CN105355985A - Nanoscale silicon oxide composite dispersion liquid and preparation method therefor, and preparation method for nanoscale silicon oxide cake material - Google Patents
Nanoscale silicon oxide composite dispersion liquid and preparation method therefor, and preparation method for nanoscale silicon oxide cake material Download PDFInfo
- Publication number
- CN105355985A CN105355985A CN201510672109.4A CN201510672109A CN105355985A CN 105355985 A CN105355985 A CN 105355985A CN 201510672109 A CN201510672109 A CN 201510672109A CN 105355985 A CN105355985 A CN 105355985A
- Authority
- CN
- China
- Prior art keywords
- silicon oxide
- nano silicon
- nano
- order reaction
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 239
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 119
- 239000007788 liquid Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000006185 dispersion Substances 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title abstract description 7
- 239000000463 material Substances 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 113
- 230000032683 aging Effects 0.000 claims abstract description 37
- 239000002270 dispersing agent Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000005543 nano-size silicon particle Substances 0.000 claims description 136
- 239000002245 particle Substances 0.000 claims description 76
- 159000000000 sodium salts Chemical class 0.000 claims description 52
- 150000007522 mineralic acids Chemical class 0.000 claims description 50
- 239000000377 silicon dioxide Substances 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 38
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 36
- 235000015895 biscuits Nutrition 0.000 claims description 35
- 239000004067 bulking agent Substances 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 239000004604 Blowing Agent Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 19
- 239000003381 stabilizer Substances 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 16
- 238000004945 emulsification Methods 0.000 claims description 16
- 235000019353 potassium silicate Nutrition 0.000 claims description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 230000006911 nucleation Effects 0.000 claims description 9
- 238000010899 nucleation Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 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 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000010612 desalination reaction Methods 0.000 claims description 7
- 230000029087 digestion Effects 0.000 claims description 7
- 238000001802 infusion Methods 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 6
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 5
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 230000009286 beneficial effect Effects 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 229920006184 cellulose methylcellulose Polymers 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 229920005646 polycarboxylate Polymers 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920001353 Dextrin Polymers 0.000 claims description 4
- 239000004375 Dextrin Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 235000019425 dextrin Nutrition 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- -1 wherein Substances 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000005484 gravity Effects 0.000 abstract 1
- 239000000084 colloidal system Substances 0.000 description 24
- 239000003292 glue Substances 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000010412 perfusion Effects 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 241000549556 Nanos Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000005641 tunneling 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
- H01M10/10—Immobilising of electrolyte
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Compounds (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses nanoscale silicon oxide composite dispersion liquid and a preparation method therefor, belongs to the technical field of nanomaterial preparation, and solves the problems of low stability, high probability of demulsification, non-ideal gel forming state, and high usage amount of gel in the existing nanoscale silicon oxide sol. The nanoscale silicon oxide composite dispersion liquid comprises nanoscale silicon oxide and deionized water, and the nanoscale silicon oxide composite dispersion liquid is colorless transparent liquid, the PH value of the composite dispersion liquid is 9-12, the specific gravity at the temperature of 25 DEG C is 1.07-1.13 g/cm3, and the viscosity at the temperature of 25 DEG C is 1.71-1.78 mPa.S; the preparation method for the nanoscale silicon oxide composite dispersion liquid comprises a step of adding a dispersing agent, a step of adding the nanoscale silicon oxide, a step of adjusting the PH value and a step of adding compatibilizer in sequence; the preparation method for the nanoscale silicon oxide cake material comprises a first-order reaction step, a second-order reaction step, an aging step and a washing step; and the obtained nanoscale silicon oxide cake material comprises nanoscale silicon oxide powder, the solid grain diameter of the nanoscale silicon oxide powder is 1.5-10 nm, and the specific surface area of the nanoscale silicon oxide powder is greater than or equal to 1, 100 m2/g.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, be specifically related to the preparation method of a kind of nano silicon oxide dispersion liquid and preparation method thereof and biscuit
Background technology
When China's lead acid accumulator production capacity is 2.8 hundred million kilovolt-amperes, exceed 2/3rds of global total amount, in recent years whole industry output with 20% speed increase, at present, lead acid accumulator also there is energy density and power density is low, the problems such as suitable environment is temperature limited, 12 plan the nuclear energy of new generation explicitly pointed out, solar thermal utilization and photovoltaic and photothermal generating, wind power technology is equipped, intelligent grid and plug-in hybrid-power automobile, the development of pure electric automobile industry, propose higher to its matching used lead accumulator product quality and service condition, harsher requirement.
Gelled lead acid battery is as the one of valve-regulated lead-acid battery, be the novel product adopting colloidal electrolyte to replace electrolyte sulfuric acid on the basis of traditional lead acid batteries, be widely used in the applications such as electric power, telecommunications, the power supply system for communications, the military communication station, electric automobile.Gelled lead acid battery have convenient transportation, acid nonleakage, slow without acid mist, water consumption, have extended cycle life, suppress pole plate to corrode and distortion, prevent active material from coming off, the advantage such as maintenance period is long.
The performance quality of gelled lead acid battery depends on its gel that uses, and gel conventional in the market mainly contains two types: one is adopt fumed nano silica to be gel, and two is adopt colloidal silica as gel.
With fumed nano silica powder for gel, after the colloidal electrolyte perfusion battery of preparation, although the performance of lead acid accumulator can be improved, extend service life cycle, prevent acid liquor leakage, but still there is shortcomings, such as: prepared in the process of colloid by gaseous oxidation silicon, dust pollution operational environment; Silicon oxide particle is assembled serious, is difficult to dispersion, perfusion difficulty in the battery, poor to the permeability of accumulator plate and dividing plate; Reach the performance promoting colloid battery, need larger silica consumption, the used in amounts of usual silica powder will reach 6 ~ 10%.
Using colloidal silica as gel, can electrolyte leakage be prevented, improve operational environment, but the colloid generated is unstable, and under the mode of operation of deep discharge, colloid easily occurs aquation, lamination, loses original colloid property, shortens the useful life of battery.Due to adding of Ludox, the capacity of lead acid accumulator is reduced.
Present invention uses nano silicon oxide, nano silicon oxide (also claiming nano silicon) is a kind of typical nano material, because its particle diameter is very little, specific area is large, superficial attractive forces is strong, surface energy is large, chemical purity is high, dispersive property is good, thermal resistance, the aspects such as resistance have special performance, with the stability that it is superior, reinforcing, thickening property and thixotropy, show unique characteristics in numerous subject and field, there is the effect do not replaced, it can be used as additive, catalyst carrier, decolorizer, delustering agent, rubber reinforcing filler, plastics filler, ink thickeners, the soft buffing compound of metal, insulation and thermal insulation filler, high-grade daily-use cosmetics filler and sprayed on material etc. are widely used in petrochemical industry, medicine, environmental protection, the various field such as storage battery.Such as, the osmosis produced due to bulk effect and quantum tunneling effect, nano-silicon dioxide particle can be deep near the π key of macromolecular compound, forms spacial framework, thus can improve the mechanical strength of macromolecular compound material, resistance to wear and durability energy.
The particle diameter of nano oxidized silicon grain and specific area are the key factors affecting its performance, and particle diameter is less and specific area is larger, then its activity is higher, affinity and reinforcing property better, the adhesion of product is stronger.Prepare more small particle diameter and the nano silicon oxide simultaneously with more high-specific surface area is the target that industry is constantly pursued.
At present, the preparation method of common nano silicon comprises " vapor phase method " and " liquid phase method " two kinds.The production technology of preparing nano silicon dioxide by vapor phase process is fairly simple, reaction condition easy to control, product purity can up to 99.8%, specific area can reach 200-400 ㎡/g, active high, surface hydroxyl is few, be applicable to the synthesis of high-purity nm silicon dioxide, but the method still there is grain diameter and specific area is uncontrollable, the defect that its microstructure, dispersiveness and porosity etc. cannot effectively ensure, make the nano silicon prepared still there is the problem that grain diameter is large, specific area is not high, the needs of present stage every profession and trade application cannot be met.
The precipitation method are typical a kind of in liquid phase method, and the method, by being mixed with other adjuvant by reactant solution, with sour decomposing soluble silicate, then adds acidulant precipitation, obtains insoluble SiO in mixed solution
2, then drying and calcining obtain nano silicon.The method is because its technique is simple, raw material sources extensively obtain research and apply widely, but the unmanageable problem of its product characteristics is not still solved preferably, the purity of the nano silicon of preparation is not high, usually about 90%, specific area less (being generally 300 ㎡/below g), and obtained product cut size is large, particle size distribution is wide, in addition, precipitation process is uncontrollable, and particle agglomeration is serious, makes product characteristics be subject to serious restriction.
Colloidal silica preparation is easy, overcomes aerosil dust, but poor stability, easily produce demulsifying phenomenon; Storage battery keeps electrolytical ability inadequate, and under different mechanics and environmental condition, easily occur hydration phenomena after gel, plastic state is undesirable, and the use amount of colloid is high; The gel time of colloid and gel strength are not easy to control, and also there is the problem of poor permeability during filling.As the colloidal silica of Akzo Nobel N.V. of Sweden, be made up of nano silicon oxide and deionized water etc., it is creamy paste pasty state, and the proportion at 25 DEG C is 1.2 ~ 1.4g/cm
3, the viscosity at 25 DEG C is 7.5mPaS; When being mixed to form electrolyte with sulfuric acid, for translucent muddiness, there is clustering phenomena; Addition under the electrolyte equal strength formed is comparatively large, and only partial penetration in storage battery, forms starchiness and pile up; The major reason of these problems is caused to be that nano silicon oxide particle diameter is wherein little not and specific area is large not.
Summary of the invention
The invention provides a kind of nano silicon oxide dispersion liquid and preparation method thereof, solve existing colloidal silica poor stability, easily produce demulsifying phenomenon, plastic state is undesirable, colloid use amount is high problem; The preparation method of nano silicon oxide biscuit used in the present invention is provided simultaneously, it is prepared nano oxidized silicon technology to the precipitation method and improves, by inorganic acid and the neutralization reaction of waterglass are set at the different reaction of high order of condition, adopt special washing process simultaneously, the particle diameter and the specific area that realize nano silicon oxide in preparation process are thus controlled, thus prepare the nano silicon oxide biscuit be made up of the nano silicon oxide of small particle diameter and superhigh specific surface area.
A kind of nano silicon oxide dispersion liquid provided by the present invention, containing nano silicon oxide and deionized water, is characterized in that:
It is made up of deionized water, nano silicon oxide and dispersant, stabilizer, alkali lye and bulking agent, wherein, dispersant, stabilizer account for the mass percent 0.5% ~ 6%, 0.1% ~ 5% of nano silicon oxide respectively, nano silicon oxide accounts for the mass percent 5% ~ 11% of nano silicon oxide dispersion liquid, and alkali lye addition makes the pH value of the deionized water containing nano silicon oxide, dispersant and stabilizer be adjusted to 9 ~ 12; Bulking agent addition accounts for the mass percent 0.1% ~ 5% of nano silicon oxide;
The particle diameter of described nano silicon oxide is 1.5 ~ 10nm, its specific area >=1100 ㎡/g;
Described nano silicon oxide dispersion liquid is colourless transparent liquid, and pH value is the proportion at 9 ~ 12,25 DEG C is 1.07 ~ 1.13g/cm
3, the viscosity at 25 DEG C is 1.71 ~ 1.78mPaS.
Described dispersant is polycarboxylate sodium, alkyl polyoxyethylene ether (paregal O), AEO, polyethylene glycol or glycerine;
Described stabilizer is dextrin, CMC, hydroxyethylcellulose or polyvinyl alcohol;
Described alkali lye is NaOH, potassium hydroxide, lithium hydroxide or ammoniacal liquor;
Described bulking agent is one or more in ammoniacal liquor, phosphoric acid, lithium hydroxide, molybdenum oxide, stannous sulfate, nano-sized carbon.
The preparation method of described nano silicon oxide dispersion liquid, order comprises and adds dispersant step, plus nano silica step, adjustment pH value step and add bulking agent step, it is characterized in that:
(1) add dispersant step: add deionized water in a kettle., then add the dispersant of mass percent 0.5% ~ 6%, the stabilizer of 0.1% ~ 5% that account for nano silicon oxide, at 20 DEG C ~ 50 DEG C temperature, stir 10 minutes ~ 15 minutes;
(2) plus nano silica step: in the liquid that step (1) obtains, add nano silicon oxide biscuit, its solids nano silicon oxide accounts for the mass percent 5% ~ 11% of nano silicon oxide dispersion liquid, at 20 DEG C ~ 50 DEG C temperature, stirs 5 minutes ~ 10 minutes; In described nano silicon oxide biscuit, nano silicon oxide particle diameter is 1.5 ~ 10nm, its specific area >=1100 ㎡/g;
(3) pH value step is adjusted: in the liquid that step (2) obtains, add alkali lye, at 20 DEG C ~ 50 DEG C temperature, stir 30 minutes ~ 120 minutes, pH value is adjusted to 9 ~ 12;
(4) bulking agent step is added: in the liquid that step (3) obtains, add the bulking agent of the mass percent 0.1% ~ 5% accounting for nano silicon oxide, at 20 DEG C ~ 50 DEG C temperature, stir 15 minutes ~ 30 minutes, obtain nano silicon oxide dispersion liquid.
In described step (1), described dispersant is polycarboxylate sodium, alkyl polyoxyethylene ether (paregal O), AEO, polyethylene glycol or glycerine; Described stabilizer is dextrin, CMC, hydroxyethylcellulose or polyvinyl alcohol;
In described step (3), described alkali lye is NaOH, potassium hydroxide, lithium hydroxide or ammoniacal liquor;
In described step (4), described bulking agent is one or more in ammoniacal liquor, phosphoric acid, lithium hydroxide, molybdenum oxide, stannous sulfate, nano-sized carbon.
Nano silicon oxide dispersion liquid provided by the present invention, is colourless transparent liquid, is mixed to form the colloidal electrolyte needed for storage battery with electrolyte sulfuric acid, after perfusion, prepare solid accumulator.
Adopt and expect without the Na rice Yangization Gui Bing dehydrating process, not only ensured its easily disperse but also had containing amount and the surface activity of its superelevation specific surface, while can reduce production cost; By adding dispersant, slurry viscosity obviously reduces, and between particle, agglomeration obviously improves;
For the stability making dispersion liquid keep higher, the isoelectric point of nano silicon oxide is positioned near pH=2, and near pH=10, the Zeta potential of particle has maximum value, higher as guidance to control its Zeta potential absolute value, controls pH value 9 ~ 12; Disperse a difficult problem when solving nano silicon oxide application, fully retain the nano-meter characteristic of its high activity, high-ratio surface simultaneously;
Get the present invention and import Japan soup shallow glue, Sweden Aksu. Asia dragon 1000 glue of Nobel company, sub-imperial 2000 glue, mix with the sulfuric acid of 1.36g/ml simultaneously, test its gelling performance, as shown in table 1:
Table 1 colloidal property and the contrast of gel outward appearance
As shown in Table 1:
(1) colloid that under the condition of identical glue consumption, the present invention and sulfuric acid are mixed to form is for block, and the colloid starchiness that other colloids and sulfuric acid are mixed to form, although its silica content is 2 ~ 3 times of the present invention, its intensity but only has of the present invention 1/2 ~ 1/3, rear the present invention's substantially anhydrousization phenomenon placed by gel, and other products all occur stratification state.
(2) for reaching the gel state of same colloid, consumption of the present invention is only 1/2 ~ 1/3 of other colloids, and silica content is only 1/3 ~ 1/5 of other import glue.
The present invention is as shown in table 2 in tank formation and the characteristic being internalized into gel time and sour temperature under sour proportion condition, measure with glue (nano silicon oxide dispersion liquid):
Table 2
As shown in Table 2:
(1) nano silicon oxide dispersion liquid consumption is at 4% (silica content 0.4%), time can form all solid state colloid storage battery;
(2) when sour proportion is higher, gel time is faster;
(3) the lower gel time of acid adding temperature is longer, and as adopted cold sour temperature often to decline 10 DEG C, gel time can extend about one times;
(4) under same sour proportion condition, nano silicon oxide dispersion liquid consumption is larger, and gel time is faster;
The rear different colloidal electrolyte proportion of glue temperature, different nano silicon oxide dispersion liquid consumption and mixing is added according to difference, gel strength time diagram can be obtained, the control of gel time can according to acid adding temperature, acid adding amount and acid adding mode, add glue (nano silicon oxide dispersion liquid) amount and control.
Due to the present invention mix with sulfuric acid after before non-gel, viscosity still like water, strictly should control to operate the gel-filling technology time, before colloidal gel, be filled in storage battery, be allowed to condition at storage battery inner gel.
When embody rule is of the present invention, should according to each producer different battery separator, different chemical synthesis technology, that difference adds glue mode is different with to the requirement of colloid battery, with reference to gel strength time diagram of the present invention (gel strength contrasts with dioxide-containing silica), determine nano silicon oxide dispersion liquid usage percentage.
The setting of gel-filling technology can refer to gel strength time diagram of the present invention, determines to add glue mode according to gel time.For the colloid formula of gel time below 40 minutes, must namely mix namely with adding glue online; For the colloid formula of gel time more than 40 minutes, the scheme of the acid metering of transformation large metering glue and hybrid system on original equipment can be adopted, by the good colloidal electrolyte of design glue acid proportions on improved glue injection equipment; Note gel time before test or production, single preparation colloid mixture total amount answers conservative control, must ensure that before formation gel, add glue completes.
Silicon oxide particle in the present invention is evenly dispersed the size to primary particle, and the viscosity of dispersion liquid, close to the viscosity of water, because the small particle diameter of its uniqueness, single dispersing are conducive to the uniformity of the network configuration of gel, makes the colloid of formation have the transparency; The specific area of its superelevation, make colloid lock acid, carry sour ability by force, be conducive to the stability of gel colloidal network configuration, gel hydration phenomena reduces, and few consumption, can reach stronger gel strength; Completely solve the stability of inlet gas phase oxidation silicon, a dispersed difficult problem technically; When overcoming the perfusion of traditional colloid, by the forced filtration of pole plate, dividing plate, colloid is separated with electrolyte seriously, and colloid is mainly collected at cluster top and side, only has trace to enter the problem of cluster internal.
The preparation method of described nano silicon oxide biscuit, comprises first order reaction step, second order reaction step, aging step and washing step, it is characterized in that:
(1) first order reaction step: by inorganic acid, waterglass, nucleator, blowing agent and deionized water, by volume percentage 15% ~ 35%:20% ~ 40%:25% ~ 45%:2% ~ 6%:4% ~ 8%, add in first order reaction still, and high speed shear emulsification is stirred, obtain the silicon oxide particle of homogenizing nucleation; The concentration controlling sodium salt in reaction system is: 0.2mol/L ~ 5mol/L; Reacting initial temperature is 10 DEG C ~ 40 DEG C, preferably 20 DEG C ~ 30 DEG C, and described high speed shear emulsification stirring speed is 1400 revs/min ~ 5000 revs/min;
(2) second order reaction step: by first order reaction product, inorganic acid, nucleator, by volume percentage 60% ~ 75%:5% ~ 10%:18% ~ 30%, add in second order reaction still and stir, the sodium salt making infusion and generation described in making realizes occupy-place pore-creating, and nano-silica particle inside forms microporous structure; Reacting initial temperature is 20 DEG C ~ 60 DEG C, preferably 30 DEG C ~ 55 DEG C, and mixing speed is 40 revs/min ~ 125 revs/min, and wherein, the addition of inorganic acid is less than 3 to pH value;
(3) aging step: carry out pH value adjustment to second order reaction afterproduct, is the strong acid condition that the pH value near the isoelectric point being in nano silicon oxide is less than 3, under this strong acid condition, carries out ageing, digestion time 20 ~ 40 hours; This ageing process makes nano-silica particle growth and shaping and the many micropore of particle is stablized, and can make near isoelectric point to form three-dimensional net structure between nano-silica particle, makes nano silicon oxide be in gel state;
(4) washing step: carry out pressure depickling desalination washing the product after ageing is less than to the condition of 3 at pH value under, obtain nano silicon oxide biscuit, it contains nano silica powder, and solids particle diameter is 1.5 ~ 10nm, its specific area >=1100 ㎡/g.
In described first order reaction step, the molar concentration of each chemical composition is 0.5 ~ 8mol/L inorganic acid, 0.125 ~ 4mol/L waterglass, 0.25 ~ 4mol/L nucleator, 0.01 ~ 0.1mol/L blowing agent;
In described second order reaction step, the molar concentration of described inorganic acid, nucleator is 0.5 ~ 8mol/L inorganic acid, 0.25 ~ 5.2mol/L nucleator.
The preparation method of described nano silicon oxide biscuit, is characterized in that: described inorganic acid is hydrochloric acid, nitric acid or sulfuric acid, preferred hydrochloric acid, and described nucleator is any one inorganic sodium; Described blowing agent is the aqueous tenside easily producing bubble, preferred alkyl APEO, the particle-stabilised dispersion of homogenizing nucleation can be made to exist, be beneficial to the generation of the stable of small particle diameter and particle hole by it.
The preparation method of described nano silicon oxide biscuit, is characterized in that:
In reactions steps at different levels, sodium salt concentration is in poised state, makes in every first order reaction, and sodium salt concentration when having fed in raw material before reaction is identical with sodium salt concentration in reacted system, within the scope of 0.2mol/L ~ 4mol/L;
In described each order reaction sodium salt concentration be in poised state by the proportioning of each order reaction Raw is realized or sodium salt concentration rises after the reaction time by add pure water and realize or sodium salt concentration declines after the reaction time realize by adding sodium salt.
Nano silicon oxide biscuit preparation method of the present invention, has following beneficial effect:
(1) reaction of high order pattern is adopted, at the first order reaction initial stage, the reaction of inorganic acid and waterglass is comparatively violent, and exothermic heat of reaction is comparatively large, keeps the concentration stabilize balance of reaction system sodium ion, reacting initial temperature is low, effectively inhibit vigorous reaction, stir and adopt high speed shear emulsification stirring reaction, stir homogenizing by high speed shear emulsification and become nuclear particle, be beneficial to the generation of small particle diameter, high-specific surface area, aid dispersion auxiliary agent is conducive to small particle diameter and becomes the stable of nuclear particle;
Second order reaction and ageing reaction adopt stirring at low speed, and the generation of the shaping and aperture that are beneficial to nano particle is stablized.
(2) because the preparation process of nano silicon oxide is an acid-base neutralization course of reaction, the matched proportion density foundation of each raw material is for making the concentration of sodium salt in first order reaction, second order reaction system equal, namely the sodium salt total amount that reaction system at different levels is introduced and reaction generates is with when keeping reaction system sodium salt concentration balance to stablize, introduce equal with the required sodium salt total amount of dissolving of water of reaction generation in reaction system, with the stable state making reaction system keep salt solution, thus effectively can control particle diameter and the specific area of the nano silicon oxide generated.
(3) in reaction, the change of pH value is very large on the impact of the specific area of nano silicon oxide, by controlling the strong acid condition that pH value is less than 3, nano-silica particle can be made to be loose structure, thus realize nano silicon oxide structure-controllable.
(4) washing process carries out be less than the strong acid condition of 3 at pH value under, and make near its isoelectric point being positioned at nano silicon oxide, nano silicon oxide is in gel state, easily traps, and easily washs, and washing time is short, and clean result is good.
Compared with similar products at home and abroad, the nano silicon oxide that nano silicon oxide dispersion liquid of the present invention uses has that particle diameter is little, even particle size distribution (being less than 10 nanometers), specific surface large (being up to 1100 ㎡/g), surface activity are strong, purity high (more than 99.8%), stably dispersing;
The invention solves existing use domestic and international colloidal electrolyte product and add the problem that glue is difficult and plastic state is undesirable, effectively promote and improve traditional storage battery product quality, develop the premium quality product that can substitute import completely.The nano-colloid electrolyte of preparation has the advantages such as activity is high, year sour ability is strong, colloid-stabilised, gel time is long, viscosity is low, thixotropy is excellent, adds glue easy to operate, is easily formed with the stable tridimensional network of many porous nanos silica.The new forms of energy storage battery utilizing it filling comparatively common lead acid accumulator has use safety, and capacity is large, and the life-span is long, fluid loss and self discharge speed less; Anacidity mist gas evolution, without electrolyte spilling, lamination; The floating current that discharge and recharge receiving ability is strong and less, less heat; The particular advantages such as suitable environment is wide.It is completely coated that its addition is only that 1/3 ~ 1/5 of aerosil can realize fluid sulphuric acid electrolyte, no liquid seepage and splashing.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the embodiment of the present invention;
Fig. 2 is the process flow diagram of nano silicon oxide biscuit preparation method in the present invention;
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is described in more detail.
Embodiment 1, nano silicon oxide dispersion liquid preparation method, as shown in Figure 1, order comprises and adds dispersant step, plus nano silica step, adjustment pH value step and add bulking agent step:
(1) add dispersant step: add deionized water in a kettle., then add the dispersant of mass percent 6%, the stabilizer of 0.1% that account for nano silicon oxide solids, at 20 DEG C of temperature, stir 15 minutes; Described dispersant is polycarboxylate sodium; Described stabilizer is CMC;
(2) plus nano silica step: in the liquid that step (1) obtains, add nano silicon oxide biscuit, its solids nano silicon oxide accounts for the mass percent 5% of nano silicon oxide dispersion liquid, at 20 DEG C, stirs 10 minutes; In described nano silicon oxide biscuit, nano silicon oxide particle diameter is 1.5 ~ 10nm, its specific area 1128 ㎡/g;
(3) pH value step is adjusted: in the liquid that step (2) obtains, add alkali lye, at 20 DEG C of temperature, stir 120 minutes, pH value is adjusted to 9; Described alkali lye is NaOH;
(4) bulking agent step is added: in the liquid that step (3) obtains, add mass percent 0.05% lithium hydroxide and 0.05% stannous sulfate, two kinds of bulking agents that account for nano silicon oxide solids, at 20 DEG C of temperature, stir 30 minutes, obtain nano silicon oxide dispersion liquid, described bulking agent is lithium hydroxide, stannous sulfate.
The nano silicon oxide composite dispersion liquid obtained is colourless transparent liquid, and pH value is the proportion at 9,25 DEG C is 1.075g/cm
3, the viscosity at 25 DEG C is 1.71mPaS.
Embodiment 2, nano silicon oxide dispersion liquid preparation method, order comprises and adds dispersant step, plus nano silica step, adjustment pH value step and add bulking agent step:
(1) add dispersant step: add deionized water in a kettle., then add the dispersant of mass percent 0.5%, the stabilizer of 5% that account for nano silicon oxide solids, at 35 DEG C, stir 15 minutes; Described dispersant is alkyl polyoxyethylene ether (paregal O); Described stabilizer is polyvinyl alcohol;
(2) plus nano silica step: in the liquid that step (1) obtains, add nano silicon oxide biscuit, its solids accounts for the mass percent 8% of nano silicon oxide dispersion liquid, at 50 DEG C of temperature, stirs 5 minutes; In described nano silicon oxide biscuit, nano silicon oxide particle diameter is 1.5 ~ 10nm, its specific area 1100 ㎡/g;
(3) pH value step is adjusted: in the liquid that step (2) obtains, add alkali lye, at 40 DEG C of temperature, stir 90 minutes, pH value is adjusted to 10.5; Described alkali lye is potassium hydroxide;
(4) bulking agent step is added: in the liquid that step (3) obtains, add the bulking agent of the mass percent 5% accounting for nano silicon oxide solids, at 45 DEG C of temperature, stir 25 minutes, obtain nano silicon oxide dispersion liquid, described bulking agent is lithium hydroxide.
What obtained is colourless transparent liquid, and pH value is the proportion at 10.5,25 DEG C is 1.122g/cm
3, the viscosity at 25 DEG C is 1.76mPaS.
Embodiment 3, nano silicon oxide dispersion liquid preparation method, order comprises and adds dispersant step, plus nano silica step, adjustment pH value step and add bulking agent step:
(1) add dispersant step: add deionized water in a kettle., then add the dispersant of mass percent 3%, the stabilizer of 2% that account for nano silicon oxide solids, at 50 DEG C of temperature, stir 10 minutes; Described dispersant is glycerine; Described stabilizer is hydroxyethylcellulose;
(2) plus nano silica step: in the liquid that step (1) obtains, add nano silicon oxide biscuit, its solids accounts for the mass percent 11% of nano silicon oxide dispersion liquid, at 40 DEG C of temperature, stirs 8 minutes; In described nano silicon oxide biscuit, nano silicon oxide particle diameter is 1.5 ~ 10nm, its specific area 1160 ㎡/g;
(3) pH value step is adjusted: in the liquid that step (2) obtains, add alkali lye, at 50 DEG C of temperature, stir 30 minutes, pH value is adjusted to 12; Described alkali lye is lithium hydroxide;
(4) bulking agent step is added: in the liquid that step (3) obtains, add the phosphoric acid of the mass percent 3% accounting for nano silicon oxide solids and Nano carbon two kinds of bulking agents of mass percent 0.1%, at 50 DEG C of temperature, stir 15 minutes, obtain nano silicon oxide dispersion liquid, described bulking agent is phosphoric acid and Nano carbon.
Embodiment 4, the preparation method of nano silicon oxide biscuit, as shown in Figure 2, comprises first order reaction step, second order reaction step, aging step and washing step:
(1) first order reaction step: by inorganic acid, waterglass, nucleator, blowing agent and deionized water, by volume percentage 15%:32%:45%:3%:5%, add in first order reaction still, and high speed shear emulsification is stirred, obtain the silicon oxide particle of homogenizing nucleation; The concentration controlling sodium salt in reaction system is: 0.2mol/L; Reacting initial temperature is 40 DEG C, and described high speed shear emulsification stirring speed is 1400 revs/min;
The molar concentration of each chemical composition is 0.5mol/L inorganic acid, 0.125mol/L waterglass, 0.25mol/L nucleator, 0.1mol/L blowing agent;
Described inorganic acid is hydrochloric acid, and described nucleator is sodium chloride; Described blowing agent is the aqueous tenside easily producing bubble, preferred alkyl sodium sulphate;
(2) second order reaction step: by first order reaction product, inorganic acid, nucleator, by volume percentage 70%:6%:24%, add in second order reaction still and stir, the sodium salt making infusion and generation described in making realizes occupy-place pore-creating, and nano-silica particle inside forms microporous structure; Reacting initial temperature is 60 DEG C, and mixing speed is 40 revs/min, and wherein, the addition of inorganic acid is less than 3 to pH value;
Described inorganic acid is hydrochloric acid, nucleator is sodium chloride, and molar concentration is 0.5mol/L inorganic acid, 0.25mol/L nucleator;
In reactions steps at different levels, sodium salt concentration is in poised state, makes in every first order reaction, and sodium salt concentration when having fed in raw material before reaction is identical with sodium salt concentration in reacted system, and in reaction system, the concentration of sodium salt remains 0.2mol/L;
(3) aging step: carry out pH value adjustment to second order reaction afterproduct, is the strong acid condition that the pH value near the isoelectric point being in nano silicon oxide is less than 3, under this strong acid condition, carries out ageing, digestion time 20 hours; This ageing process makes nano-silica particle growth and shaping and the many micropore of particle is stablized, and can make near isoelectric point to form three-dimensional net structure between nano-silica particle, makes nano silicon oxide be in gel state;
(4) washing step: carry out pressure depickling desalination washing the product after ageing is less than to the condition of 3 at pH value under, obtain nano silicon oxide biscuit, it contains nano silica powder, and solids particle diameter is 1.5 ~ 10nm, its specific area 1108 ㎡/g.
Embodiment 5, the preparation method of nano silicon oxide biscuit, comprises first order reaction step, second order reaction step, aging step and washing step:
(1) first order reaction step: by inorganic acid, waterglass, nucleator, blowing agent and deionized water, by volume percentage 35%:20%:35%:6%:4%, add in first order reaction still, and high speed shear emulsification is stirred, obtain the silicon oxide particle of homogenizing nucleation; The concentration controlling sodium salt in reaction system is: 1mol/L; Reacting initial temperature is 30 DEG C, and described high speed shear emulsification stirring speed is 3000 revs/min;
The molar concentration of each chemical composition is 1.58mol/L inorganic acid, 1.4mol/L waterglass, 1.26mol/L nucleator, 0.05mol/L blowing agent;
Described inorganic acid is nitric acid, and described nucleator is sodium nitrate; Described blowing agent is the aqueous tenside easily producing bubble, preferred alkyl benzene sulfonic acid sodium salt;
(2) second order reaction step: by first order reaction product, inorganic acid, nucleator, by volume percentage 75%:5%:20%, add in second order reaction still and stir, the sodium salt making infusion and generation described in making realizes occupy-place pore-creating, and nano-silica particle inside forms microporous structure; Reacting initial temperature is 30 DEG C, and mixing speed is 83 revs/min, and wherein, the addition of inorganic acid is less than 3 to pH value;
Described inorganic acid is nitric acid, nucleator is sodium nitrate, and molar concentration is 1.58mol/L inorganic acid, 1.26mol/L nucleator sodium nitrate;
In reactions steps at different levels, sodium salt concentration is in poised state, makes in every first order reaction, and sodium salt concentration when having fed in raw material before reaction is identical with sodium salt concentration in reacted system, and in reaction system, the concentration of sodium salt remains 1mol/L;
(3) aging step: carry out pH value adjustment to second order reaction afterproduct, is the strong acid condition that the pH value near the isoelectric point being in nano silicon oxide is less than 3, under this strong acid condition, carries out ageing, digestion time 30 hours; This ageing process makes nano-silica particle growth and shaping and the many micropore of particle is stablized, and can make near isoelectric point to form three-dimensional net structure between nano-silica particle, makes nano silicon oxide be in gel state;
(4) washing step: carry out pressure depickling desalination washing the product after ageing is less than to the condition of 3 at pH value under, obtain nano silicon oxide biscuit, it contains nano silica powder, and solids particle diameter is 1.5 ~ 10nm, its specific area 1160 ㎡/g.
Embodiment 6, the preparation method of nano silicon oxide biscuit, comprises first order reaction step, second order reaction step, aging step and washing step:
(1) first order reaction step: by inorganic acid, waterglass, nucleator, blowing agent and deionized water, by volume percentage 26%:35%:25%:6%:8%, add in first order reaction still, and high speed shear emulsification is stirred, obtain the silicon oxide particle of homogenizing nucleation; The concentration controlling sodium salt in reaction system is: 3mol/L; Reacting initial temperature is 10 DEG C, and described high speed shear emulsification stirring speed is 5000 revs/min;
The molar concentration of each chemical composition is 8mol/L inorganic acid, 2.86mol/L waterglass, 4mol/L nucleator, 0.01mol/L blowing agent;
Described inorganic acid is hydrochloric acid, and described nucleator is sodium sulphate; Described blowing agent is the aqueous tenside easily producing bubble, preferred alkyl APEO;
(2) second order reaction step: by first order reaction product, inorganic acid, nucleator, by volume percentage 60%:10%:30%, add in second order reaction still and stir, the sodium salt making infusion and generation described in making realizes occupy-place pore-creating, and nano-silica particle inside forms microporous structure; Reacting initial temperature is 20 DEG C, and mixing speed is 125 revs/min, and wherein, the addition of inorganic acid is less than 3 to pH value;
The molar concentration of described inorganic acid, nucleator is 8mol/L hydrochloric acid, 4mol/L sodium sulphate;
In reactions steps at different levels, sodium salt concentration is in poised state, makes in every first order reaction, and in the sodium salt concentration before reaction when having fed in raw material and reacted system, in sodium salt concentration same reaction system, the concentration of sodium salt remains 3mol/L;
(3) aging step: carry out pH value adjustment to second order reaction afterproduct, is the strong acid condition that the pH value near the isoelectric point being in nano silicon oxide is less than 3, under this strong acid condition, carries out ageing, digestion time 40 hours; This ageing process makes nano-silica particle growth and shaping and the many micropore of particle is stablized, and can make near isoelectric point to form three-dimensional net structure between nano-silica particle, makes nano silicon oxide be in gel state;
(4) washing step: carry out pressure depickling desalination washing the product after ageing is less than to the condition of 3 at pH value under, obtain nano silicon oxide biscuit, it contains nano silica powder, and solids particle diameter is 1.5 ~ 10nm, its specific area 1130 ㎡/g.
Embodiment 7, the preparation method of nano silicon oxide biscuit, as shown in Figure 2, comprises first order reaction step, second order reaction step, aging step and washing step:
(1) first order reaction step: by inorganic acid, waterglass, nucleator, blowing agent and deionized water, by volume percentage 30%:27.2%:35%:2%:5.8%, add in first order reaction still, and high speed shear emulsification is stirred, obtain the silicon oxide particle of homogenizing nucleation; The concentration controlling sodium salt in reaction system is: 5mol/L; Reacting initial temperature is 20 DEG C, and described high speed shear emulsification stirring speed is 3000 revs/min;
The molar concentration of each chemical composition is 7.1mol/L inorganic acid, 4mol/L waterglass, 5.2mol/L nucleator, 0.03mol/L blowing agent;
Described inorganic acid is hydrochloric acid, and described nucleator is sodium chloride; Described blowing agent is the aqueous tenside easily producing bubble, preferred alkyl APEO;
(2) second order reaction step: by first order reaction product, inorganic acid, nucleator, by volume percentage 75%:7%:18%, add in second order reaction still and stir, the sodium salt making infusion and generation described in making realizes occupy-place pore-creating, and nano-silica particle inside forms microporous structure; Reacting initial temperature is 20 DEG C ~ 60 DEG C, preferably 55 DEG C, and mixing speed is 40 revs/min, and wherein, the addition of inorganic acid is less than 3 to pH value;
The molar concentration of described inorganic acid hydrochloric acid, nucleator sodium chloride is 7.1mol/L inorganic acid, 5.2mol/L nucleator;
In reactions steps at different levels, sodium salt concentration is in poised state, makes in every first order reaction, and sodium salt concentration when having fed in raw material before reaction is identical with sodium salt concentration in reacted system, and in reaction system, the concentration of sodium salt remains 4mol/L;
(3) aging step: carry out pH value adjustment to second order reaction afterproduct, is the strong acid condition that the pH value near the isoelectric point being in nano silicon oxide is less than 3, under this strong acid condition, carries out ageing, digestion time 40 hours; This ageing process makes nano-silica particle growth and shaping and the many micropore of particle is stablized, and can make near isoelectric point to form three-dimensional net structure between nano-silica particle, makes nano silicon oxide be in gel state;
(4) washing step: carry out pressure depickling desalination washing the product after ageing is less than to the condition of 3 at pH value under, obtain nano silicon oxide biscuit, it contains nano silica powder, and solids particle diameter is 1.5 ~ 10nm, its specific area 1131 ㎡/g.
Embodiment 8, the preparation method of nano silicon oxide biscuit, as shown in Figure 2, comprises first order reaction step, second order reaction step, aging step and washing step:
(1) first order reaction step: by inorganic acid, waterglass, nucleator, blowing agent and deionized water, by volume percentage 20%:40%:27%:5%:8%, add in first order reaction still, and high speed shear emulsification is stirred, obtain the silicon oxide particle of homogenizing nucleation; The concentration controlling sodium salt in reaction system is: 0.5mol/L; Reacting initial temperature is 35 DEG C, and described high speed shear emulsification stirring speed is 1400 revs/min;
The molar concentration of each chemical composition is 1.61mol/L inorganic acid, 0.41mol/L waterglass, 0.625mol/L nucleator, 0.08mol/L blowing agent;
Described inorganic acid is hydrochloric acid, and described nucleator is sodium chloride; Described blowing agent is the aqueous tenside easily producing bubble, preferred alkyl sodium sulphate;
(2) second order reaction step: by first order reaction product, inorganic acid, nucleator, by volume percentage 65%:7%:28%, add in second order reaction still and stir, the sodium salt making infusion and generation described in making realizes occupy-place pore-creating, and nano-silica particle inside forms microporous structure; Reacting initial temperature is 60 DEG C, and mixing speed is 40 revs/min, and wherein, the addition of inorganic acid is less than 3 to pH value;
Described inorganic acid is hydrochloric acid, nucleator is sodium chloride, and molar concentration is 1.61mol/L inorganic acid, 0.625mol/L nucleator;
In reactions steps at different levels, sodium salt concentration is in poised state, makes in every first order reaction, and sodium salt concentration when having fed in raw material before reaction is identical with sodium salt concentration in reacted system, and in reaction system, the concentration of sodium salt remains 0.5mol/L;
(3) aging step: carry out pH value adjustment to second order reaction afterproduct, is the strong acid condition that the pH value near the isoelectric point being in nano silicon oxide is less than 3, under this strong acid condition, carries out ageing, digestion time 25 hours; This ageing process makes nano-silica particle growth and shaping and the many micropore of particle is stablized, and can make near isoelectric point to form three-dimensional net structure between nano-silica particle, makes nano silicon oxide be in gel state;
(4) washing step: carry out pressure depickling desalination washing the product after ageing is less than to the condition of 3 at pH value under, obtain nano silicon oxide biscuit, it contains nano silica powder, and solids particle diameter is 1.5 ~ 10nm, its specific area 1128 ㎡/g.
Claims (8)
1. a nano silicon oxide dispersion liquid, containing nano silicon oxide and deionized water, is characterized in that:
It is made up of deionized water, nano silicon oxide and dispersant, stabilizer, alkali lye and bulking agent, wherein, dispersant, stabilizer account for the mass percent 0.5% ~ 6%, 0.1% ~ 5% of nano silicon oxide respectively, nano silicon oxide accounts for the mass percent 5% ~ 11% of nano silicon oxide dispersion liquid, and alkali lye addition makes the pH value of the deionized water containing nano silicon oxide, dispersant and stabilizer be adjusted to 9 ~ 12; Bulking agent addition accounts for the mass percent 0.1% ~ 5% of nano silicon oxide;
The particle diameter of described nano silicon oxide is 1.5 ~ 10nm, its specific area >=1100 ㎡/g;
Described nano silicon oxide dispersion liquid is colourless transparent liquid, and pH value is the proportion at 9 ~ 12,25 DEG C is 1.07 ~ 1.13g/cm
3, the viscosity at 25 DEG C is 1.71 ~ 1.78mPaS.
2. nano silicon oxide dispersion liquid as claimed in claim 1, is characterized in that:
Described dispersant is polycarboxylate sodium, alkyl polyoxyethylene ether, AEO, polyethylene glycol or glycerine;
Described stabilizer is dextrin, CMC, hydroxyethylcellulose or polyvinyl alcohol;
Described alkali lye is NaOH, potassium hydroxide, lithium hydroxide or ammoniacal liquor;
Described bulking agent is one or more in ammoniacal liquor, phosphoric acid, lithium hydroxide, molybdenum oxide, stannous sulfate, nano-sized carbon.
3. the preparation method of nano silicon oxide dispersion liquid described in claim 1 or 2, order comprises and adds dispersant step, plus nano silica step, adjustment pH value step and add bulking agent step, it is characterized in that:
(1) add dispersant step: add deionized water in a kettle., then add the dispersant of mass percent 0.5% ~ 6%, the stabilizer of 0.1% ~ 5% that account for nano silicon oxide, at 20 DEG C ~ 50 DEG C temperature, stir 10 minutes ~ 15 minutes;
(2) plus nano silica step: in the liquid that step (1) obtains, add nano silicon oxide biscuit, its solids nano silicon oxide accounts for the mass percent 5% ~ 11% of nano silicon oxide dispersion liquid, at 20 DEG C ~ 50 DEG C temperature, stirs 5 minutes ~ 10 minutes; In described nano silicon oxide biscuit, nano silicon oxide particle diameter is 1.5 ~ 10nm, its specific area >=1100 ㎡/g;
(3) pH value step is adjusted: in the liquid that step (2) obtains, add alkali lye, at 20 DEG C ~ 50 DEG C temperature, stir 30 minutes ~ 120 minutes, pH value is adjusted to 9 ~ 12;
(4) bulking agent step is added: in the liquid that step (3) obtains, add the bulking agent of the mass percent 0.1% ~ 5% accounting for nano silicon oxide, at 20 DEG C ~ 50 DEG C temperature, stir 15 minutes ~ 30 minutes, obtain nano silicon oxide dispersion liquid.
4. preparation method as claimed in claim 3, is characterized in that:
In described step (1), described dispersant is polycarboxylate sodium, alkyl polyoxyethylene ether (paregal O), AEO, polyethylene glycol or glycerine; Described stabilizer is dextrin, CMC, hydroxyethylcellulose or polyvinyl alcohol;
In described step (3), described alkali lye is NaOH, potassium hydroxide, lithium hydroxide or ammoniacal liquor;
In described step (4), described bulking agent is one or more in ammoniacal liquor, phosphoric acid, lithium hydroxide, molybdenum oxide, stannous sulfate, nano-sized carbon.
5. the preparation method of nano silicon oxide biscuit described in claim 3 or claim 4, comprises first order reaction step, second order reaction step, aging step and washing step, it is characterized in that:
(1) first order reaction step: by inorganic acid, waterglass, nucleator, blowing agent and deionized water, by volume percentage 15% ~ 35%:20% ~ 40%:25% ~ 45%:2% ~ 6%:4% ~ 8%, add in first order reaction still, and high speed shear emulsification is stirred, obtain the silicon oxide particle of homogenizing nucleation; The concentration controlling sodium salt in reaction system is: 0.2mol/L ~ 5mol/L; Reacting initial temperature is 10 DEG C ~ 40 DEG C, preferably 20 DEG C ~ 30 DEG C, and described high speed shear emulsification stirring speed is 1400 revs/min ~ 5000 revs/min;
(2) second order reaction step: by first order reaction product, inorganic acid, nucleator, by volume percentage 60% ~ 75%:5% ~ 10%:18% ~ 30%, add in second order reaction still and stir, the sodium salt making infusion and generation described in making realizes occupy-place pore-creating, and nano-silica particle inside forms microporous structure; Reacting initial temperature is 20 DEG C ~ 60 DEG C, preferably 30 DEG C ~ 55 DEG C, and mixing speed is 40 revs/min ~ 125 revs/min, and wherein, the addition of inorganic acid is less than 3 to pH value;
(3) aging step: carry out pH value adjustment to second order reaction afterproduct, is the strong acid condition that the pH value near the isoelectric point being in nano silicon oxide is less than 3, under this strong acid condition, carries out ageing, digestion time 20 ~ 40 hours; This ageing process makes nano-silica particle growth and shaping and the many micropore of particle is stablized, and can make near isoelectric point to form three-dimensional net structure between nano-silica particle, makes nano silicon oxide be in gel state;
(4) washing step: carry out pressure depickling desalination washing the product after ageing is less than to the condition of 3 at pH value under, obtain nano silicon oxide biscuit, it contains nano silica powder, and solids particle diameter is 1.5 ~ 10nm, its specific area >=1100 ㎡/g.
6. the preparation method of nano silicon oxide biscuit as claimed in claim 5, is characterized in that:
In described first order reaction step, the molar concentration of each chemical composition is 0.5 ~ 8mol/L inorganic acid, 0.125 ~ 4mol/L waterglass, 0.25 ~ 4mol/L nucleator, 0.01 ~ 0.1mol/L blowing agent;
In described second order reaction step, the molar concentration of described inorganic acid, nucleator is 0.5 ~ 8mol/L inorganic acid, 0.25 ~ 5.2mol/L nucleator.
7. the preparation method of the nano silicon oxide biscuit as described in claim 5 or 6, is characterized in that: described inorganic acid is hydrochloric acid, nitric acid or sulfuric acid, preferred hydrochloric acid, and described nucleator is any one inorganic sodium; Described blowing agent is the aqueous tenside easily producing bubble, preferred alkyl APEO, the particle-stabilised dispersion of homogenizing nucleation can be made to exist, be beneficial to the generation of the stable of small particle diameter and particle hole by it.
8. the preparation method of the nano silicon oxide biscuit as described in claim 5 or 6, is characterized in that:
In reactions steps at different levels, sodium salt concentration is in poised state, makes in every first order reaction, and sodium salt concentration when having fed in raw material before reaction is identical with sodium salt concentration in reacted system, within the scope of 0.2mol/L ~ 4mol/L;
In described each order reaction sodium salt concentration be in poised state by the proportioning of each order reaction Raw is realized or sodium salt concentration rises after the reaction time by add pure water and realize or sodium salt concentration declines after the reaction time realize by adding sodium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510672109.4A CN105355985B (en) | 2015-10-16 | 2015-10-16 | The preparation method of nano silicon oxide dispersion liquid and preparation method thereof and biscuit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510672109.4A CN105355985B (en) | 2015-10-16 | 2015-10-16 | The preparation method of nano silicon oxide dispersion liquid and preparation method thereof and biscuit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105355985A true CN105355985A (en) | 2016-02-24 |
| CN105355985B CN105355985B (en) | 2017-09-01 |
Family
ID=55331902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510672109.4A Active CN105355985B (en) | 2015-10-16 | 2015-10-16 | The preparation method of nano silicon oxide dispersion liquid and preparation method thereof and biscuit |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105355985B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105870515A (en) * | 2016-06-08 | 2016-08-17 | 田泽狄 | Silica gel salt surface colloid electrolyte and preparing method thereof |
| CN106145123A (en) * | 2016-08-19 | 2016-11-23 | 安徽元琛环保科技股份有限公司 | A kind of Ludox preparation method of simple and fast |
| CN111545136B (en) * | 2020-04-05 | 2021-02-19 | 北京化工大学 | Preparation method and application of self-suspended polymer aerogel with efficient photothermal conversion |
| CN114433117A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of heavy diesel oil fraction hydrofining catalyst |
| CN114433204A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN114433203A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of vulcanization type hydrocracking catalyst |
| CN114471594A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101894979A (en) * | 2010-07-15 | 2010-11-24 | 山东康洋电源有限公司 | Electrolyte of nano-colloid storage battery |
| CN103346357A (en) * | 2013-06-09 | 2013-10-09 | 长兴亿创纳米科技有限公司 | Colloid additive and preparation method thereof |
| TW201424084A (en) * | 2012-12-14 | 2014-06-16 | Taiwan Yuasa Battery Co Ltd | Electrolyte additive for lead acid battery |
| CN104817092A (en) * | 2015-05-08 | 2015-08-05 | 江西纳宇纳米新材料有限公司 | Preparation method of small-particle-size and ultrahigh-specific-surface-area nano silicon oxide |
| CN104828828A (en) * | 2015-05-08 | 2015-08-12 | 江西纳宇纳米新材料有限公司 | Small-particle-size ultrahigh-specific-area nano silicon oxide |
-
2015
- 2015-10-16 CN CN201510672109.4A patent/CN105355985B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101894979A (en) * | 2010-07-15 | 2010-11-24 | 山东康洋电源有限公司 | Electrolyte of nano-colloid storage battery |
| TW201424084A (en) * | 2012-12-14 | 2014-06-16 | Taiwan Yuasa Battery Co Ltd | Electrolyte additive for lead acid battery |
| CN103346357A (en) * | 2013-06-09 | 2013-10-09 | 长兴亿创纳米科技有限公司 | Colloid additive and preparation method thereof |
| CN104817092A (en) * | 2015-05-08 | 2015-08-05 | 江西纳宇纳米新材料有限公司 | Preparation method of small-particle-size and ultrahigh-specific-surface-area nano silicon oxide |
| CN104828828A (en) * | 2015-05-08 | 2015-08-12 | 江西纳宇纳米新材料有限公司 | Small-particle-size ultrahigh-specific-area nano silicon oxide |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105870515A (en) * | 2016-06-08 | 2016-08-17 | 田泽狄 | Silica gel salt surface colloid electrolyte and preparing method thereof |
| CN105870515B (en) * | 2016-06-08 | 2018-12-28 | 田泽狄 | A kind of silica gel salt surface colloidal electrolyte and preparation method thereof |
| CN106145123A (en) * | 2016-08-19 | 2016-11-23 | 安徽元琛环保科技股份有限公司 | A kind of Ludox preparation method of simple and fast |
| CN111545136B (en) * | 2020-04-05 | 2021-02-19 | 北京化工大学 | Preparation method and application of self-suspended polymer aerogel with efficient photothermal conversion |
| CN114433117A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of heavy diesel oil fraction hydrofining catalyst |
| CN114433204A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN114433203A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of vulcanization type hydrocracking catalyst |
| CN114433204B (en) * | 2020-10-19 | 2023-09-01 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN114433203B (en) * | 2020-10-19 | 2023-09-01 | 中国石油化工股份有限公司 | Preparation method of vulcanized hydrocracking catalyst |
| CN114433117B (en) * | 2020-10-19 | 2023-09-01 | 中国石油化工股份有限公司 | Preparation method of heavy diesel fraction hydrofining catalyst |
| CN114471594A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method thereof |
| CN114471594B (en) * | 2020-10-26 | 2024-01-12 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105355985B (en) | 2017-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105355985A (en) | Nanoscale silicon oxide composite dispersion liquid and preparation method therefor, and preparation method for nanoscale silicon oxide cake material | |
| CN110451525B (en) | Method for rapidly preparing Prussian blue analogue with monoclinic crystal structure | |
| CN106816602B (en) | Two selenium of one kind (sulphur) change molybdenum (tungsten)/carbon composite and its preparation method and application | |
| CN102583292A (en) | Ferric phosphate having micro-nano structure and preparation method thereof as well as lithium iron phosphate material | |
| CN103227322B (en) | Quaternary lithium-ion battery positive electrode material and preparation method thereof | |
| CN105140475A (en) | Preparation method of anode material Fe3O4/MoS2 for lithium ion battery | |
| CN110078096A (en) | A kind of Prussian blue material and preparation method thereof | |
| CN112537805B (en) | Preparation method of modified nickel-manganese binary precursor | |
| CN108242540A (en) | A kind of carbon coating vanadium phosphate sodium microballoon and preparation method thereof and the application as sodium-ion battery positive material | |
| CN110407194A (en) | The hollow Nano carbon balls of three-dimensional porous N doping and its controllable method for preparing and application | |
| CN105609769A (en) | Preparation method for multi-level structured molybdenum disulfide microsphere negative electrode material of lithium battery | |
| CN110085846A (en) | A kind of graphene-silicon dioxide composite aerogel carries sulfur materials and its preparation method and application | |
| CN108666586A (en) | The method for preparing the ordered mesoporous carbon material of containing transition metal sulfide | |
| CN109775762A (en) | A kind of Fe of hollow graded structure2O3And Fe2O3The preparation method of/CNT composite material | |
| CN108878174A (en) | A kind of preparation method of di-iron trioxide nanometer sheet/Graphene electrodes material | |
| CN108630928A (en) | A kind of self-supporting grading-hole positive electrode, preparation method and its application on lithium-sulfur cell | |
| CN107017394B (en) | A kind of pyrophosphoric acid cobalt sodium/carbon graphite alkene anode composite material, preparation and application | |
| CN103078120B (en) | Ferrous silicate lithium ion battery cathode material with hierarchical structure and preparation method | |
| CN107819149A (en) | A kind of method that growth in situ prepares all-solid sodium ion battery | |
| CN114573033A (en) | Cluster MnO 2 Preparation method of the positive electrode material, secondary zinc-manganese battery and secondary zinc-manganese battery | |
| CN108428948B (en) | Electrolyte of lead crystal storage battery, preparation method of electrolyte and lead crystal storage battery | |
| CN108847481A (en) | A kind of preparation and application of the porous manganese sesquioxide managnic oxide cube negative electrode material of high performance lithium ion battery carbon coating | |
| CN109261170B (en) | Pd @ Pd4S-porous carbon nano material and preparation method and application thereof | |
| CN103579581A (en) | Monocrystalline porous iron oxide powder material and preparation method thereof | |
| CN114335459B (en) | Negative electrode material for secondary battery, preparation method thereof, negative electrode sheet and secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221205 Address after: 335500 East side of the new Honggang old line in Fengchao Industrial Park, Wannian County, Shangrao City, Jiangxi Province Patentee after: Shangrao Annatuo New Materials Co.,Ltd. Address before: 335500 Shizhen Characteristic Industrial Park, Wannian County, Shangrao City, Jiangxi Province Patentee before: JIANGXI NAYU NANO NEW MATERIAL CO.,LTD. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240307 Address after: 335,500 Shizhen Characteristic Industrial Park, Wannian County, Shangrao City, Jiangxi Province Patentee after: JIANGXI NAYU NANO NEW MATERIAL CO.,LTD. Country or region after: China Address before: 335500 East side of the new Honggang old line in Fengchao Industrial Park, Wannian County, Shangrao City, Jiangxi Province Patentee before: Shangrao Annatuo New Materials Co.,Ltd. Country or region before: China |