CN108033486B - 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 PDF

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CN108033486B
CN108033486B CN201711344806.2A CN201711344806A CN108033486B CN 108033486 B CN108033486 B CN 108033486B CN 201711344806 A CN201711344806 A CN 201711344806A CN 108033486 B CN108033486 B CN 108033486B
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titanium dioxide
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张建平
张川
张千
张潇
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HEBEI MILSON TITANIUM DIOXIDE CO Ltd
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Abstract

A kind of preparation method of conductive mesoporous nano titanium dioxide, belongs to the technical field of conductive mesoporous material, comprising the following steps: metatitanic acid A, is added to desalted water slurrying, controls TiO2Concentration is 350-400g/L, and sal volatile, stirring is added, and filtering, calcining are crushed to 325 mesh screen residues less than 0.1%, obtain calcinated titanium dioxide powder；B, desalted water slurrying is added in calcinated titanium dioxide powder, sodium silicate solution is then added thereto, control slurry concentration TiO2600-700g/L, particle of the grinding distribution to partial size less than 0.5 μm account for 97%；C, by the pulp dilution after above-mentioned steps B dispersion to TiO2350-400g/L is warming up to 60-70 DEG C, adds calgon, stirs evenly, and adds sulfuric acid solution of tin and antimony sulfate solution, cures 1-2h, is filtered, washed, dry, pulverize to 325 mesh screen residues less than 0.01%, obtain conductive mesoporous nano titanium dioxide.Preparation method of the present invention is simply, it can be achieved that the industrialized production of conductive mesoporous nano titanium dioxide, technology controlling and process precision are high.

Description

A kind of preparation method of conductive mesoporous nano titanium dioxide
Technical field
The invention belongs to the technical field of conductive mesoporous material, it 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 technique
With the increase of economic development and the size of population, demand of the mankind to the energy sharply expands, non-renewable fossil energy Source gradually decreases, final exhausted.Serious environmental problem, clean reproducible energy, such as solar energy, wind energy is brought to utilize simultaneously 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 from the beginning of the seventies in last century with its superiority.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 speed, safety factors are to restrict the main reason for lithium battery is enlarged.It is excellent The acquisition of good electrode material is one of basic reason, especially negative electrode material.
TiO2With open crystal structure, the flexible electronic structure of titanium ion, so that TiO2The electricity of acceptable foreign ion Son, and the lithium ion for insertion provides vacancy.TiO2Intercalation potential is higher than carbon, about 1.75V, can solve lithium in cathode and generate branch Brilliant problem；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 changes is destroyed, and the cycle performance and service life of material are improved.
TiO2It is 310mAh/g as lithium cell cathode material theoretical capacity, stability and safety are preferable, but due to Cathode TiO when charging2There are Ti4+It obtains electronics and becomes Ti3+, Li+With Ti2O3Generate LiTiO2For irreversible reaction, lead to TiO2 Irreversible capacity is high, and discharge-rate is not high.Therefore it solves the above problems and urgently pursues at present.
Summary 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 and process is simple, clean and environmental protection, passes through the collocation and stringent control of process, the TiO of preparation2Using rear reversible good.
The present invention be realize its purpose the technical solution adopted is that:
A kind of preparation method of conductive mesoporous nano titanium dioxide, comprising the following steps:
A, metatitanic acid is added into desalted water slurrying, controls TiO2Concentration is 350-400g/L, and sal volatile is added, and 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 could be sent out in calcining to make salt treatment agent sufficiently be adsorbed on metatitanic acid particle surface or be entrained among gap Best salt treatment effect is waved, metatitanic acid slurry concentration is too low, and inorganic agent is easy to be lost, and reduces what reality was adsorbed by metatitanic acid Amount, influences salt treatment effect；Metatitanic acid slurry concentration is excessively high, then additive cannot be evenly dispersed in slurry, also will affect salt Treatment effect.
B, desalted water slurrying is added in calcinated titanium dioxide powder, sodium silicate solution is then added thereto, control slurry is dense Spend TiO2600-700g/L, particle of the grinding distribution to partial size less than 0.5 μm account for 97%；In order to which silicon fine dispersion forms silica gel packet Cover control slurry concentration TiO2600-700g/L, too low or excessive concentrations, it is difficult to disperse, coating is bad, and granularity is not after crushing Good, properties of product are poor.It is summarized through research, there are 0.5 μm or more bulky grain, covering power, tinting strength, tinting power, bottom form and aspect for titanium dioxide Etc. performance indicators can decreased significantly, therefore need particle of the grinding distribution to partial size less than 0.5 μm to account for 97% in the step.
C, by the pulp dilution after above-mentioned steps B dispersion 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, is filtered, washed, dry, pulverize to 325 meshes It is remaining less than 0.01%, obtain conductive mesoporous nano titanium dioxide.In order to which back is evenly 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 crossed and is exceeded to realize silicon coating condition It is low not fine and close, effect of the calgon as dispersing agent.In order to guarantee to adulterate effect, 1-2h need to be cured by control, it is too short to mix Miscellaneous metal ion is insufficient, the too long mixture easy to form being in a mess.
In step A, the mass concentration of the sal volatile is 30-40%, additional amount 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 the key that influence dispersion, and too short or too long will lead to is dispersed unevenly.
In step B, the mass concentration of the sodium silicate solution is 50 ± 5g/L, and the additional amount of sodium silicate solution is with SiO2/ TiO2It is calculated as 0.2-0.3%.The control of sodium metasilicate capacity concentration and additional amount is in order to avoid forming gallimaufry, well Dispersion forms the condition of 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, washing is to filtrate conductivity less than 50 μ s/cm.
Dry using vacuum drying in step C, controlled at 140-150 DEG C, dry 10-11h, water content is less than 0.5%.The control of drying temperature is not slough the crystallization water in order to only slough surface water or combine water, can keep coating in this way The structure of hydrous oxide in object；Temperature is excessively high to be will cause titanium dioxide granule condensation and is difficult to crush, and dispersibility is reduced.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, is easy blocking Pipeline.Can the control of moisture content be the condition in order to judge be crushed.
In step C, when 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, guarantees particle diameter requirement, enhances product performance.The Granularity Distribution of air-flow crushing is seldom It changes over time, the quality of product is more stable；The abrasion of air-flow crushing machinery is small, is not easy to pollute to pulverized material.Though Right air-flow crushing is most effective crushing, but its operating cost is high, and energy source consumption is more, and the operating cost being mechanically pulverized compared with It is low.It is crushed using substep, reduces power consumption, improve crush efficiency.
The beneficial effects of the present invention are:
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, need consider by nano-titanium dioxide be applied to battery after irreversible situation and influence, thus I Have studied one preparation for battery conductive mesoporous nano titanium dioxide preparation method, clean and environmental protection, the conduction of preparation Mesohole nano-titanium dioxide easily disperses than the nanoparticle of general concept, is handled by metatianate, calcining SnO2/Sb2O3Doping Prepare conductive mesoporous nano TiO2Large specific surface area, good conductivity belong to pioneering for lithium electronics negative electrode material.
The additional amount of sal volatile affects the feature of titanium dioxide, the addition of sal volatile, in 150 DEG C or more heat It decomposes, TiO can be made2Particle is loose.Through studying, sal volatile additional amount is controlled in 5-10%, it is ensured that crystal particles, two Secondary particle diameter is stablized.If the titanium dioxide specific surface area that sal volatile additional amount less than 5%, obtains is small, mesopore diameter It is small, aggregate particle size is unstable；If sal volatile additional amount is greater 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 The problems such as addition will cause solids bonding, aperture is small.To solve this problem, temperature and calcining that the present invention passes through control calcining Time solves, and is 300-500 DEG C by control calcination temperature, makes dehydration completely, remnants (NH after calcining4)2CO3It is few, 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.Calcination temperature and calcination time are Xiang Fuxiang At, Calcine Strength can be improved in the control of calcination time, and calcination time is less than 4h, specific surface area is caused seriously to become smaller；Calcining Time is greater than 5h, and crystal particle diameter grows up, also results in specific surface knot and become smaller, therefore need 300-500 DEG C of strict control calcination temperature, forge Burn time 4-5h.
The addition of sulfuric acid solution of tin can reduce meso-porous nano TiO2Resistivity make conduction by controlling its additional amount TiO210 Ω cm of resistivity <；To further increase conductive TiO2Electric conductivity, by while sulfuric acid solution of tin is added Antimony sulfate solution is added, and controls Sb2O3/SnO2Value is 0.1-0.14, and it is not only unfavorable that antimony sulfate solution is added if less than 0.1 It can be that electric conductivity declines instead in electric conductivity；If more than 0.14, resistivity decline is smaller, is also unfavorable for the raising of electric conductivity； Only control could improve conduction TiO in 0.1-0.142Electric conductivity, obtain excellent electric conductivity.
Detailed description of the invention
Fig. 1 is different multiplying discharge performance figure.
Fig. 2 is charge-discharge property curve graph.
Fig. 3 is charge-discharge performance figure.
Fig. 4 is cyclic voltammetry scan curve graph.
Fig. 5 is SnO2To resistivity effects figure.
Fig. 6 is Sb2O3/SnO2To the influence diagram of resistivity.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
One, specific embodiment
Embodiment 1
A, metatitanic acid is added to desalted water slurrying in salt treatment reactor, controls TiO2Concentration is 350g/L, and concentration is added For 30-40% sal volatile 5% (relative to metatitanic acid quality, NH3/TiO2), 1h is stirred, vacuum filter, filter cake is in resistance It is calcined in furnace, 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 obtains calcinated titanium dioxide powder less than 0.1%；
B, desalted water slurrying is added in calcinated titanium dioxide powder, 0.2% (SiO is then added thereto2/TiO2) sodium metasilicate Solution (50g ± 5g/L) controls slurry concentration TiO2600g/L, particle of the grinder grinding distribution to partial size less than 0.5 μm account for 97%；
C, the slurry after above-mentioned steps B dispersion is diluted to TiO with desalted water in coating slot2350g/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/SnO2It is 0.1, sulfuric acid tune pH value cures 1h, vacuum filter washing, filtrate Conductivity is less than 50 μ s/cm, and filter cake is in 140 DEG C of vacuum oven dry 11h, and water content is less than 0.5%, then with omnipotent crushing Machine is crushed to 325 mesh screen residues less than 0.1%, then with air-flow crushing to 325 mesh screen residues less than 0.01%, obtain conductive mesoporous nano Titanium dioxide.
Embodiment 2
A, metatitanic acid is added to desalted water slurrying in salt treatment reactor, controls TiO2Concentration is 400g/L, and concentration is added For 40% sal volatile 10%, 1.5h, vacuum filter are stirred, filter cake is calcined in resistance furnace, control the temperature of calcining Degree is 500 DEG C, and 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, desalted water slurrying is added in calcinated titanium dioxide powder, 0.2% (SiO is then added thereto2/TiO2) sodium metasilicate Solution (50g ± 5g/L) controls slurry concentration TiO2700g/L, particle of the grinder grinding distribution to partial size less than 0.5 μm account for 97%；
C, the slurry after above-mentioned steps B dispersion is diluted to TiO with desalted water in coating slot2400g/L is warming up to 70 DEG C, Add 0.2% calgon, stir evenly, adds 15-16% sulfuric acid solution of tin (250 ± 5g/L of concentration) and antimony sulfate solution (dense Spend 250 ± 5g/L), Sb2O3/SnO2It is 0.14, sulfuric acid tune pH value cures 2h, and vacuum filter washing, filtrate conductivity is less than 50 μ Then s/cm, filter cake are crushed to 325 mesh with Universalpulverizer less than 0.5% in 150 DEG C of vacuum oven dry 10h, water content Tail over less than 0.1%, then with air-flow crushing to 325 mesh screen residues less than 0.01%, obtain conductive mesoporous nano titanium dioxide.
Embodiment 3
A, metatitanic acid is added to desalted water slurrying in salt treatment reactor, controls TiO2Concentration is 365g/L, and concentration is added For 35% sal volatile 6%, 1.2h, vacuum filter are stirred, filter cake is calcined in resistance furnace, control the temperature of calcining Degree is 400 DEG C, and 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, desalted water slurrying is added in calcinated titanium dioxide powder, 0.2% (SiO is then added thereto2/TiO2) sodium metasilicate Solution (50g ± 5g/L) controls slurry concentration TiO2650g/L, particle of the grinder grinding distribution to partial size less than 0.5 μm account for 97%；
C, the slurry after above-mentioned steps B dispersion is diluted to TiO with desalted water in coating slot2365g/L is warming up to 65 DEG C, Add 0.2% calgon, stir evenly, adds 15% sulfuric acid solution of tin (250 ± 5g/L of concentration) and antimony sulfate solution (concentration 250 ± 5g/L), Sb2O3/SnO2It is 0.11, sulfuric acid tune pH value cures 1.5h, and vacuum filter washing, filtrate conductivity is less than 50 μ Then s/cm, filter cake are crushed to 325 with Universalpulverizer less than 0.5% in 145 DEG C of vacuum oven dry 10.5h, water content Mesh screen residue less than 0.1%, then with air-flow crushing to 325 mesh screen residues less than 0.01%, obtain conductive mesoporous nano titanium dioxide.
Embodiment 4
A, metatitanic acid is added to desalted water slurrying in salt treatment reactor, controls TiO2Concentration is 375g/L, and concentration is added For 33% sal volatile 7%, 1.3h, vacuum filter are stirred, filter cake is calcined in resistance furnace, control the temperature of calcining Degree is 350 DEG C, and 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, desalted water slurrying is added in calcinated titanium dioxide powder, 0.2% (SiO is then added thereto2/TiO2) sodium metasilicate Solution (50g ± 5g/L) controls slurry concentration TiO2630g/L, particle of the grinder grinding distribution to partial size less than 0.5 μm account for 97%；
C, the slurry after above-mentioned steps B dispersion is diluted to TiO with desalted water in coating slot2375g/L is warming up to 63 DEG C, Add 0.2% calgon, stir evenly, adds 16% sulfuric acid solution of tin (250 ± 5g/L of concentration) and antimony sulfate solution (concentration 250 ± 5g/L), Sb2O3/SnO2It is 0.12, sulfuric acid tune pH value cures 1.3h, and vacuum filter washing, filtrate conductivity is less than 50 μ Then s/cm, filter cake are crushed to 325 with Universalpulverizer less than 0.5% in 143 DEG C of vacuum oven dry 10.3h, water content Mesh screen residue less than 0.1%, then with air-flow crushing to 325 mesh screen residues less than 0.01%, obtain conductive mesoporous nano titanium dioxide.
Embodiment 5
A, metatitanic acid is added to desalted water slurrying in salt treatment reactor, controls TiO2Concentration is 385g/L, and concentration is added 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, desalted water slurrying is added in calcinated titanium dioxide powder, 0.2% (SiO is then added thereto2/TiO2) sodium metasilicate Solution (50g ± 5g/L) controls slurry concentration TiO2680g/L, particle of the grinder grinding distribution to partial size less than 0.5 μm account for 97%；
C, the slurry after above-mentioned steps B dispersion is diluted to TiO with desalted water in coating slot2385g/L is warming up to 68 DEG C, Add 0.2% calgon, stir evenly, adds 15% sulfuric acid solution of tin (250 ± 5g/L of concentration) and antimony sulfate solution (concentration 250 ± 5g/L), Sb2O3/SnO2It is 0.13, sulfuric acid tune pH value cures 1.8h, and vacuum filter washing, filtrate conductivity is less than 50 μ Then s/cm, filter cake are crushed to 325 with Universalpulverizer less than 0.5% in 147 DEG C of vacuum oven dry 10.8h, water content Mesh screen residue less than 0.1%, then with air-flow crushing to 325 mesh screen residues less than 0.01%, obtain conductive mesoporous nano titanium dioxide.
Two, application test
1, 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 test more than carry out, experiment keep room temperature it is constant.It tests the charging and discharging capacity of negative electrode material, fill Discharge-rate, charge and discharge cycles number.Charge and discharge: interval 5 minutes, constant current discharge value 1V is spaced 3 minutes, constant-current charge 3V. First negative electrode material is activated: using 0.2C rate charge-discharge 3 times, is then carrying out experiment test job.
According to optimal conditions (NH4)2CO3Dosage is 5%, 500 DEG C of calcination temperature, calcination time 4h, SnO2Dosage is 15%, Sb2O3/SnO2It is 0.10, prepares 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 decline, but it is more stable that 20 specific discharge capacities are recycled under each multiplying power.Since the electric conductivity of material is preferable, reversible capacity ratio More stable, from 0.2C to 5C, specific discharge capacity only declines 15.83%.
Fig. 2 is battery 5C charge-discharge performance curve for the first time, from figure it is found that only one discharge platform of battery, and it is 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 be battery 5C charge-discharge performance curve, battery first discharge specific capacity be 218.57mAh/g, 100 times circulation, Discharge capacity 212.97mAh/g, 100 cycle efficienies are maintained at 97.08%, and battery has preferable cycle performance.
2, cyclic voltammetry tests battery
With optimal conditions (NH4)2CO3Dosage is 5%, 500 DEG C of calcining temperature, calcination time 4h, SnO2Dosage is 15%, Sb2O3/SnO2It is 0.10, prepares sample assembly battery, the electrochemical analyser produced with Beijing Envirolution, INC., Hui Longhuan section CHI660E carries out cyclic voltammetry test, scanning speed 0.2mv/s.Test result referring to fig. 4
As can be seen from Figure 4, mesoporous TiO2The position anodizing reaction potential about 1.75V, 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.
3, the verifying that sal volatile influences conductive mesoporous nano titanium dioxide feature
500 DEG C of calcination temperature, calcination time 4 hours of setting.(NH4)2CO3Dosage (NH3/TiO2) take less than 5%, 5-10% Be greater 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 is as follows table 1.
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 increases, TiO210% slurry pH value increases, TiO2In (NH4)2CO3Content increase Add, improves TiO2Slurry pH value, crystal particles, offspring partial size are substantially stable, (NH4)2CO3In 150 DEG C or more heat point Solution, TiO2Particle is loose.
4, the verifying influenced on conductive mesoporous nano titanium dioxide feature is calcined
Calcination temperature is to TiO2The influence of appearance features is verified
Set (NH4)2CO3Dosage (NH3/TiO2) 5%, calcination time 4 hours.Calcination temperature is set less than 300 DEG C, 300- 500 DEG C and the parameter greater 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), calcination temperature is investigated to TiO2The shadow of the features such as 10% slurry pH value, crystal particle diameter, aggregate particle size, aperture, specific surface area It rings, test result is as follows table 2.
Table 2
It is learnt from table 2,200 DEG C of calcination temperature, dehydration is incomplete, remaining (NH4)2CO3It is more, pH high, solids bonding, hole Diameter 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 of appearance features is verified
Under the premise of certain calcination temperature, improving calcination time can be improved Calcine Strength, and calcination temperature improves, can be with Accelerate calcining, shorten calcination time, can suitably reduce calcination temperature by extending calcination time.Set (NH4)2CO3Dosage is 5%, 500 DEG C of calcination temperature.Calcination time is set and is less than 3h, 3-4h and is investigated greater 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 partial size, aperture, specific surface area, test result is as follows table 3.
Table 3
By the data verification of table 2 and table 3 it is found that the control of calcination condition is to the feature of conductive mesoporous nano titanium dioxide It is influential.
5, the influence verifying 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 calcination temperature, calcination time 4h, Sb2O3/SnO2It is 0.10.Referring to figure 5, with Sn (SO4)2Dosage increases, porous nano TiO2Resistivity reduces.Control SnO2Dosage 15-16%, conductive TiO2Electricity 10 Ω cm of resistance rate < requirement.
Antimony sulfate/STANNOUS SULPHATE CRYSTALLINE dosage ratio (Sb2O3/SnO2) to TiO2The verifying of Conductivity
Set (NH4)2CO3Dosage is 5%, 500 DEG C of calcination temperature, calcination time 4h, SnO2Dosage is 15%, setting 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 greater than 0.1, and 10 Ω cm of resistivity < works as Sb2O3/SnO2> 0.14, electricity The decline of resistance rate is 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 is prominent, and (1) micro- mesohole nano-titanium dioxide easily divides than the nanoparticle of general concept It dissipates, is handled by metatianate, calcining SnO2/Sb2O3Doping prepares meso-porous nano TiO2Large specific surface area, good conductivity, are used for Lithium electronics negative electrode material belongs to pioneering.(2) mesohole nano-titanium dioxide of the invention preparation is prepared than existing nano-titanium dioxide Simple process, clean and environmental protection.Prepare mesohole nano-titanium dioxide process belong to it is pioneering.

Claims (5)

1. a kind of preparation method of conductive mesoporous nano titanium dioxide, which comprises the following steps:
A, metatitanic acid is added into desalted water slurrying, controls TiO2Concentration is 350-400g/L, and sal volatile is added, and is stirred, filtering, Calcining, is crushed to 325 mesh screen residues less than 0.1%, obtains calcinated titanium dioxide powder；
B, desalted water slurrying is added in calcinated titanium dioxide powder, sodium silicate solution is then added thereto, control slurry concentration TiO2600-700g/L, particle of the grinding distribution to partial size less than 0.5 μm account for 97%；
C, by the pulp dilution after above-mentioned steps B dispersion to TiO2350-400g/L is warming up to 60-70 DEG C, adds calgon, It stirs evenly, adds sulfuric acid solution of tin and antimony sulfate solution, cure 1-2h, be filtered, washed, dry, pulverize to 325 mesh screen residues and be less than 0.01%, obtain conductive mesoporous nano titanium dioxide；
In step A, the mass concentration of the sal volatile is 30-40%, and additional amount is the 5-10% of metatitanic acid quality；
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；
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 the 15-16% of stock quality, The concentration of antimony sulfate solution is 250 ± 5g/L, Sb2O3/SnO2For 0.1-0.14.
2. a kind of preparation method of conductive mesoporous nano titanium dioxide according to claim 1, which is characterized in that step B In, the mass concentration of the sodium silicate solution is 50 ± 5g/L, and the additional amount of sodium silicate solution is with SiO2/TiO2It is calculated as 0.2- 0.3%.
3. a kind of preparation method of conductive mesoporous nano titanium dioxide according to claim 1, which is characterized in that step C In, washing is to filtrate conductivity less than 50 μ s/cm.
4. a kind of preparation method of conductive mesoporous nano titanium dioxide according to claim 1, which is characterized 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%.
5. a kind of preparation method of conductive mesoporous nano titanium dioxide according to claim 1, which is characterized in that step C In, when 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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