation, elution processing, is dried in vacuo；
D. material C and dispersant, deionized water obtained by c will be operated according to weight ratio 12:5:96 are mixed, then by step
（4）Treated, and agricultural residues powder is immersed in this solution, is filtered out agricultural residues powder after supersound process 2.5h spare；
E. the agricultural residues powder obtained by operation d is put into drying box spare after being dried；
（6）Carbonization treatment：
By step（5）Treated, and agricultural residues powder puts into that carbonization treatment is carried out in carbonizing apparatus, is during which to protect with nitrogen
Retaining ring border, the temperature for controlling carbonization are 560 DEG C, are taken out after heat preservation carbonization treatment 2.3h.
Further, step（1）Described in sodium hydroxide solution in sodium hydroxide mass fraction be 10%.
Further, step（3）Described in Steam explosion treatment operation be specifically into steam blasting tank to be passed through temperature
For 105 DEG C of vapor, while the pressure in steam blasting tank is increased into 0.55MPa, after heat-insulation pressure keeping handles 22min, then at
Steam blasting tank is unloaded to normal temperature and pressure in 2min, finally takes out agricultural crop straw.
Further, step（4）Described in tartaric acid solution mesotartaric acid mass fraction be 4%.
Further, step（5）The grain diameter for operating the stannite powder described in b is 0.1 ~ 1 μm.
Further, step（5）The elution processing operated described in c is to carry out elution processing using anhydrous ether.
Further, step（5）It is low molecule wax class dispersant, the supersound process to operate the dispersant described in d
When ultrasonic wave frequency be 330kHz.
Further, step（5）Temperature when operating the drying process described in e in control drying box is 78 DEG C.
Embodiment 3
A kind of preparation method of the biological carbon with good electrical properties, includes the following steps：
（1）Boiling is handled：
Agricultural crop straw is put into sodium hydroxide solution and is heated to boiling, is then boiled crops straw after boiling processing 30min
Stalk takes out spare；
（2）Aoxidize immersion treatment：
By step（1）Treated, and agricultural crop straw is put into immersion treatment 6h in the hydrogen peroxide solution that volume fraction is 25%, takes
It is spare after being washed with deionized to neutrality after going out；
（3）Steam explosion treatment：
By step（2）Treated, and agricultural crop straw is put into progress Steam explosion treatment in steam blasting tank, takes out after the completion,
It is spare to obtain agricultural residues powder for 100 mesh excessively after drying and crushing；
（4）Activation process：
By step（3）The agricultural residues powder of gained is put into tartaric acid solution and is taken out after immersion treatment 7min, and deionization is used
Drying for standby after water washing to neutrality；
（5）Modification：
A. argon gas is passed through into reaction kettle, then by methyltriethoxysilane and diisopropanolamine (DIPA) according to weight ratio 1:2.4 into
It goes and mixes, it is 124 DEG C that then heating, which keeps the temperature in reaction kettle, is stirred to react after handling 7h and is filtered, depressurized, at distillation
It is spare to obtain mixture A after the completion for reason；
B. it is passed through argon gas into reaction kettle, then will operate mixture A and absolute methanol, R- epoxychloropropane, second two made from a
Amine tetraacethyl disodium, sodium cellulosate, sodium molybdate, stannite powder are according to weight ratio 8: 70: 7: 0.25：0.5: 4：9 are mixed
Close, then heating keep reaction kettle in temperature be 50 DEG C, be stirred to react processing 3h after take out mixture B is spare；
C. it is spare to obtain material C after mixture B made from operation b being carried out rotary evaporation, elution processing, is dried in vacuo；
D. material C and dispersant, deionized water obtained by c will be operated according to weight ratio 14:6:100 are mixed, then will step
Suddenly（4）Treated, and agricultural residues powder is immersed in this solution, is filtered out agricultural residues powder after supersound process 3h spare；
E. the agricultural residues powder obtained by operation d is put into drying box spare after being dried；
（6）Carbonization treatment：
By step（5）Treated, and agricultural residues powder puts into that carbonization treatment is carried out in carbonizing apparatus, is during which to protect with nitrogen
Retaining ring border, the temperature for controlling carbonization are 580 DEG C, are taken out after heat preservation carbonization treatment 2.5h.
Further, step（1）Described in sodium hydroxide solution in sodium hydroxide mass fraction be 12%.
Further, step（3）Described in Steam explosion treatment operation be specifically into steam blasting tank to be passed through temperature
For 108 DEG C of vapor, while the pressure in steam blasting tank is increased into 0.6MPa, after heat-insulation pressure keeping handles 24min, then at
Steam blasting tank is unloaded to normal temperature and pressure in 2min, finally takes out agricultural crop straw.
Further, step（4）Described in tartaric acid solution mesotartaric acid mass fraction be 5%.
Further, step（5）The grain diameter for operating the stannite powder described in b is 0.1 ~ 1 μm.
Further, step（5）The elution processing operated described in c is to carry out elution processing using anhydrous ether.
Further, step（5）It is low molecule wax class dispersant, the supersound process to operate the dispersant described in d
When ultrasonic wave frequency be 350kHz.
Further, step（5）Temperature when operating the drying process described in e in control drying box is 80 DEG C.
Comparative example 1
This comparative example 1 compared with Example 2, eliminates step（5）Operation a, operation b in modification and operation c, and
With etc. mass parts stannite powder substitution operation d in material C ingredients, method and step all same in addition to this.
Comparative example 2
This comparative example 2 compared with Example 2, by step（5）Modification and step（6）The process of carbonization treatment carries out pair
It adjusts, that is, uses step（5）Modification processing method is directly modified processing to biological carbon, method and step all same in addition to this.
Control group
Existing agricultural crop straw carbonization treatment technique.
In order to compare effect of the present invention, above-described embodiment 2, comparative example 1, comparative example 2, control group are corresponded into system
The biological carbon obtained is processed into negative material by same process, then presses same procedure again and carries out charge and discharge test, controls lithium ion
The current density of cell negative electrode material is 100mAhg-1, voltage range is 0.01 ~ 3V, is then carried out to the electrical property of negative material
Test, specific correction data are as shown in table 1 below：
Table 1
The biological carbon electrical property quality made from the method for the present invention it can be seen from upper table 1 is obviously improved, enhance its as lithium from
The quality and value of sub- cell negative electrode material provide a kind of better processing scheme of foreground for the recycling of agricultural crop straw,
With good economic benefit.
Claims (8)
1. a kind of preparation method of the biological carbon with good electrical properties, which is characterized in that include the following steps：
（1）Boiling is handled：
Agricultural crop straw is put into sodium hydroxide solution and is heated to boiling, is then boiled crops after boiling 20 ~ 30min of processing
Stalk takes out spare；
（2）Aoxidize immersion treatment：
By step（1）Immersion treatment 4 in the hydrogen peroxide solution that agricultural crop straw is put into volume fraction that treated is 20 ~ 25% ~
6h, it is spare after being washed with deionized to neutrality after taking-up；
（3）Steam explosion treatment：
By step（2）Treated, and agricultural crop straw is put into progress Steam explosion treatment in steam blasting tank, takes out after the completion,
It is spare to obtain agricultural residues powder for 100 mesh excessively after drying and crushing；
（4）Activation process：
By step（3）The agricultural residues powder of gained is put into tartaric acid solution and is taken out after 5 ~ 7min of immersion treatment, spend from
Drying for standby after sub- water washing to neutrality；
（5）Modification：
A. argon gas is passed through into reaction kettle, then by methyltriethoxysilane and diisopropanolamine (DIPA) according to weight ratio 1:2~2.4
It is mixed, it is 118 ~ 124 DEG C that then heating, which keeps the temperature in reaction kettle, is stirred to react after 5 ~ 7h of processing and is filtered, subtracted
Pressure, distillation processing, it is spare to obtain mixture A after the completion；
B. it is passed through argon gas into reaction kettle, then will operate mixture A and absolute methanol, R- epoxychloropropane, second two made from a
Amine tetraacethyl disodium, sodium cellulosate, sodium molybdate, stannite powder are according to weight ratio 6 ~ 8:65~70:5~7:0.15~0.25：0.2~
0.5: 2~4：7 ~ 9 are mixed, and it is 44 ~ 50 DEG C that then heating, which keeps the temperature in reaction kettle, is taken after being stirred to react 2 ~ 3h of processing
Go out mixture B is spare；
C. it is spare to obtain material C after mixture B made from operation b being carried out rotary evaporation, elution processing, is dried in vacuo；
D. material C and dispersant, deionized water obtained by c will be operated according to weight ratio 10 ~ 14:3~6:90 ~ 100 are mixed,
Then by step（4）Treated, and agricultural residues powder is immersed in this solution, by agricultural residues powder after 2 ~ 3h of supersound process
It filters out spare；
E. the agricultural residues powder obtained by operation d is put into drying box spare after being dried；
（6）Carbonization treatment：
By step（5）Treated, and agricultural residues powder puts into that carbonization treatment is carried out in carbonizing apparatus, is during which to protect with nitrogen
Retaining ring border, the temperature for controlling carbonization are 520 ~ 580 DEG C, are taken out after 2 ~ 2.5h of heat preservation carbonization treatment.
2. a kind of preparation method of biological carbon with good electrical properties according to claim 1, which is characterized in that step
（1）Described in sodium hydroxide solution in sodium hydroxide mass fraction be 8 ~ 12%.
3. a kind of preparation method of biological carbon with good electrical properties according to claim 1, which is characterized in that step
（3）Described in Steam explosion treatment operation be specifically that temperature is passed through into steam blasting tank is 103 ~ 108 DEG C of vapor, together
When the pressure in steam blasting tank increased into 0.5 ~ 0.6MPa, after heat-insulation pressure keeping handles 20 ~ 24min, by steam in 2min
Cavity charge containers are unloaded to normal temperature and pressure, finally take out agricultural crop straw.
4. a kind of preparation method of biological carbon with good electrical properties according to claim 1, which is characterized in that step
（4）Described in tartaric acid solution mesotartaric acid mass fraction be 3 ~ 5%.
5. a kind of preparation method of biological carbon with good electrical properties according to claim 1, which is characterized in that step
（5）The grain diameter for operating the stannite powder described in b is 0.1 ~ 1 μm.
6. a kind of preparation method of biological carbon with good electrical properties according to claim 1, which is characterized in that step
（5）The elution processing operated described in c is to carry out elution processing using anhydrous ether.
7. a kind of preparation method of biological carbon with good electrical properties according to claim 1, which is characterized in that step
（5）The dispersant operated described in d is low molecule wax class dispersant, when the supersound process frequency of ultrasonic wave be 300 ~
350kHz。
8. a kind of preparation method of biological carbon with good electrical properties according to claim 1, which is characterized in that step
（5）Temperature when operating the drying process described in e in control drying box is 75 ~ 80 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109535855A (en) * | 2018-10-29 | 2019-03-29 | 刘凡领 | A kind of preparation method of efficient electric hotting mask |
| CN111087263A (en) * | 2019-11-13 | 2020-05-01 | 刘海威 | Composite repairing agent for organic contaminated soil, preparation method and application thereof |
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|---|---|---|---|---|
| WO2010123081A1 (en) * | 2009-04-24 | 2010-10-28 | トヨタ自動車株式会社 | Carbon material and method for producing same |
| CN103466619A (en) * | 2013-09-26 | 2013-12-25 | 山东大学 | Method for preparing active carbon by organic alcohol or organic acid doping modification |
| CN105602590A (en) * | 2016-01-26 | 2016-05-25 | 安徽大地节能科技有限公司 | Carbonizing technology for waste crop straw resources |
| KR101802129B1 (en) * | 2016-06-15 | 2017-11-28 | 한국원자력연구원 | Method for modification of carbon based materials using surfactant and surfactant modified carbon based materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010123081A1 (en) * | 2009-04-24 | 2010-10-28 | トヨタ自動車株式会社 | Carbon material and method for producing same |
| CN103466619A (en) * | 2013-09-26 | 2013-12-25 | 山东大学 | Method for preparing active carbon by organic alcohol or organic acid doping modification |
| CN105602590A (en) * | 2016-01-26 | 2016-05-25 | 安徽大地节能科技有限公司 | Carbonizing technology for waste crop straw resources |
| KR101802129B1 (en) * | 2016-06-15 | 2017-11-28 | 한국원자력연구원 | Method for modification of carbon based materials using surfactant and surfactant modified carbon based materials |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535855A (en) * | 2018-10-29 | 2019-03-29 | 刘凡领 | A kind of preparation method of efficient electric hotting mask |
| CN111087263A (en) * | 2019-11-13 | 2020-05-01 | 刘海威 | Composite repairing agent for organic contaminated soil, preparation method and application thereof |
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