CN105977470B - Silicon dioxide activity carbon composite, preparation method and lead carbon battery - Google Patents
Silicon dioxide activity carbon composite, preparation method and lead carbon battery Download PDFInfo
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- CN105977470B CN105977470B CN201610522873.8A CN201610522873A CN105977470B CN 105977470 B CN105977470 B CN 105977470B CN 201610522873 A CN201610522873 A CN 201610522873A CN 105977470 B CN105977470 B CN 105977470B
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- rice husk
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 37
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 230000000694 effects Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 241000209094 Oryza Species 0.000 claims abstract description 51
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 51
- 235000009566 rice Nutrition 0.000 claims abstract description 51
- 239000010903 husk Substances 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 31
- 238000003763 carbonization Methods 0.000 claims abstract description 22
- 239000003610 charcoal Substances 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 239000002250 absorbent Substances 0.000 claims abstract description 11
- 230000002745 absorbent Effects 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000001994 activation Methods 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000012159 carrier gas Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000011505 plaster Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000006182 cathode active material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 12
- 230000002427 irreversible effect Effects 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 6
- 238000007600 charging Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000019635 sulfation Effects 0.000 description 4
- 238000005670 sulfation reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 235000019750 Crude protein Nutrition 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052924 anglesite Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000011026 diafiltration Methods 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
-
- 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
-
- 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
Abstract
The present invention relates to a kind of silicon dioxide activity carbon composite, preparation method and lead carbon batteries.Preparation method is：1) rice husk inorganic strong acid solution is impregnated, purification；2) purified rice husk is dry, carbonization and an activation process, wherein three sections of heating cycle point, obtain carbonization rice husk；3) carbonization rice husk is put into inorganic strong alkali solution, is then slowly added into dilute inorganic strong acid solution, dilute inorganic strong acid solution and the solute mole ratio in inorganic strong alkali solution of addition are 1~10:1, it stirs, obtain presoma after filtration washing；4) presoma is dried and is activated again, obtain silicon dioxide activity carbon composite.Porous superfine silicon dioxide absorbent charcoal composite material prepared by the present invention, applies it in lead-acid battery cathode active material, improves lead carbon battery cycle life and high current charge-discharge ability to accept, and lead-acid battery cycle life extends one times or more.
Description
Technical field
The invention belongs to battery technology fields, and in particular to a kind of lead carbon battery is multiple with porous superfine silicon dioxide activated carbon
Condensation material and preparation method thereof.
Background technology
Lead-acid accumulator has many advantages, such as cheap, safe, electric performance stablity, and regeneration is at low cost, extensively
Applied to industries such as electric vehicle, the communications industry, power industry energy storage field and rapid development new-energy automobiles.With lithium ion
The hair of the emerging battery technology such as battery, polymer Li-ion battery, Proton Exchange Membrane Fuel Cells, direct methanol fuel cell
The shortcomings that exhibition, lead-acid battery is because of its own, competitiveness weaken.It is being reduced in the share of traditional field.Its disadvantage has：Mass ratio
Energy is low, energy density per unit volume is low, cycle life is short, quick charge ability to accept is weak, low temperature charging and discharging capabilities difference etc..Lead-acid battery
Overdischarge and it is long-term store in the discharged condition when, cathode will be formed it is a kind of it is coarse, be difficult to receive the sulfuric acid of charging
Lead crystallizes, i.e., irreversible sulfation.In the battery failure of dynamic property VRLA lead-acid batteries, 70%-80% is that battery is negative
Caused by " the irreversible sulfation " of pole.Therefore the irreversible sulfate problem of lead-acid battery is overcome, for entire lead-acid battery
Industry development is extremely important.
The addition of Carbon Materials can significantly improve lead-acid battery charge-discharge performance.Effect machine of the Carbon Materials in lead cathode
Reason includes mainly the following：(a) Carbon Materials enhance the electric conductivity of entire cathode；(b) charcoal presence can hinder in cathode
PbSO4Crystal growth is conducive to little particle PbSO independent, easy to dissolve4It is formed；(c) charcoal plays similar molecule in cathode
The effect of pump can promote sulfuric acid to the transmission inside active material in high power charging-discharging.The excellent performance of lead carbon battery
Make it that there is huge application prospect and market value in fields such as hybrid vehicle, energy storage, communication, electric power, aerospaces.
Therefore the Carbon Materials for preparing electrochemical performance are very necessary and highly important for exploitation lead carbon battery.
Porous silica have the characteristics that it is a series of, such as：Chemical property is stablized, acidproof, and purity is high, and density is low, specific surface
Product is big, and pore structure is flourishing.It can be with the light base of silicon of Dry matter formation hydrogen bond if surface is contained.Therefore porous silica is in many
Field obtains application.1890, German company replaced sulfate liquid electrolyte with the translucent gel-like electrolyte of milky,
Colloid battery is obtained, colloid battery has significant advantage, have benefited from following effect compared with conventional lead acid battery：1. colloid grains
The formation of hydrogen bond and hydrophobic bond and breaking is reversible between son, and colloidal electrolyte is made to deform thixotropy；2. shape between colloidal particle
It is an irreversible procedure at silica chemical bond, forms three-dimensional network skeleton that is strong and assembling, colloid is made to have centainly
Intensity and elasticity.
Existing lead carbon battery is made a general survey of, cycle life and high current charge-discharge ability to accept are still less desirable.
Invention content
The present invention, which combines silica and absorbent charcoal material, to be applied in lead carbon battery negative electrode active material, to
Further increase lead carbon battery cycle life and high current charge-discharge ability to accept.
Rice husk main component is that moisture, crude fibre, lignin, crude protein and ash grade, and wherein ash content is mainly titanium dioxide
Silicon.
Rice husk extremely derivative is recycled and prepares lead carbon battery porous silica porous active by the present invention
Carbon composite.
The technical scheme is that:A kind of preparation method of silicon dioxide activity carbon composite, including following steps
Suddenly：
1) rice husk inorganic strong acid solution is impregnated, purification；
2) purified rice husk is dry, carbonization and an activation process, wherein three sections of heating cycle point：
Stage 1：It is warming up to 95~105 DEG C and keeps the temperature；
Stage 2：It is passed through inert protective gas, be warming up to 550~650 DEG C and is kept the temperature；
Stage 3：It is passed through vapor or CO2, it is warming up to 750~850 DEG C and keeps the temperature, then proceedes to logical gas cooling, obtain
To carbonization rice husk；
3) carbonization rice husk is put into inorganic strong alkali solution, is then slowly added into dilute inorganic strong acid solution, dilute nothing of addition
Machine strong acid solution is 1~10 with solute mole ratio in inorganic strong alkali solution:1, it stirs, obtain presoma after filtration washing；
4) presoma is dried and is activated again, wherein heating cycle is：
Stage 1：It is warming up to 95~105 DEG C and keeps the temperature；
Stage 2：It is passed through vapor or CO2, it is warming up to 750~850 DEG C and keeps the temperature, then proceedes to logical gas cooling and obtain
Silicon dioxide activity carbon composite.
In a specific embodiment, the inorganic acid is sulfuric acid or hydrochloric acid solution, and inorganic strong alkali is sodium hydroxide
Or potassium hydroxide solution.
In a specific embodiment, rice husk is impregnated 12~36h, inorganic acid by step 1) in inorganic strong acid solution
0.85~1.25mol/L of concentration.
In a specific embodiment, the step 2) stage 1,2.5~3.5 DEG C/min of heating rate, heat preservation 15~
30min；Stage 2, flow rate of carrier gas 4~6L/min of rate, 5~8 DEG C/min of heating rate keep the temperature 90~120min；Stage 3, carrier gas
Flow velocity 4~6L/min of rate, 5~8 DEG C/min of heating rate keep the temperature 50~80min.
In a specific embodiment, step 3) inorganic strong alkali solution concentration 0.01-1mol/L, inorganic strong alkali solution with
Carbonization rice husk liquid-solid ratio is 1-10:1, inorganic strong acid solution a concentration of 0.01-1mol/L, rate of addition 1-20mL/min are stirred
It is 50-500r/min to mix speed.
In a specific embodiment, the step 4) stage 1,2.5~3.5 DEG C/min of heating rate, heat preservation 15~
30min；Stage 2, flow rate of carrier gas 4~6L/min of rate, 5~8 DEG C/min of heating rate keep the temperature 50~80min.
The present invention also provides a kind of silicon dioxide activity carbon composites being prepared using the above method.
The present invention also provides a kind of cathode lead plasters for lead carbon battery, including above-mentioned silicon dioxide activity charcoal composite wood
Material.
The present invention also provides a kind of negative plate of lead-carbon battery, are prepared as a raw material using the cathode lead plaster.
The present invention also provides a kind of lead carbon batteries, including above-mentioned negative plates.
The present invention utilizes the absorbent charcoal material of porous silica and high-specific surface area, specific mechanism as follows：
High-specific surface area Carbon Materials have capacitive property, and buffer current is played in high power charging-discharging, protect lead cathode
Effect；The certain impurity for including in Carbon Materials can inhibit liberation of hydrogen, therefore can enhance cathode charge acceptance.
Porous silica can form irreversible silicon oxygen bond, form firm three-dimensional network skeleton, apply it to lead
In sour cell active materials, have the advantage that：
1. improving the porosity of negative electrode active material, the sulfuric acid leading crystal to be formed and the shape in pole plate can be effectively isolated
Enable electrolyte ion fast transferring at duct, promotes dissolving of the lead sulfate in recharge process to recycle, to inhibit
The growth of lead sulfate inhibits irreversible sulfation, increases active area, improves cathode charge acceptance；
2. protecting lead-acid battery electrode plate, negative electrode active material is also easy to produce volume contraction and expansion when carrying out charge and discharge；It crosses
The fragile battery cartridge of big dilation, service-strong three-dimensional framework being capable of largely stabilizing actives.
Compared with prior art, the present invention has following advantage：
1. improving the recovery utilization rate of rice husk, new direction is provided for the recovery utilization rate of rice husk, environmental pollution is small, warp
It helps profitable.Traditional rice husk utilization ways are single, only play its combustion heat value, but cause serious pollution to the environment.Although in recent years, will
Research of the rice husk for prepared by activated carbon and silica associated materials is more, but practical application is less.
2. giving full play in rice husk ash, amorphous silicon di-oxide purity is high, rice husk matrix activated carbon material distribution of pores is flourishing
The features such as, prepare the controllable porous superfine silicon dioxide absorbent charcoal composite material of dioxide-containing silica.
3. one-step method prepares porous superfine silicon dioxide absorbent charcoal composite material, avoid porous high-specific surface area activity
Charcoal and porous superfine silicon dioxide are separately prepared, and equipment is simple, are easily realized, and be evenly distributed.
It, will be porous super 4. porous superfine silicon dioxide absorbent charcoal composite material is applied in lead-acid battery cathode active material
The advantage and absorbent charcoal material that fine silica is applied in lead-acid battery are applied to the advantage in lead-acid battery and combine, and carry
The distribution of high sulfuric acid in the negative active material improves negative electrode active material conductive capability, inhibits bulky grain lead sulfate to be formed, carries
High negative plate high current charge-discharge ability to accept, retention of charge inhibit irreversible sulfation, protect negative plate, extend
Battery cycle life.
Porous superfine silicon dioxide absorbent charcoal composite material prepared by the present invention applies it to lead-acid battery cathode activity
In substance, lead-acid battery cycle life extends one times or more.
Specific implementation mode
Embodiment 1
By rice husk extremely derivative comprehensive reutilization and prepares lead carbon battery and answered with porous superfine silicon dioxide activated carbon
The method of condensation material, includes the following steps：
1) rice husk is put into sulfuric acid solution and is impregnated for 24 hours, sulfuric acid concentration 1mol/L after filtration washing, is purified rice husk；
2) purification rice husk is put into tube furnace, by drying, carbonization and an activation process, obtains carbonization rice husk；
Three temperature control stages of heating cycle point：
Temperature rise period 1,3 DEG C/min of heating rate keep the temperature 20min to 100 DEG C；
Temperature rise period 2, it is passed through N2, flow rate of carrier gas rate 5L/min, 6 DEG C/min of heating rate keep the temperature 100min to 600 DEG C；
Temperature rise period 3, it is passed through vapor, flow rate of carrier gas rate 5L/min, 6 DEG C/min of heating rate are kept the temperature to 800 DEG C
Then 60min stops heating, continue ventilation body to room temperature；
3) carbonization rice husk is put into sodium hydroxide solution (concentration 0.1mol/L), sodium hydroxide solution and carbonization rice husk liquid
Gu than being 5:1 (mass ratio)；It is then slowly added into dilute sulfuric acid (a concentration of 0.1mol/L), dilute sulfuric acid rate of addition is 10mL/
Min, solute mole ratio is 2 in the dilution heat of sulfuric acid and sodium hydroxide solution of instillation:1, stir (mixing speed 100r/
Min) presoma is obtained after filtration washing；
4) presoma is placed in tube furnace, is activated by drying and again, be dried to obtain porous superfine silicon dioxide and live
Property carbon composite；
Heating cycle is：Temperature rise period 1,3 DEG C/min of heating rate keep the temperature 20min to 100 DEG C；It temperature rise period 2, is passed through
Vapor, flow rate of carrier gas rate 5L/min, 6 DEG C/min of heating rate keep the temperature 60min to 800 DEG C, then stop heating, continue to lead to
Gas is to room temperature.
Rice husk of the present invention extremely derivative includes rice husk, rice hull carbon and rice hull ash, if using rice hull carbon and rice husk
Ash can directly carry out third step sodium hydroxide solution processing.
Embodiment 2
By rice husk extremely derivative comprehensive reutilization and prepares lead carbon battery and answered with porous superfine silicon dioxide activated carbon
The method of condensation material, includes the following steps：
1) rice husk is put into sulfuric acid solution and impregnates 36h, sulfuric acid concentration 0.85mol/L after filtration washing, is purified rice
Shell；
2) purification rice husk is put into tube furnace, by drying, carbonization and an activation process, obtains carbonization rice husk；
Three temperature control stages of heating cycle point：
Temperature rise period 1,2.5 DEG C/min of heating rate keep the temperature 30min to 95 DEG C；
Temperature rise period 2, it is passed through N2, flow rate of carrier gas rate 4L/min, 5 DEG C/min of heating rate keep the temperature 120min to 550 DEG C；
Temperature rise period 3, it is passed through CO2, flow rate of carrier gas rate 4L/min, 5 DEG C/min of heating rate, to 750 DEG C, heat preservation 80min,
Then stop heating, continue ventilation body to room temperature；
3) carbonization rice husk is put into sodium hydroxide solution (concentration 1mol/L), sodium hydroxide solution and carbonization rice husk liquid are solid
Than being 1:1 (mass ratio)；It is then slowly added into dilute sulfuric acid (a concentration of 1mol/L), dilute sulfuric acid rate of addition is 1mL/min, is instilled
Dilution heat of sulfuric acid and sodium hydroxide solution in solute mole ratio be 1:1, diafiltration is crossed in stirring (mixing speed 500r/min)
Presoma is obtained after washing；
4) presoma is placed in tube furnace, is activated by drying and again, be dried to obtain porous superfine silicon dioxide and live
Property carbon composite；
Heating cycle is：Temperature rise period 1,3.5 DEG C/min of heating rate keep the temperature 15min to 105 DEG C；Temperature rise period 2 leads to
Enter CO2, flow rate of carrier gas rate 6L/min, 8 DEG C/min of heating rate keep the temperature 50min to 850 DEG C, then stop heating, continue to lead to
Gas is to room temperature.
Embodiment 3
By rice husk extremely derivative comprehensive reutilization and prepares lead carbon battery and answered with porous superfine silicon dioxide activated carbon
The method of condensation material, includes the following steps：
1) rice husk is put into hydrochloric acid solution and impregnates 12h, concentration of hydrochloric acid 1.25mol/L after filtration washing, is purified rice
Shell；
2) purification rice husk is put into tube furnace, by drying, carbonization and an activation process, obtains carbonization rice husk；
Three temperature control stages of heating cycle point：
Temperature rise period 1,3.5 DEG C/min of heating rate keep the temperature 15min to 105 DEG C；
Temperature rise period 2, it is passed through N2, flow rate of carrier gas rate 6L/min, 8 DEG C/min of heating rate keep the temperature 90min to 650 DEG C；
Temperature rise period 3, it is passed through vapor, flow rate of carrier gas rate 6L/min, 8 DEG C/min of heating rate are kept the temperature to 850 DEG C
Then 50min stops heating, continue ventilation body to room temperature；
3) carbonization rice husk is put into potassium hydroxide solution (concentration 0.01mol/L), potassium hydroxide solution and carbonization rice husk
Liquid-solid ratio is 10:1 (mass ratio)；It is then slowly added into dilute hydrochloric acid (a concentration of 0.01mol/L), dilute hydrochloric acid rate of addition is
20mL/min, solute mole ratio is 10 in the dilute hydrochloric acid solution and potassium hydroxide solution of instillation:1, (mixing speed is for stirring
Presoma 50r/min) is obtained after filtration washing；
4) presoma is placed in tube furnace, is activated by drying and again, be dried to obtain porous superfine silicon dioxide and live
Property carbon composite；
Heating cycle is：Temperature rise period 1,2.5 DEG C/min of heating rate keep the temperature 30min to 95 DEG C；Temperature rise period 2 leads to
Enter CO2, flow rate of carrier gas rate 4L/min, 5 DEG C/min of heating rate keep the temperature 80min to 750 DEG C, then stop heating, continue to lead to
Gas is to room temperature.
To test its electrical property, following cathode lead plaster is prepared：Lead paste formula (mass parts) is：100 (oxidizability of lead powder
75%), carbon fiber 0.05, barium sulfate 0.4, humic acid 0.7, pure water 6-7, carbon black 0.2, sulfuric acid (density 1.20gcm-3) 14,
Adjust water：1~2, absorbent charcoal composite material is added in 1% ratio.Weigh corresponding proportion lead plaster siccative and activated carbon composite wood
Expect, is placed in grinding 30min in mortar and is uniformly mixed to material, sulfuric acid stirring is added, addition adjusts water and adjusts humidity of materials, stirring
Lead plaster slurry is obtained after uniformly.
Cathode lead plaster obtained above is coated on negative electrode grid, and carries out polar plate solidification and chemical conversion, lead charcoal electricity is made
The negative plates in pond.By negative plates together with other necessary components such as anode plate, partition board, battery container cover, electrolyte
It is assembled into lead carbon battery.Absorbent charcoal composite material is replaced to prepare lead carbon battery with normal activated carbon, as a comparison battery.
The lead carbon battery of above-mentioned preparation is tested for the property as follows：
(3) large current discharging capability
After battery is fully charged, 5h is stood, then with 4I3A current discharges are to 1.50V, and discharge time is multiplied by discharge current, just
Discharge capacity of the cell can be obtained.
(2) quick charge capability
After battery is fully charged, 5h is stood, is discharged to 1.65V, then 6I3A constant-current charges are to 2.5V again with 2.5V constant pressures
It charges, after two sections of charging time total 1h, battery standing 5h, with I3For A current discharges to 1.65V, discharge time is multiplied by electric discharge electricity
Stream, can obtain quickly charging battery capacity.
(3) the HRPSoC pulse cycles service life
After battery is fully charged, it is discharged to certain charging state.Then with 2.5I3Discharge 30s, stands 7s, 2.5I3Pressure limiting
2.5V chargings 31s, standing 7s are a pulse charge and discharge cycles, are recycled to battery discharge current potential and end less than 1.75V, record follows
Ring number.
Test result is as follows shown in table：
Claims (8)
1. a kind of preparation method of silicon dioxide activity carbon composite, it is characterised in that including following steps：
1）Rice husk inorganic strong acid solution is impregnated, purification；
A concentration of 0.85 ~ 1.25mol/L of the inorganic strong acid solution；
2）Purified rice husk is dry, carbonization and an activation process, wherein three sections of heating cycle point：
Stage 1：It is warming up to 95 ~ 105 DEG C and keeps the temperature；
Stage 2：It is passed through inert protective gas, be warming up to 550 ~ 650 DEG C and is kept the temperature；
Stage 3：It is passed through vapor or CO2, it is warming up to 750 ~ 850 DEG C and keeps the temperature, then proceedes to logical gas cooling, be carbonized
Rice husk；
Stage 1 in the step 2), 2.5 ~ 3.5 DEG C/min of heating rate keep the temperature 15 ~ 30min；Stage 2, flow rate of carrier gas rate 4 ~
6L/min, 5 ~ 8 DEG C/min of heating rate keep the temperature 90 ~ 120min；Stage 3, flow rate of carrier gas 4 ~ 6L/min of rate, heating rate 5 ~ 8
DEG C/min, keep the temperature 50 ~ 80min；
3）Carbonization rice husk is put into inorganic strong alkali solution, is then slowly added into dilute inorganic strong acid solution, addition it is dilute inorganic strong
Acid solution is 1 ~ 10 with solute mole ratio in inorganic strong alkali solution:1, it stirs, obtain presoma after filtration washing；
A concentration of 0.01-1mol/L of the inorganic strong alkali solution, a concentration of 0.01- of inorganic strong acid solution in the step 3)
1mol/L；
4）Presoma is dried and is activated again, wherein heating cycle is：
Stage 1：It is warming up to 95 ~ 105 DEG C and keeps the temperature；
Stage 2：It is passed through vapor or CO2, it is warming up to 750 ~ 850 DEG C and keeps the temperature, then proceedes to logical gas cooling and obtain titanium dioxide
Silicon absorbent charcoal composite material；
Stage 1 in the step 4), 2.5 ~ 3.5 DEG C/min of heating rate keep the temperature 15 ~ 30min；Stage 2, flow rate of carrier gas rate 4 ~
6L/min, 5 ~ 8 DEG C/min of heating rate keep the temperature 50 ~ 80min.
2. the preparation method of silicon dioxide activity carbon composite according to claim 1, it is characterised in that described inorganic
Strong acid solution is sulfuric acid or hydrochloric acid solution, and inorganic strong alkali solution is sodium hydroxide or potassium hydroxide solution.
3. the preparation method of silicon dioxide activity carbon composite according to claim 1 or 2, it is characterised in that step 1）
Rice husk is impregnated into 12~36h in inorganic strong acid solution.
4. the preparation method of silicon dioxide activity carbon composite according to claim 1, it is characterised in that step 3）In
Inorganic strong alkali solution is 1-10 with carbonization rice husk liquid-solid ratio:1, rate of addition 1-20mL/min, mixing speed are 50-500 r/
min。
5. a kind of silicon dioxide activity carbon composite being prepared using one of claim 1 ~ 4 the method.
6. a kind of cathode lead plaster for lead carbon battery, it is characterised in that including the silicon dioxide activity charcoal described in claim 5
Composite material.
7. a kind of negative plate of lead-carbon battery, it is characterised in that use the cathode lead plaster described in claim 6 for raw material prepare and
At.
8. a kind of lead carbon battery, it is characterised in that including the negative plates described in claim 7.
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| CN106981644A (en) * | 2017-05-24 | 2017-07-25 | 华中科技大学 | A kind of porous carbon based on biomass/sulphur composite material and preparation method thereof and its application |
| CN107732244A (en) * | 2017-10-10 | 2018-02-23 | 吉林省凯禹电化学储能技术发展有限公司 | A kind of rice husk base charcoal based additive for lead carbon battery negative pole |
| CN110571433A (en) * | 2019-08-21 | 2019-12-13 | 吉林大学 | negative electrode carbon additive for improving charge acceptance of lead-carbon battery and application thereof |
| CN110713188A (en) * | 2019-10-18 | 2020-01-21 | 中国石油大学(华东) | Method for preparing silicon-carbon negative electrode material for lithium ion battery from rice hulls |
| CN111627718A (en) * | 2020-06-09 | 2020-09-04 | 吉林大学 | Preparation method of lead-carbon supercapacitor positive electrode |
| CN113832137A (en) * | 2021-10-25 | 2021-12-24 | 西安热工研究院有限公司 | Active coke immobilized carbonic anhydrase and preparation method and application thereof |
| CN114039041B (en) * | 2021-11-04 | 2022-09-09 | 昆明理工恒达科技股份有限公司 | High-capacity lead-carbon energy storage battery and preparation method thereof |
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