CN108033486A - A kind of preparation method of conductive mesoporous nano titanium dioxide - Google Patents
A kind of preparation method of conductive mesoporous nano titanium dioxide Download PDFInfo
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- CN108033486A CN108033486A CN201711344806.2A CN201711344806A CN108033486A CN 108033486 A CN108033486 A CN 108033486A CN 201711344806 A CN201711344806 A CN 201711344806A CN 108033486 A CN108033486 A CN 108033486A
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 106
- 238000001354 calcination Methods 0.000 claims abstract description 59
- 239000000243 solution Substances 0.000 claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 19
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000379 antimony sulfate Inorganic materials 0.000 claims abstract description 15
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 13
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 8
- 238000010792 warming Methods 0.000 claims abstract description 8
- 238000010790 dilution Methods 0.000 claims abstract description 3
- 239000012895 dilution Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 31
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 20
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000013335 mesoporous material Substances 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 239000012065 filter cake Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000012795 verification Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 235000019795 sodium metasilicate Nutrition 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 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 description 1
- 229910012675 LiTiO2 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910009973 Ti2O3 Inorganic materials 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013524 data verification Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Geology (AREA)
- Conductive Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of preparation method of conductive mesoporous nano titanium dioxide, belongs to the technical field of conductive mesoporous material, comprises the following steps：A, metatitanic acid is added into desalted water slurrying, controls TiO2Concentration is 350 400g/L, adds sal volatile, stirring, filtering, calcining, are crushed to 325 mesh screen residues less than 0.1%, obtain calcinated titanium dioxide powder；B, calcinated titanium dioxide powder is added into desalted water slurrying, then adds sodium silicate solution, control slurry concentration TiO thereto2600 700g/L, particle of the grinding distribution to particle diameter less than 0.5 μm account for 97%；C, pulp dilution after above-mentioned steps B is disperseed is to TiO2350 400g/L, are warming up to 60 70 DEG C, add calgon, stir evenly, and add sulfuric acid solution of tin and antimony sulfate solution, cure 1 2h, filter, wash, dry, pulverize to 325 mesh screen residues less than 0.01%, obtaining conductive mesoporous nano titanium dioxide.Preparation method of the present invention is simple, it can be achieved that the industrialized production of conductive mesoporous nano titanium dioxide, technology controlling and process precision are high.
Description
Technical field
The invention belongs to the technical field of conductive mesoporous material, is related to the conductive mesoporous nano titanium dioxide for lithium battery
A kind of titanium, and in particular to preparation method of conductive mesoporous nano titanium dioxide.Preparation method of the present invention is simple, it can be achieved that conductive be situated between
The industrialized production of hole nano-titanium dioxide, technology controlling and process precision are high.
Background technology
With economic development and the increase of the size of population, the mankind drastically expand the demand of the energy, non-renewable fossil energy
Source gradually decreases, final exhausted.Serious environmental problem is brought at the same time, and clean reproducible energy, such as solar energy, wind energy utilize
It is the important means of alleviating energy crisis, but the poor continuity of these energy, efficiently use these energy, it is necessary to by accumulator
Part, in numerous energy storage devices, lithium ion battery just obtains World Focusing with its superiority from the beginning of the seventies in last century.Last century
There is business secondary lithium battery the nineties.In the 21st century, lithium ion battery is rapidly developed, global lithium in 2005
Battery requirements amount is 8.2GWh, 110.1GWh, average growth rate 26.63% is reached by 2016, but compact lithium cell accounts for
Than great, compact lithium cell in 2016 accounts for the 73.43% of total amount, and the large and medium-sized electrical storage device accounting such as power vehicle and industrial energy storage
Less than 1/3.Three capacity of lithium battery, charge/discharge rates, security factors are the main reason for restricting lithium battery maximization.It is excellent
The acquisition of good electrode material is one of basic reason, especially negative material.
TiO2With open crystal structure, the flexible electronic structure of titanium ion so that TiO2The electricity of acceptable foreign ion
Son, and provide room for embedded lithium ion.TiO2Intercalation potential is higher than carbon, about 1.75V, can solve lithium and produce branch in anode
The problem of brilliant；Solubility in organic electrolyte is smaller, and the structure change during embedding de- lithium is small, can avoid embedding de- lithium process
Structure caused by middle material volume change is destroyed, and improves the cycle performance and service life of material.
TiO2It is 310mAh/g as lithium cell cathode material theoretical capacity, stability and security are preferable, but due to
Anode TiO during charging2There are Ti4+Obtain electronics and become Ti3+, Li+With Ti2O3Generate LiTiO2For irreversible reaction, cause TiO2
Irreversible capacity is high, and discharge-rate is not high.Therefore solve the above problems and urgently pursue at present.
The content of the invention
The present invention is to solve the above problems, provide a kind of preparation method of conductive mesoporous nano titanium dioxide, this preparation
Method technique is simple, clean environment firendly, collocation and stringent control by process, the TiO of preparation2Using rear reversible good.
The present invention is to realize that the technical solution that its purpose uses is：
A kind of preparation method of conductive mesoporous nano titanium dioxide, comprises the following steps：
A, metatitanic acid is added into desalted water slurrying, controls TiO2Concentration is 350-400g/L, adds sal volatile, is stirred,
Filtering, calcining, are crushed to 325 mesh screen residues less than 0.1%, obtain calcinated titanium dioxide powder；The TiO of control herein2Concentration is 350-
400g/L be in order to make salt treatment agent fully adsorb in metatitanic acid particle surface or be entrained in gap among, could be sent out in calcining
Best salt treatment effect is waved, metatitanic acid slurry concentration is too low, and inorganic agent is easily lost in, and reduces reality by metatitanic acid absorption
Amount, influences salt treatment effect；Metatitanic acid slurry concentration is excessive, then additive cannot be dispersed in slurry, can also influence salt
Treatment effect.
B, calcinated titanium dioxide powder is added into desalted water slurrying, then adds sodium silicate solution thereto, control slurry is dense
Spend TiO2600-700g/L, particle of the grinding distribution to particle diameter less than 0.5 μm account for 97%；In order to which silicon fine dispersion forms silica gel bag
Cover control slurry concentration TiO2600-700g/L, too low or excessive concentrations, it is difficult to which scattered, coating is bad, and granularity is not after crushing
Good, properties of product are poor.Summarized through research, there are more than 0.5 μm bulky grain, its covering power, tinting strength, tinting power, bottom form and aspect for titanium dioxide
Have and be decreased obviously etc. performance indicator, therefore need particle of the grinding distribution to particle diameter less than 0.5 μm to account for 97% in the step.
C, pulp dilution after above-mentioned steps B is disperseed is to TiO2350-400g/L, is warming up to 60-70 DEG C, adds six inclined phosphorus
Sour sodium, stirs evenly, and adds sulfuric acid solution of tin and antimony sulfate solution, cures 1-2h, filters, washs, dry, pulverize to 325 mesh sieves
It is remaining to be less than 0.01%, obtain conductive mesoporous nano titanium dioxide.In order to which back is dispersed, doping is needed slurry in the step
Again TiO is diluted back2350-400g/L.60-70 DEG C of temperature in this step is controlled, is to realize silicon coating condition, crosses and exceed
It is low not fine and close, effect of the calgon as dispersant.In order to ensure to adulterate effect, 1-2h need to be cured by control, it is too short to mix
Miscellaneous metal ion deficiency, it is long easily to form the mixture being in a mess.
In step A, the mass concentration of the sal volatile is 30-40%, addition 5-10%.
In step A, mixing time 1-1.5h, the temperature of calcining is 300-500 DEG C, and the time of calcining is 4-5h.Stirring
The length of time is to influence scattered key, it is too short or it is long can cause it is scattered uneven.
In step B, the mass concentration of the sodium silicate solution is 50 ± 5g/L, and the addition of sodium silicate solution is with SiO2/
TiO2It is calculated as 0.2-0.3%.The control of sodium metasilicate capacity concentration and addition, is in order to avoid forming gallimaufry, well
The scattered condition for forming fine and close cladding.
In step C, the concentration of sulfuric acid solution of tin is 250 ± 5g/L, and the dosage of sulfuric acid solution of tin is 15-16%, antimony sulfate
The concentration of solution is 250 ± 5g/L, Sb2O3/SnO2For 0.1-0.14.
In step C, wash to filtrate electrical conductivity and be less than 50 μ s/cm.
In step C, dry using vacuum drying, controlled at 140-150 DEG C, dry 10-11h, water content is less than
0.5%.The control of drying temperature, is to only slough surface water, does not slough the crystallization water or with reference to water, can so keep coating
The structure of hydrous oxide in thing；Temperature is excessive to cause titanium dioxide granule condensation to be difficult to crush, and reduce dispersiveness.It is dry
The control of time, is to be able to preferably condense, excessively not soft, and product stickiness otherwise after crushed is big, easily blocks
Pipeline.Can the control of moisture be to judge the condition that crushed.
In step C, during crushing, 325 mesh screen residues are first crushed to less than 0.1% using Universalpulverizer, then air-flow powder again
325 mesh screen residues are broken to less than 0.01%.Universalpulverizer carries out coarse crushing, avoids overcrushing；Although Universalpulverizer also can
Powder obtains very thin, but is extremely difficult to require from particle diameter distribution, shape of particle, product purity etc..Therefore airslide disintegrating mill is needed
Finely divided, depolymerization particle is carried out, ensures particle diameter requirement, enhances product performance.The Granularity Distribution of air-flow crushing is seldom
Change over time, the quality of product is more stable；Air-flow crushing machinery abrasion is small, and pulverized material is not easy to pollute.Though
Right air-flow crushing is most effective crushing, but its running cost is high, and energy source consumption is more, and the running cost of mechanical crushing compared with
It is low.Crushed using substep, reduce power consumption, improve crush efficiency.
The beneficial effects of the invention are as follows：
For preparation method of the present invention mainly in the preparation of the nano-titanium dioxide for battery, this is different from common receive
Rice titanium dioxide preparation, it is necessary to consider by nano-titanium dioxide be applied to battery after irreversible situation and influence, for this I
Have studied one prepare for battery conductive mesoporous nano titanium dioxide preparation method, clean environment firendly, the conduction of preparation
Mesohole nano-titanium dioxide is easily more scattered than the nano-particle of general concept, is handled by metatianate, calcines SnO2/Sb2O3Doping
Prepare conductive mesoporous nano TiO2Specific surface area is big, good conductivity, belongs to pioneering for lithium electronics negative material.
The addition of sal volatile affects the feature of titanium dioxide, and the addition of sal volatile is hot more than 150 DEG C
Decompose, TiO can be made2Particle is loose.Through research, sal volatile addition is controlled in 5-10%, it is ensured that crystal particles, two
Secondary particle diameter is stablized.If sal volatile addition is less than 5%, the titanium dioxide specific surface area obtained is small, mesopore diameter
It is small, aggregate particle size is unstable；If sal volatile addition is more than 10%, the titanium dioxide specific surface area obtained is small.
Although the addition of sal volatile can make TiO2Particle is loose, but finds sal volatile in the course of the research
Addition can cause the problems such as solids is cohesive, aperture is small.To solve the problems, such as this, the present invention is by controlling the temperature calcined and calcining
Time solves, and is 300-500 DEG C by controlling calcining heat, makes dehydration complete, remnants (NH after calcining4)2CO3It is few, so as to keep away
Exempted from solids bonding, so ensure that therefore caused by aperture and specific surface area problem.If temperature is less than 300 DEG C, dehydration
Incomplete remnants (NH4)2CO3More, pH high, causes solids surface to bond so that aperture is small, specific surface area is small.If temperature is higher than
500 DEG C, crystal particles and offspring are all grown up, and it is small to will also result in specific surface area.Calcining heat is mutually auxiliary phase with calcination time
Into, the control of calcination time can improve Calcine Strength, and calcination time is less than 4h, causes specific surface area seriously to diminish；Calcining
Time is more than 5h, and crystal particle diameter is grown up, and also results in and diminishes than surface knot, therefore need to strictly control 300-500 DEG C of calcining heat, forges
Burn time 4-5h.
The addition of sulfuric acid solution of tin can reduce meso-porous nano TiO2Resistivity, by controlling its addition, make conduction
TiO210 Ω cm of resistivity ＜；To further improve conductive TiO2Electric conductivity, by while sulfuric acid solution of tin is added
Antimony sulfate solution is added, and controls Sb2O3/SnO2It is worth for 0.1-0.14, it is not only unfavorable that antimony sulfate solution is added if less than 0.1
Can be that electric conductivity declines on the contrary in electric conductivity；If more than 0.14, resistivity decline is smaller, is also unfavorable for the raising of electric conductivity；
Only control in 0.1-0.14, conduction TiO could be improved2Electric conductivity, obtain excellent electric conductivity.
Brief description of the drawings
Fig. 1 is different multiplying discharge performance figure.
Fig. 2 is charge-discharge property curve map.
Fig. 3 is charge-discharge performance figure.
Fig. 4 is cyclic voltammetry scan curve map.
Fig. 5 is SnO2To resistivity effects figure.
Fig. 6 is Sb2O3/SnO2Influence figure to resistivity.
Embodiment
With reference to specific embodiment, the present invention is further illustrated.
First, specific embodiment
Embodiment 1
A, metatitanic acid is added into desalted water slurrying in salt treatment reactor, controls TiO2Concentration is 350g/L, adds concentration
For 30-40% sal volatile 5% (relative to metatitanic acid quality, NH3/TiO2), 1h is stirred, vacuum filter, filter cake is in resistance
Calcined in stove, the temperature for controlling calcining is 300 DEG C, and the time of calcining is 5h, is then crushed to 325 with Universalpulverizer
Mesh screen residue is less than 0.1%, obtains calcinated titanium dioxide powder；
B, calcinated titanium dioxide powder is added into desalted water slurrying, then adds 0.2% (SiO thereto2/TiO2) sodium metasilicate
Solution (50g ± 5g/L), control slurry concentration TiO2600g/L, particle of the grinder grinding distribution to particle diameter less than 0.5 μm account for
97%；
C, the slurry after above-mentioned steps B is disperseed is diluted to TiO in coating groove with desalted water2350g/L, is warming up to 60 DEG C,
Add 0.2% calgon (relative to stock quality), stir evenly, add 15% sulfuric acid solution of tin (250 ± 5g/L of concentration) and
Antimony sulfate solution (250 ± 5g/L of concentration), Sb2O3/SnO2For 0.1, sulfuric acid tune pH value, cures 1h, vacuum filter washing, filtrate
Electrical conductivity is less than 50 μ s/cm, and filter cake is in 140 DEG C of dry 11h of vacuum drying chamber, and water content is less than 0.5%, then with omnipotent crushing
Machine is crushed to 325 mesh screen residues and is less than 0.01% less than 0.1%, then with air-flow crushing to 325 mesh screen residues, obtains conductive mesoporous nano
Titanium dioxide.
Embodiment 2
A, metatitanic acid is added into desalted water slurrying in salt treatment reactor, controls TiO2Concentration is 400g/L, adds concentration
For 40% sal volatile 10%, 1.5h, vacuum filter are stirred, filter cake is calcined in resistance furnace, control the temperature of calcining
Spend for 500 DEG C, the time of calcining is 4h, is then crushed to 325 mesh screen residues less than 0.1% with Universalpulverizer, obtains calcining dioxy
Change titanium valve；
B, calcinated titanium dioxide powder is added into desalted water slurrying, then adds 0.2% (SiO thereto2/TiO2) sodium metasilicate
Solution (50g ± 5g/L), control slurry concentration TiO2700g/L, particle of the grinder grinding distribution to particle diameter less than 0.5 μm account for
97%；
C, the slurry after above-mentioned steps B is disperseed is diluted to TiO in coating groove with desalted water2400g/L, is warming up to 70 DEG C,
Add 0.2% calgon, stir evenly, add 15-16% sulfuric acid solution of tin (250 ± 5g/L of concentration) and antimony sulfate solution (dense
Spend 250 ± 5g/L), Sb2O3/SnO2For 0.14, sulfuric acid tune pH value cures 2h, vacuum filter washing, and filtrate electrical conductivity is less than 50 μ
S/cm, filter cake are less than 0.5%, are then crushed to 325 mesh with Universalpulverizer in 150 DEG C of dry 10h of vacuum drying chamber, water content
Tail over less than 0.1%, then be less than 0.01% with air-flow crushing to 325 mesh screen residues, obtain conductive mesoporous nano titanium dioxide.
Embodiment 3
A, metatitanic acid is added into desalted water slurrying in salt treatment reactor, controls TiO2Concentration is 365g/L, adds concentration
For 35% sal volatile 6%, 1.2h, vacuum filter are stirred, filter cake is calcined in resistance furnace, control the temperature of calcining
Spend for 400 DEG C, the time of calcining is 4.5h, is then crushed to 325 mesh screen residues less than 0.1% with Universalpulverizer, obtains calcining two
Titanium oxide powder；
B, calcinated titanium dioxide powder is added into desalted water slurrying, then adds 0.2% (SiO thereto2/TiO2) sodium metasilicate
Solution (50g ± 5g/L), control slurry concentration TiO2650g/L, particle of the grinder grinding distribution to particle diameter less than 0.5 μm account for
97%；
C, the slurry after above-mentioned steps B is disperseed is diluted to TiO in coating groove with desalted water2365g/L, is warming up to 65 DEG C,
Add 0.2% calgon, stir evenly, add 15% sulfuric acid solution of tin (250 ± 5g/L of concentration) and antimony sulfate solution (concentration
250 ± 5g/L), Sb2O3/SnO2For 0.11, sulfuric acid tune pH value cures 1.5h, vacuum filter washing, and filtrate electrical conductivity is less than 50 μ
S/cm, filter cake are less than 0.5%, are then crushed to 325 with Universalpulverizer in 145 DEG C of dry 10.5h of vacuum drying chamber, water content
Mesh screen residue is less than 0.1%, then is less than 0.01% with air-flow crushing to 325 mesh screen residues, obtains conductive mesoporous nano titanium dioxide.
Embodiment 4
A, metatitanic acid is added into desalted water slurrying in salt treatment reactor, controls TiO2Concentration is 375g/L, adds concentration
For 33% sal volatile 7%, 1.3h, vacuum filter are stirred, filter cake is calcined in resistance furnace, control the temperature of calcining
Spend for 350 DEG C, the time of calcining is 4.3h, is then crushed to 325 mesh screen residues less than 0.1% with Universalpulverizer, obtains calcining two
Titanium oxide powder；
B, calcinated titanium dioxide powder is added into desalted water slurrying, then adds 0.2% (SiO thereto2/TiO2) sodium metasilicate
Solution (50g ± 5g/L), control slurry concentration TiO2630g/L, particle of the grinder grinding distribution to particle diameter less than 0.5 μm account for
97%；
C, the slurry after above-mentioned steps B is disperseed is diluted to TiO in coating groove with desalted water2375g/L, is warming up to 63 DEG C,
Add 0.2% calgon, stir evenly, add 16% sulfuric acid solution of tin (250 ± 5g/L of concentration) and antimony sulfate solution (concentration
250 ± 5g/L), Sb2O3/SnO2For 0.12, sulfuric acid tune pH value cures 1.3h, vacuum filter washing, and filtrate electrical conductivity is less than 50 μ
S/cm, filter cake are less than 0.5%, are then crushed to 325 with Universalpulverizer in 143 DEG C of dry 10.3h of vacuum drying chamber, water content
Mesh screen residue is less than 0.1%, then is less than 0.01% with air-flow crushing to 325 mesh screen residues, obtains conductive mesoporous nano titanium dioxide.
Embodiment 5
A, metatitanic acid is added into desalted water slurrying in salt treatment reactor, controls TiO2Concentration is 385g/L, adds concentration
For the sal volatile 8% of 30-40%, 1.4h, vacuum filter are stirred, filter cake is calcined in resistance furnace, control calcining
Temperature is 450 DEG C, and the time of calcining is 4.7h, is then crushed to 325 mesh screen residues less than 0.1% with Universalpulverizer, must calcine
Titanium dioxide powder；
B, calcinated titanium dioxide powder is added into desalted water slurrying, then adds 0.2% (SiO thereto2/TiO2) sodium metasilicate
Solution (50g ± 5g/L), control slurry concentration TiO2680g/L, particle of the grinder grinding distribution to particle diameter less than 0.5 μm account for
97%；
C, the slurry after above-mentioned steps B is disperseed is diluted to TiO in coating groove with desalted water2385g/L, is warming up to 68 DEG C,
Add 0.2% calgon, stir evenly, add 15% sulfuric acid solution of tin (250 ± 5g/L of concentration) and antimony sulfate solution (concentration
250 ± 5g/L), Sb2O3/SnO2For 0.13, sulfuric acid tune pH value cures 1.8h, vacuum filter washing, and filtrate electrical conductivity is less than 50 μ
S/cm, filter cake are less than 0.5%, are then crushed to 325 with Universalpulverizer in 147 DEG C of dry 10.8h of vacuum drying chamber, water content
Mesh screen residue is less than 0.1%, then is less than 0.01% with air-flow crushing to 325 mesh screen residues, obtains conductive mesoporous nano titanium dioxide.
2nd, application test
1st, battery charging and discharging is tested
In this experimentation, the constant current charge-discharge test of the battery assembled is produced in Shenzhen Weir electronics scientific technology co
BTS-5V5 battery performance tests more than carry out, experiment keep room temperature it is constant.Test the charging and discharging capacity of negative material, fill
Discharge-rate, charge and discharge cycles number.Discharge and recharge：Interval 5 minutes, constant current discharge value 1V, is spaced 3 minutes, constant-current charge 3V.
First to negative material activation process：With 0.2C rate charge-discharges 3 times, then experiment test work is being carried out.
According to optimal conditions (NH4)2CO3Dosage is 5%, 500 DEG C of calcining heat, calcination time 4h, SnO2Dosage is
15%, Sb2O3/SnO2For 0.10, prepare sample and carry out battery charging and discharging test, test result sees below Fig. 1,2,3.
From fig. 1, it can be seen that different discharge-rate guiding discharge specific capacities is different, as discharge-rate improves, discharge specific volume
Amount declines, but it is more stable that 20 specific discharge capacities are circulated under each multiplying power.Since the electric conductivity of material is preferable, reversible capacity ratio
Relatively stablize, from 0.2C to 5C, specific discharge capacity only declines 15.83%.
Fig. 2 is battery 5C charge-discharge performances curve first, and it was found from figure, battery only has a discharge platform, and relatively more flat
Steady 1.51-1.55V, first charge-discharge specific capacity are respectively 208.95mAh/g, 218.57mAh/g, there is higher first charge-discharge
Efficiency 95.60%, illustrates that material property is preferable.
Fig. 3 is battery 5C charge-discharge performance curves, and battery first discharge specific capacity is 218.57mAh/g, 100 circulations,
Discharge capacity 212.97mAh/g, 100 cycle efficienies are maintained at 97.08%, and battery has preferable cycle performance.
2nd, cyclic voltammetry test battery
With optimal conditions (NH4)2CO3Dosage is 5%, 500 DEG C of calcining temperature, calcination time 4h, SnO2Dosage is 15%,
Sb2O3/SnO2For 0.10, sample assembly battery is prepared, the electrochemical analyser produced with Beijing Hui Long Huan Ke Envirolution, INC.
CHI660E carries out cyclic voltammetry test, sweep speed 0.2mv/s.Test result is referring to Fig. 4
As can be seen from Figure 4, mesoporous TiO2Anodizing reaction potential about 1.75V positions, reduction potential 1.52V, redox
Potential difference is 0.23V, and image symmetrical characteristic is relatively good, and redox peaks are relatively narrow, illustrates that the invertibity of electrode is preferable, cycle performance compared with
It is good.
3rd, the verification that sal volatile influences conductive mesoporous nano titanium dioxide feature
500 DEG C of calcining heat is set, when calcination time 4 is small.(NH4)2CO3Dosage (NH3/TiO2) take less than 5%, 5-10%
With more than 10%, example：0 (A1), 1% (B1), 5% (C1), 10% (D1), 15% (E1).Investigate (NH4)2CO3Dosage pair
TiO2The influence of the features such as 10% slurry pH value, crystal particle diameter, aggregate particle size, aperture, specific surface area.Test result such as table 1 below.
Table 1
It can be verified from the data experiments of table 1, the addition of sal volatile is the spy to conductive mesoporous nano silica
Sign is influential.With (NH4)2CO3Dosage increase, TiO2The increase of 10% slurry pH value, TiO2In (NH4)2CO3Content increase
Add, improve TiO2Slurry pH value, crystal particles, offspring particle diameter are substantially stablized, (NH4)2CO3The heat point more than 150 DEG C
Solution, TiO2Particle is loose.
4th, the verification that calcining influences conductive mesoporous nano titanium dioxide feature
Calcining heat is to TiO2The influence verification of appearance features
Set (NH4)2CO3Dosage (NH3/TiO2) 5%, when calcination time 4 is small.Calcining heat is set to be less than 300 DEG C, 300-
500 DEG C and the parameter more than 500 DEG C, such as：200 DEG C (A2), 300 DEG C (B2), 400 DEG C (C2), 500 DEG C (D2), 600 DEG C
(E2), calcining heat is investigated to TiO2The shadow of the features such as 10% slurry pH value, crystal particle diameter, aggregate particle size, aperture, specific surface area
Ring, test result such as table 2 below.
Table 2
Learnt from table 2,200 DEG C of calcining heat, dehydration is incomplete, remaining (NH4)2CO3More, pH high, solids bonds, hole
Footpath is small, and specific surface area is small.Temperature reaches 600 DEG C, and crystal particles and offspring are all grown up, and specific surface area is small.Demonstrate calcining
Influence of the temperature to conductive mesoporous nano titanium dioxide feature.
Calcination time is to TiO2The influence verification of appearance features
Under the premise of certain calcining heat, Calcine Strength can be improved by improving calcination time, and calcining heat improves, can be with
Accelerate calcining, shorten calcination time, calcining heat can be suitably reduced by extending calcination time.Set (NH4)2CO3Dosage is
5%, 500 DEG C of calcining heat.Set calcination time to be less than 3h, 3-4h and investigated more than 4h, such as 2.0h (A3), 3.0h
(B3)、4.0h(C3)、5.0h(D3)、6.0h(E3).Calcination time is investigated to TiO2It is 10% slurry pH value, crystal particle diameter, secondary
The influence of the features such as particle diameter, aperture, specific surface area, test result such as table 3 below.
Table 3
By the data verification of table 2 and table 3, the feature of the control of calcination condition to conductive mesoporous nano titanium dioxide
It is influential.
5th, the influence verification of sulfuric acid solution of tin and antimony sulfate solution to conductive mesoporous nano titanium dioxide electric conductivity
Set (NH4)2CO3Dosage is 5%, 500 DEG C of calcining heat, calcination time 4h, Sb2O3/SnO2For 0.10.Referring to figure
5, with Sn (SO4)2Dosage increase, porous nano TiO2Resistivity reduces.Control SnO2Dosage 15-16%, conductive TiO2Electricity
10 Ω cm of resistance rate ＜ requirements.
Antimony sulfate/STANNOUS SULPHATE CRYSTALLINE dosage ratio (Sb2O3/SnO2) to TiO2The verification of Conductivity
Set (NH4)2CO3Dosage is 5%, 500 DEG C of calcining heat, calcination time 4h, SnO2Dosage is 15%, is set
Sb2O3/SnO2Ratio 0.02,0.04,0.06,0.08,0.10,0.12,0.14,0.16,0.18.Investigate Sb2O3/SnO2Size pair
TiO2The influence of resistivity.
As can be seen from Figure 6, with Sb2O3/SnO2Raising, TiO2Resistivity reduce, electric conductivity improve, work as STANNOUS SULPHATE CRYSTALLINE
Dosage is 15% (SnO2/TiO2), Sb2O3/SnO2Value is more than 0.1, and 10 Ω cm of resistivity ＜, work as Sb2O3/SnO2＞ 0.14, electricity
Resistance rate declines smaller.
Conduction of the addition of this experimental verification sulfuric acid solution of tin and antimony sulfate solution to conductive mesoporous nano titanium dioxide
Property is influential.
Preparation method progress of the present invention protrudes, and (1) micro- mesohole nano-titanium dioxide easily divides than the nano-particle of general concept
Dissipate, handled by metatianate, calcine SnO2/Sb2O3Doping prepares meso-porous nano TiO2Specific surface area is big, good conductivity, is used for
Lithium electronics negative material belongs to pioneering.(2) prepared by mesohole nano-titanium dioxide of the invention prepares than existing nano-titanium dioxide
Technique is simple, clean environment firendly.Prepare mesohole nano-titanium dioxide process and belong to pioneering.
Claims (8)
1. a kind of preparation method of conductive mesoporous nano titanium dioxide, it is characterised in that comprise the following steps：
A, metatitanic acid is added into desalted water slurrying, controls TiO2Concentration is 350-400g/L, adds sal volatile, is stirred, filtering,
Calcining, is crushed to 325 mesh screen residues less than 0.1%, obtains calcinated titanium dioxide powder；
B, calcinated titanium dioxide powder is added into desalted water slurrying, then adds sodium silicate solution thereto, control slurry concentration
TiO2600-700g/L, particle of the grinding distribution to particle diameter less than 0.5 μm account for 97%；
C, pulp dilution after above-mentioned steps B is disperseed is to TiO2350-400g/L, is warming up to 60-70 DEG C, adds calgon,
Stir evenly, add sulfuric acid solution of tin and antimony sulfate solution, cure 1-2h, filter, wash, dry, pulverize to 325 mesh screen residues and be less than
0.01%, obtain conductive mesoporous nano titanium dioxide.
A kind of 2. preparation method of conductive mesoporous nano titanium dioxide according to claim 1, it is characterised in that step A
In, the mass concentration of the sal volatile is 30-40%, and addition is the 5-10% of metatitanic acid quality.
A kind of 3. preparation method of conductive mesoporous nano titanium dioxide according to claim 1, it is characterised in that step A
In, mixing time 1-1.5h, the temperature of calcining is 300-500 DEG C, and the time of calcining is 4-5h.
A kind of 4. preparation method of conductive mesoporous nano titanium dioxide according to claim 1, it is characterised in that step B
In, the mass concentration of the sodium silicate solution is 50 ± 5g/L, and the addition of sodium silicate solution is with SiO2/TiO2It is calculated as 0.2-
0.3%.
A kind of 5. preparation method of conductive mesoporous nano titanium dioxide according to claim 1, it is characterised in that step C
In, the concentration of sulfuric acid solution of tin is 250 ± 5g/L, and the dosage of sulfuric acid solution of tin is the 15-16% of stock quality, antimony sulfate solution
Concentration be 250 ± 5g/L, Sb2O3/SnO2For 0.1-0.14.
A kind of 6. preparation method of conductive mesoporous nano titanium dioxide according to claim 1, it is characterised in that step C
In, wash to filtrate electrical conductivity and be less than 50 μ s/cm.
A kind of 7. preparation method of conductive mesoporous nano titanium dioxide according to claim 1, it is characterised in that step C
In, dry using vacuum drying, controlled at 140-150 DEG C, dry 10-11h, water content is less than 0.5%.
A kind of 8. preparation method of conductive mesoporous nano titanium dioxide according to claim 1, it is characterised in that step C
In, during crushing, 325 mesh screen residues are first crushed to less than 0.1% using Universalpulverizer, then again air-flow crushing to 325 mesh screen residues
Less than 0.01%.
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