CN105977470A - Silicon dioxide active carbon composite material and preparation method thereof as well as lead-carbon battery - Google Patents
Silicon dioxide active carbon composite material and preparation method thereof as well as lead-carbon battery Download PDFInfo
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- CN105977470A CN105977470A CN201610522873.8A CN201610522873A CN105977470A CN 105977470 A CN105977470 A CN 105977470A CN 201610522873 A CN201610522873 A CN 201610522873A CN 105977470 A CN105977470 A CN 105977470A
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- silicon dioxide
- lead
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 49
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 37
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 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
- 238000010438 heat treatment Methods 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 28
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 230000004913 activation Effects 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000010903 husk Substances 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 239000003610 charcoal Substances 0.000 claims description 19
- 238000003763 carbonization Methods 0.000 claims description 18
- 239000002250 absorbent Substances 0.000 claims description 16
- 230000002745 absorbent Effects 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 16
- 239000012159 carrier gas Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000011505 plaster Substances 0.000 claims description 8
- 238000009423 ventilation Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 241000790917 Dioxys <bee> Species 0.000 claims description 3
- 229910003978 SiClx Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims 1
- 239000013543 active substance Substances 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 5
- 230000003213 activating effect Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- 230000002035 prolonged effect Effects 0.000 abstract 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 230000008901 benefit Effects 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 6
- 241001597008 Nomeidae Species 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 230000002427 irreversible effect Effects 0.000 description 5
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 230000019635 sulfation Effects 0.000 description 4
- 238000005670 sulfation reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000126 substance Substances 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
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 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
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 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
- 230000002441 reversible effect Effects 0.000 description 2
- 238000012360 testing method Methods 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-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
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 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
- 238000005184 irreversible process Methods 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 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
- 239000000203 mixture Substances 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 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
- 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
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001629 suppression 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 invention relates to a silicon dioxide active carbon composite material and a preparation method thereof as well as a lead-carbon battery. The preparation method comprises the following steps: (1) soaking rice hulls with an inorganic strong acid solution and purifying; (2) drying and carbonizing the purified rice hulls and carrying out activation treatment for the first time to obtain carbonized rice hulls, wherein a heating system is divided into three sections; (3) putting the carbonized rice hulls into an inorganic strong alkali solution, and slowly adding a diluted inorganic strong acid solution, wherein the mol ratio of solutes in the added inorganic strong acid solution and inorganic strong alkali solution is (1 to 10): 1; stirring, filtering and washing, thus obtaining a precursor; (4) drying and activating the precursor for the second time to obtain the silicon dioxide active carbon composite material. The porous ultrafine silicon dioxide active carbon composite material prepared by the preparation method is applied into active substances of a negative pole of a lead acid battery, so that the cycle life of the lead-carbon battery is prolonged, and a large-current charging/discharging accepting capability of the lead-carbon battery is improved; the cycle life of the lead acid battery is prolonged by more than one time.
Description
Technical field
The invention belongs to cell art, be specifically related to a kind of lead carbon battery porous superfine silicon dioxide absorbent charcoal composite material
And preparation method thereof.
Background technology
Lead-acid accumulator have cheap, safety is high, electric performance stablity, regeneration low cost and other advantages, extensively apply
In electric motor car, the communications industry, power industry energy storage field and develop rapidly the industries such as new-energy automobile.Along with lithium ion battery,
The development of the emerging battery technologies such as polymer Li-ion battery, Proton Exchange Membrane Fuel Cells, DMFC, plumbic acid
Battery weakens because of the shortcoming of himself, competitiveness.Share in traditional field reduces.Its shortcoming has: specific 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 is being put excessively
Electricity and when storing in the discharged condition for a long time, its negative pole will form a kind of lead sulfate crystallization thick, that be difficult to accept charging,
The most irreversible sulfation.In the battery failure of dynamic property VRLA lead-acid battery, have 70%-80% be battery cathode " no
Reversible sulfation " cause.Therefore the irreversible sulfate problem of lead-acid battery is overcome, for whole lead-acid battery industry development,
It is extremely important.
The addition of Carbon Materials, it is possible to significantly improve lead-acid battery charge-discharge performance.The Carbon Materials mechanism of action in lead negative pole is main
Including following some: (a) Carbon Materials enhances the electric conductivity of whole negative pole；B () charcoal exists can hinder PbSO in negative pole4
Crystal growth, the most independent, to be prone to dissolving little granule PbSO4Formed；C () charcoal plays similar molecular pump in negative pole
Effect, can promote that when high power charging-discharging sulphuric acid is to the transmission within active substance.The excellent performance of lead carbon battery makes it
In fields such as hybrid vehicle, energy storage, communication, electric power, Aero-Space, there is huge application prospect and market value.Cause
This prepares the Carbon Materials of electrochemical performance, is the most necessary and highly important for exploitation lead carbon battery.
Porous silica has a series of feature, such as: stable chemical nature, acidproof, and purity is high, and density is low, specific surface area
Greatly, pore structure is flourishing.If surface contain can with the silicon of Dry matter formation hydrogen bond light base.Therefore porous silica is led in many
Territory obtains application.1890, German company replaced sulfate liquid electrolyte with the translucent gel-like electrolyte of milky,
To colloid battery, colloid battery, compared with conventional lead acid battery, has significant advantage, has benefited from following effect: 1. colloidal particle
Between hydrogen bond and the formation of hydrophobic bond and to break be reversible, make colloidal electrolyte deform thixotropy；2. between colloidal particle, form silicon
Oxygen chemical key is an irreversible process, forms three-dimensional network skeleton that is strong and that assemble, make colloid have certain intensity and
Elastic.
Making a general survey of existing lead carbon battery, its cycle life and high current charge-discharge ability to accept are the most less desirable.
Summary of the invention
Silicon dioxide and absorbent charcoal material are combined and are applied in lead carbon battery negative electrode active material by the present invention, thus further
Improve lead carbon battery cycle life and high current charge-discharge ability to accept.
Rice husk is mainly composed of moisture, crude fibre, lignin, crude protein and ash and grades, and wherein ash is mainly silicon dioxide.
Rice husk extremely derivant is recycled and prepares lead carbon battery porous silica porous activated carbon composite wood by the present invention
Material.
The technical scheme is that the preparation method of a kind of silicon dioxide activity carbon composite, the step including following:
1) rice husk inorganic strong acid solution is soaked, purifies；
2) rice husk after purifying is dried, carbonization and an activation processing, and wherein heating cycle divides three sections:
Stage 1: be warmed up to 95～105 DEG C and be incubated；
In the stage 2: be passed through inert protective gas, it is warmed up to 550～650 DEG C and is incubated；
Stage 3: be passed through steam or CO2, it is warmed up to 750～850 DEG C and is incubated, then proceeding to body cooling of ventilating, obtain carbon
Change rice husk；
3) carbonization rice husk is put in inorganic strong alkali solution, be then slowly added into dilute inorganic strong acid solution, dilute inorganic acid of addition
Solution is 1～10:1 with solute mole ratio in inorganic strong alkali solution, obtains presoma after stirring, filtration washing；
4) being dried by presoma and again activate, wherein heating cycle is:
Stage 1: be warmed up to 95～105 DEG C and be incubated；
Stage 2: be passed through steam or CO2, it is warmed up to 750～850 DEG C and is incubated, then proceeding to ventilation body cooling and obtain dioxy
SiClx absorbent charcoal composite material.
In a detailed description of the invention, described inorganic acid is sulphuric acid or hydrochloric acid solution, and inorganic strong alkali is sodium hydroxide or hydrogen-oxygen
Change potassium solution.
In a detailed description of the invention, step 1) rice husk soaked in inorganic strong acid solution 12～36h, inorganic acid concentration
0.85～1.25mol/L.
In a detailed description of the invention, step 2) stage 1, heating rate 2.5～3.5 DEG C/min, it is incubated 15～30min；Rank
Section 2, flow rate of carrier gas rate 4～6L/min, heating rate 5～8 DEG C/min, it is incubated 90～120min；Stage 3, flow rate of carrier gas rate
4～6L/min, heating rate 5～8 DEG C/min, it is incubated 50～80min.
In a detailed description of the invention, step 3) inorganic strong alkali solution concentration 0.01-1mol/L, inorganic strong alkali solution and carbonization
Rice husk liquid-solid ratio is 1-10:1, and inorganic strong acid solution concentration is 0.01-1mol/L, and rate of addition is 1-20mL/min, mixing speed
For 50-500r/min.
In a detailed description of the invention, step 4) stage 1, heating rate 2.5～3.5 DEG C/min, it is incubated 15～30min；Rank
Section 2, flow rate of carrier gas rate 4～6L/min, heating rate 5～8 DEG C/min, it is incubated 50～80min.
The present invention also provides for a kind of silicon dioxide activity carbon composite using said method to prepare.
The present invention also provides for a kind of cathode lead plaster for lead carbon battery, including above-mentioned silicon dioxide activity carbon composite.
The present invention also provides for a kind of negative plate of lead-carbon battery, and the cathode lead plaster described in employing is that raw material is prepared from.
The present invention also provides for a kind of lead carbon battery, including above-mentioned negative plates.
The present invention utilizes the absorbent charcoal material of porous silica and high-specific surface area, and concrete mechanism is as follows:
High-specific surface area Carbon Materials has capacitive property, plays buffer current, the effect of protection lead negative pole when high power charging-discharging；
Some impurity comprised in Carbon Materials can suppress liberation of hydrogen, therefore, it is possible to strengthen negative pole charge acceptance.
Porous silica can form irreversible siliconoxygen bond, forms firm three-dimensional network skeleton, applies it to lead-acid battery
In active substance, have the advantage that
1. improve the porosity of negative electrode active material, it is possible to be effectively isolated the lead sulfate crystal of formation and in pole plate, form duct
Enable electrolyte ion fast transferring, promote lead sulfate dissolving recycling during recharging, thus suppress lead sulfate
Growth, suppresses irreversible sulfation, increases active area, improves negative pole charge acceptance；
2. protection lead-acid battery electrode plate, negative electrode active material, when carrying out discharge and recharge, is easily generated volume contraction and expansion；Excessive
The fragile battery cartridge of dilation, service-strong three-dimensional framework can stabilizing actives to a great extent.
Compared with prior art, the present invention has the advantage that
1. improving the recovery utilization rate of rice husk, the recovery utilization rate for rice husk provides new direction, and environmental pollution is little, economic effect
Benefit is good.Tradition rice husk utilization ways is single, simply plays its combustion heat value, but big for environment pollution.Although in recent years, by rice
The research that shell is prepared for activated carbon and silicon dioxide associated materials is more, but actual application is less.
2. give full play to the features such as amorphous silicon di-oxide purity in rice husk ash is high, rice husk matrix activated carbon material distribution of pores is flourishing,
Prepare the porous superfine silicon dioxide absorbent charcoal composite material that dioxide-containing silica is controlled.
3. one-step method prepares porous superfine silicon dioxide absorbent charcoal composite material, it is to avoid by porous active carbon with high specific surface area with many
Hole superfine silicon dioxide is separately prepared, and equipment is simple, easily realizes, and is evenly distributed.
4. during porous superfine silicon dioxide absorbent charcoal composite material is applied to lead-acid battery cathode active substance, by ultra-fine for porous dioxy
Advantage that SiClx is applied in lead-acid battery and the advantage that absorbent charcoal material is applied in lead-acid battery combine, and improve sulphuric acid and exist
Distribution in negative electrode active material, improves negative electrode active material conductive capability, and suppression bulky grain lead sulfate is formed, and improves negative plate
High current charge-discharge ability to accept, retention of charge, suppress irreversible sulfation, protects negative plate, extends circulating battery
Life-span.
Porous superfine silicon dioxide absorbent charcoal composite material prepared by the present invention, applies it to lead-acid battery cathode active substance
In, lead-acid battery cycle life extends more than one times.
Detailed description of the invention
Embodiment 1
By rice husk extremely derivant comprehensive reutilization and prepare lead carbon battery porous superfine silicon dioxide absorbent charcoal composite material
Method, comprises the following steps:
1) rice husk is put into immersion 24h, sulfuric acid concentration 1mol/L in sulfuric acid solution, after filtration washing, is purified rice husk；
2) purification rice husk is put into tube furnace, through dry, carbonization and an activation processing, obtain carbonization rice husk；
Heating cycle is divided three temperature control stages:
Temperature rise period 1,3 DEG C/min of heating rate, to 100 DEG C, it is incubated 20min；
Temperature rise period 2, it is passed through N2, flow rate of carrier gas rate 5L/min, 6 DEG C/min of heating rate, to 600 DEG C, it is incubated 100min；
Temperature rise period 3, it is passed through steam, flow rate of carrier gas rate 5L/min, 6 DEG C/min of heating rate, to 800 DEG C, is incubated 60min,
Then stop heating, continue ventilation body to room temperature；
3) carbonization rice husk is put in sodium hydroxide solution (concentration 0.1mol/L), sodium hydroxide solution and carbonization rice husk liquid-solid ratio
For 5:1 (mass ratio)；Being then slowly added into dilute sulfuric acid (concentration is 0.1mol/L), dilute sulfuric acid rate of addition is 10mL/min,
In the dilution heat of sulfuric acid instilled and sodium hydroxide solution, solute mole ratio is for 2:1, stirs (mixing speed is 100r/min) mistake
Presoma is obtained after filter washing；
4) presoma is placed in tube furnace, through being dried and again activating, is dried to obtain porous superfine silicon dioxide activated carbon multiple
Condensation material；
Heating cycle is: the temperature rise period 1,3 DEG C/min of heating rate, to 100 DEG C, is incubated 20min；Temperature rise period 2, it is passed through
Steam, flow rate of carrier gas rate 5L/min, 6 DEG C/min of heating rate, to 800 DEG C, it is incubated 60min, then stops heating, continue
Continuous ventilation body is to room temperature.
Rice husk of the present invention extremely derivant includes rice husk, rice hull carbon and rice hull ash, if using rice hull carbon and rice hull ash permissible
Directly carry out the 3rd step sodium hydroxide solution to process.
Embodiment 2
By rice husk extremely derivant comprehensive reutilization and prepare lead carbon battery porous superfine silicon dioxide absorbent charcoal composite material
Method, comprises the following steps:
1) rice husk is put into immersion 36h, sulfuric acid concentration 0.85mol/L in sulfuric acid solution, after filtration washing, is purified rice husk；
2) purification rice husk is put into tube furnace, through dry, carbonization and an activation processing, obtain carbonization rice husk；
Heating cycle is divided three temperature control stages:
Temperature rise period 1,2.5 DEG C/min of heating rate, to 95 DEG C, it is incubated 30min；
Temperature rise period 2, it is passed through N2, flow rate of carrier gas rate 4L/min, 5 DEG C/min of heating rate, to 550 DEG C, it is incubated 120min；
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, it is incubated 80min,
Then stop heating, continue ventilation body to room temperature；
3) carbonization rice husk is put in sodium hydroxide solution (concentration 1mol/L), sodium hydroxide solution and carbonization rice husk liquid-solid ratio
For 1:1 (mass ratio)；Being then slowly added into dilute sulfuric acid (concentration is 1mol/L), dilute sulfuric acid rate of addition is 1mL/min, drips
In the dilution heat of sulfuric acid entered and sodium hydroxide solution, solute mole ratio is for 1:1, and stirring (mixing speed is 500r/min) is filtered
Presoma is obtained after washing；
4) presoma is placed in tube furnace, through being dried and again activating, is dried to obtain porous superfine silicon dioxide activated carbon multiple
Condensation material；
Heating cycle is: the temperature rise period 1,3.5 DEG C/min of heating rate, to 105 DEG C, is incubated 15min；Temperature rise period 2, logical
Enter CO2, flow rate of carrier gas rate 6L/min, 8 DEG C/min of heating rate, to 850 DEG C, it is incubated 50min, then stops heating, continue
Continuous ventilation body is to room temperature.
Embodiment 3
By rice husk extremely derivant comprehensive reutilization and prepare lead carbon battery porous superfine silicon dioxide absorbent charcoal composite material
Method, comprises the following steps:
1) rice husk is put into immersion 12h, concentration of hydrochloric acid 1.25mol/L in hydrochloric acid solution, after filtration washing, is purified rice husk；
2) purification rice husk is put into tube furnace, through dry, carbonization and an activation processing, obtain carbonization rice husk；
Heating cycle is divided three temperature control stages:
Temperature rise period 1,3.5 DEG C/min of heating rate, to 105 DEG C, it is incubated 15min；
Temperature rise period 2, it is passed through N2, flow rate of carrier gas rate 6L/min, 8 DEG C/min of heating rate, to 650 DEG C, it is incubated 90min；
Temperature rise period 3, it is passed through steam, flow rate of carrier gas rate 6L/min, 8 DEG C/min of heating rate, to 850 DEG C, is incubated 50min,
Then stop heating, continue ventilation body to room temperature；
3) being put into by carbonization rice husk in potassium hydroxide solution (concentration 0.01mol/L), potassium hydroxide solution and carbonization rice husk are liquid-solid
Ratio is 10:1 (mass ratio)；Being then slowly added into dilute hydrochloric acid (concentration is 0.01mol/L), dilute hydrochloric acid rate of addition is 20mL/min,
In the dilute hydrochloric acid solution instilled and potassium hydroxide solution, solute mole ratio is for 10:1, stirs (mixing speed is 50r/min) mistake
Presoma is obtained after filter washing；
4) presoma is placed in tube furnace, through being dried and again activating, is dried to obtain porous superfine silicon dioxide activated carbon multiple
Condensation material；
Heating cycle is: the temperature rise period 1,2.5 DEG C/min of heating rate, to 95 DEG C, is incubated 30min；Temperature rise period 2, logical
Enter CO2, flow rate of carrier gas rate 4L/min, 5 DEG C/min of heating rate, to 750 DEG C, it is incubated 80min, then stops heating, continue
Continuous ventilation body is to room temperature.
For testing its electrical property, prepare following cathode lead plaster: lead paste formula (mass parts) is: Hydrocerussitum (Ceruse) 100 (oxidizability 75%),
Carbon fiber 0.05, barium sulfate 0.4, humic acid 0.7, pure water 6-7, white carbon black 0.2, sulphuric acid (density 1.20g cm-3) 14, adjust
Whole water: 1～2, absorbent charcoal composite material is added in the ratio of 1%.Weigh corresponding proportion lead plaster siccative and absorbent charcoal composite material,
It is placed in mortar grinding 30min to adjust humidity of materials to material mix homogeneously, addition sulphuric acid stirring, addition adjustment water, stir all
Lead plaster slurry is obtained after even.
Above-mentioned prepared cathode lead plaster is coated on negative electrode grid, and carries out polar plate solidification and chemical conversion, make the negative of lead carbon battery
Pole pole plate.Negative plates is assembled into together with other necessary assembly such as anode plate, dividing plate, battery container cover, electrolyte etc.
Lead carbon battery.Absorbent charcoal composite material is replaced to prepare lead carbon battery with normal activated carbon, battery as a comparison.
The lead carbon battery of above-mentioned preparation is carried out as follows performance test:
(3) large current discharging capability
After battery is fully charged, stand 5h, then with 4I3A current discharge is multiplied by discharge current to 1.50V, discharge time, just may be used
Obtain discharge capacity of the cell.
(2) quick charge capability
After battery is fully charged, stands 5h, be discharged to 1.65V, then 6I3A constant-current charge fills with 2.5V constant voltage to 2.5V again
Electricity, two periods of charging intervals amount to 1h, after battery standing 5h, with I3A current discharge, to 1.65V, is multiplied by electric discharge electricity discharge time
Stream, just can get quickly charging battery capacity.
(3) the HRPSoC pulse cycle life-span
After battery is fully charged, it is discharged to certain charging state.Then with 2.5I3Electric discharge 30s, stands 7s, 2.5I3Pressure limiting 2.5V
Charging 31s, standing 7s is a pulse charge and discharge cycles, is recycled to battery discharge current potential and ends less than 1.75V, record circulation
The number of turns.
Test result is as shown in the table:
Claims (10)
1. the preparation method of a silicon dioxide activity carbon composite, it is characterised in that include following step:
1) rice husk inorganic strong acid solution is soaked, purifies；
2) rice husk after purifying is dried, carbonization and an activation processing, and wherein heating cycle divides three sections:
Stage 1: be warmed up to 95～105 DEG C and be incubated；
In the stage 2: be passed through inert protective gas, it is warmed up to 550～650 DEG C and is incubated；
Stage 3: be passed through steam or CO2, it is warmed up to 750～850 DEG C and is incubated, then proceeding to body cooling of ventilating, obtain carbon
Change rice husk；
3) carbonization rice husk is put in inorganic strong alkali solution, be then slowly added into dilute inorganic strong acid solution, dilute inorganic acid of addition
Solution is 1～10:1 with solute mole ratio in inorganic strong alkali solution, obtains presoma after stirring, filtration washing；
4) being dried by presoma and again activate, wherein heating cycle is:
Stage 1: be warmed up to 95～105 DEG C and be incubated；
Stage 2: be passed through steam or CO2, it is warmed up to 750～850 DEG C and is incubated, then proceeding to ventilation body cooling and obtain dioxy
SiClx absorbent charcoal composite material.
The preparation method of silicon dioxide activity carbon composite the most according to claim 1, it is characterised in that described inorganic acid is
Sulphuric acid or hydrochloric acid solution, inorganic strong alkali is sodium hydroxide or potassium hydroxide solution.
The preparation method of silicon dioxide activity carbon composite the most according to claim 1 and 2, it is characterised in that step 1) will
Rice husk soaks 12～36h in inorganic strong acid solution, inorganic acid concentration 0.85～1.25mol/L.
The preparation method of silicon dioxide activity carbon composite the most according to claim 1, it is characterised in that step 2) stage 1,
Heating rate 2.5～3.5 DEG C/min, is incubated 15～30min；Stage 2, flow rate of carrier gas rate 4～6L/min, heating rate 5～8 DEG C/min,
Insulation 90～120min；Stage 3, flow rate of carrier gas rate 4～6L/min, heating rate 5～8 DEG C/min, it is incubated 50～80min.
The preparation method of silicon dioxide activity carbon composite the most according to claim 1, it is characterised in that step 3) inorganic by force
Alkaline concentration 0.01-1mol/L, inorganic strong alkali solution and carbonization rice husk liquid-solid ratio are 1-10:1, and inorganic strong acid solution concentration is
0.01-1mol/L, rate of addition is 1-20mL/min, and mixing speed is 50-500r/min.
6. according to the preparation method of the silicon dioxide activity carbon composite described in claim 1,4 or 5, it is characterised in that step 4)
Stage 1, heating rate 2.5～3.5 DEG C/min, it is incubated 15～30min；Stage 2, flow rate of carrier gas rate 4～6L/min, heating rate
5～8 DEG C/min, it is incubated 50～80min.
7. one kind uses the silicon dioxide activity carbon composite that one of claim 1～6 described method prepares.
8. the cathode lead plaster for lead carbon battery, it is characterised in that include the silicon dioxide activity charcoal composite wood described in claim 7
Material.
9. a negative plate of lead-carbon battery, it is characterised in that using the cathode lead plaster described in claim 8 is that raw material is prepared from.
10. a lead carbon battery, it is characterised in that include the negative plates described in claim 9.
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| CN106684336A (en) * | 2016-12-25 | 2017-05-17 | 常州亚环环保科技有限公司 | Preparation method for high-combination degree lithium battery carbon silicon anode material |
| 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 |
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| CN111627718A (en) * | 2020-06-09 | 2020-09-04 | 吉林大学 | Preparation method of lead-carbon supercapacitor positive electrode |
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| CN114039041A (en) * | 2021-11-04 | 2022-02-11 | 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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