CN108039473A - Lithium battery special-purpose nanometer lithium titanate composite material preparation system - Google Patents
Lithium battery special-purpose nanometer lithium titanate composite material preparation system Download PDFInfo
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- CN108039473A CN108039473A CN201711317143.5A CN201711317143A CN108039473A CN 108039473 A CN108039473 A CN 108039473A CN 201711317143 A CN201711317143 A CN 201711317143A CN 108039473 A CN108039473 A CN 108039473A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The preparation system of lithium battery special-purpose nanometer lithium titanate composite material, titanium dioxide, aluminium salt, carbon source, lithium salts, magnesium salts are mixed, titanium dioxide is beaten first, aluminium salt, magnesium salts, lithium salts are dissolved, will be mixed in titanium dioxide, aluminium salt, magnesium salts, lithium salts input dispersant；And it is dried in vacuo and obtains presoma；Wherein titanium, aluminium, magnesium, lithium, the molar ratio of carbon are 5: (0.05~0.3): (0.1~0.4): (4.95~4.7): (2~20), presoma is put into the calcining of inert gas heating furnace high temperature, 800~1000 DEG C of temperature, when time is small more than 8, then the product after calcining is dropped into room temperature and obtains carbon-coated lithium titanate composite material.
Description
Technical field
The present invention relates to the production field of the preparation field of lithium battery, especially lithium titanate composite material.
Background technology
Conventional lithium-ion battery has the advantages that high-energy-density, high-specific-power, high-energy conversion efficiency, long circulation life, but
The problems such as there are being difficult to discharge and charge during low temperature.And lithium titanate battery uses lithium titanate as negative material, nano-silica is added
Change titanium is auxiliary material, and the core technology such as increase compression strain constant pressure valve, is a kind of safe and environment-friendly, the long-life lithium of new generation
Battery product, has all surmounted other lithium batteries significantly in performance and volume ratio.Common lithium battery charge and discharge below 0 DEG C
Electric energy power is very low, can not work normally, and in the case of -30 DEG C to 55 DEG C, the round-trip energy of discharge and recharge turns nano barium titanate lithium battery
Change efficiency more than 86%~91%, performance is very superior.Conventional lithium-ion battery charge and discharge circulation life at 5000 times or so,
Nano barium titanate lithium battery cycle life is up to more than 20000 times, and service life was more than 15 years.At present, the lithium titanate battery is wide
It is general to be applied to electric automobile, electric bicycle, electri forklift, carrier, cruiser, tour bus, it can be additionally used in the future to battery
The fields such as the higher electric bus of security requirement, mining engineering truck and military and space flight.
But in lithium titanate battery technique is produced, the requirement to titanium dioxide, lithium titanate composite material is very high, it is necessary to dioxy
Change titanium and reach nano-scale.But the titanium dioxide that produces in the prior art, lithium titanate composite material granularity, degree of purity etc. because
It is extremely difficult to apply the demand in lithium titanate battery on element, it is difficult to mass produce, rest on laboratory level.The mesh of the present invention
In view of the problems of the existing technology, the prior art is improved, improves the work of the special lithium titanate composite material of lithium battery
Yield rate prepared by industryization.
The content of the invention
In view of the deficiencies of the prior art, it is an object of the invention to provide a kind of lithium battery special-purpose nanometer lithium titanate composite material
Preparation system, including：Step 1, crush；Step 2, acidolysis；Step 3, sedimentation；Step 4, crystallization；Step 5, hydrolysis；Step 6, one
Secondary washing；Step 7, bleaching；Step 8, secondary washing；The preparation of step 9, crystal seed；Step 10, salt treatment；Step 11, calcining；
Step 12, crush；The synthesis of step 13, lithium titanate composite material；Step 14, wash three times；Step 15, press dry；Step 16, dodge
It is evaporated dry；Step 17, micrometer crusher；Step 18, select powder to be classified；Step 19, pulse dust removal.
Wherein step 5：Processed crystal seed is injected in hydrolytic tank and is hydrolyzed, the titanyl sulfate in titanium liquid is in heating
Under the conditions of, it is hydrolyzed by the induction of active seed, the hydrated titanium dioxide with certain particle diameter is made.
5.1st, the titanium liquid prepared is measured and squeezes into hydrolysis foreheater and crystal seed titanium liquid bath respectively, when liquid level reaches agitating paddle
When, that is, foreheater stirring is opened, the liquid caustic soda for preparing concentration is measured to throw crystal seed lye tank (vat) into spare.
5.2nd, after having broken material, foreheater steam inlet valve to be opened, is heated up to titanium liquid, heating outlet temperature is controlled at 96 DEG C,
Etc. crystal seed to be added.When foreheater titanium liquid temperature degree is raised to 75 DEG C, crystal seed titanium liquid bath steam inlet valve is opened, gives crystal seed titanium liquid liter
Temperature；Then open liquid caustic soda groove steam inlet valve and be warming up to 85 DEG C to liquid caustic soda, and keep this temperature；Treat that crystal seed titanium liquid is warming up to 85 DEG C
When, start crystal seed and make groove stirring, open liquid caustic soda groove baiting valve and liquid caustic soda is quickly put into crystal seed making groove, then open crystal seed titanium
And, continue to heat crystal seed making groove after discharging crystal seed titanium liquid during liquid bath baiting valve makes crystal seed titanium liquid and liquid caustic soda in crystal seed making groove
In material at 96 DEG C stop heating, quickly detect its stability, quickly opened when stability is in 130ml crystal seed make groove
Outlet valve, quickly puts the crystal seed made into and is preheating to 96 DEG C of foreheater titanium liquid.The titanium liquid of foreheater is allowed to be warming up to 96
Crystal seed is waited to carry out DEG C again, it is impossible to allow crystal seed to make and wait titanium liquid to heat up, otherwise crystal seed stability can drastically decline, and influence whole pot matter
Amount.
5.3rd, stirred 10 minutes after adding crystal seed, open hydrolyzer inlet valve, foreheater baiting valve is opened, foreheater
Titanium liquid is put into hydrolyzer, while starts hydrolyzer stirring.
5.4th, after foreheater titanium liquid is put into hydrolyzer, hydrolyzer live (open) steam inlet valve is opened, starts hydrolysis heating.
5.5th, (from time requirement≤28 minute for being warming up to boiling) after Hydrolysis of Titanium liquid once seethes with excitement, turn steam down, prevent
Transition boiling；When hydrolysis, which reaches 1: 1, turns white, stop steam, stop stirring insulation 30 minutes.
5.6th, insulation terminates, then opens stirring and steam progress secondary temperature elevation, and allows Hydrolysis of Titanium liquid to reach two in 20 minutes
Secondary boiling.
5.7th, rinse the foreheater of titanium liquid well and crystal seed makes pot, its flushing liquor is discharged into hydrolyzer when dilution water use, punching
Wash to finish and close valve.
5.8th, turning down live (open) steam valve keeps slight boiling condition (to keep pot inner pressure in 90~120mmH2O) 150 minutes.
5.9th, pressurize terminates, and opens the exhaust-valve of hydrolyzer, adds quantitative dilution water, concentration is reduced to 140~
(add volume 13.5m after water between 155g/l3), it is continuously heating to seethe with excitement, keeps slightly boiling 50 minutes.
5.10th, hydrolysis terminates, steam off valve.
5.11st, quantitative lignocellulosic is added toward the metatitanic acid after hydrolysis, and stirring 10 minutes can blowing.
5.12nd, open the bottom of a pan baiting valve and metatitanic acid after hydrolysis is sent to cooling system.
5.13rd, after blowing, rinse hydrolyzer inner wall to no plain boiled water well and flow out.Flushing finishes, and closes hydrolyzer and puts
Expect valve, wait use next time.
Wherein step 6：After hydrolysis, by graphite heat exchanger, once washed.
Wherein step 7：After once washing, bleached.
7.1st, clay kettle bottom baiting valve is closed, opens pot mouth inlet valve, rear metatitanic acid 45m is washed toward the interior addition one of clay kettle3,
Start stirring；
7.2nd, toward concentrated sulfuric acid measuring tank, accurately metering should add concentrated sulfuric acid volume；
7.3rd, toward titanous measuring tank, accurately metering should add titanous volume；
7.4th, stirring after ten minutes, first adds the concentrated sulfuric acid measured in past clay kettle；
7.5th, again toward adding the trivalent titanium solution that measures in clay kettle；
7.6th, the steam admission valve of clay kettle is opened, slurry is heated to 90 DEG C, when constant temperature insulation 2 is small；
7.7th, insulation terminates, steam off admission valve, inspection by sampling trivalent Ti content and effective acid content, if meeting work
Skill requirement, then bleach work and terminate.
If the 7.8th, Ti3+≤ 0.30g/l, then will add titanous depending on departure, and continue reduction 30 minutes, it is ensured that after bleaching
Slurry Ti3+Between 0.30~0.4g/l；
7.9th, after inspection by sampling bleaching after slurry qualified, slowly plus water is cooled to slurry≤75 DEG C；
Wherein step 8：Secondary washing is carried out after bleaching.
Open metatitanic acid storage tank baiting valve after floating, conveying metatitanic acid to 400m2Filter press.Washed with qualified water, most
Whole metatitanic acid iron-holder≤30ppm after the mashing of inclined titanium scraping blade hollander tub.Qualified metatitanic acid is delivered to two and washes qualified inclined titanium
Sour storage tank.
Wherein step 9：The preparation of crystal seed；
9.1st, alkali fusion：Filter press filtration washing qualification (its iron content is less than 50ppm) TiO is washed through two2Hydrate, with first
Crystal seed prepares and is pumped into metatitanic acid heating measuring tank, NaOH is heated separately to 60 DEG C and 90 DEG C after alkali heating measuring tank metering
Afterwards, by TiO2Hydrate NaOH and being put into alkali fusion tank carries out reaction and 50%NaOH solution reactions, generates positive sodium titanate.Through cold
But afterwards with the second crystal seed prepare pump squeeze into filter press by upper piece, washing, discharging, filter cake mashing, positive sodium titanate from containing big
To measure and separated in the filtrate of free NaOH solution, the NaOH filtrates of content 15% flow into lye collecting tank, then with the 3rd crystal seed
Preparation is pumped into external system and is used as tail gas spray.Special filter press, which is prepared, with crystal seed washs NaOH in positive sodium titanate filter cake, when
Measure after filtrate NaOH content is less than 1500ppm, discharging enters hollander tub, then again with 10% hydrochloric acid be neutralized to pH value to 3.5~
4.0 scope, with the 4th crystal seed prepare pump squeeze into crystal seed prepare Special filter press again by upper piece, washing, until washing filtrate
When pH value is more than 7, discharging, filter cake mashing, are made TiO2Concentration is controlled in 200~220g/l, is prepared into positive metatitanic acid intermediate products.
9.2nd, prepared by crystal seed：30% hydrochloric acid reaction generation titanium chloride peptization of positive sodium titanate, is that rutile-type is brilliant
Kind, used for salt treatment post.Peptization reaction carries out in the molten tank of crystal seed preparation vessel acid, and the crystal seed made squeezes into storage tank with pump
In.
Wherein, the chemical equation of rutile titanium dioxide crystal seed is as follows：
a、TiO2·nH2O+4NaOH=Na4TiO4+(n+1)H2O
b、Na4TiO4+4H2O=4NaOH+H4TiO4
c、Na4TiO4+ 4HCl=H4TiO4+4NaCl
d、H4TiO4+ 2HCl=TiOCl2+3H2O
Technic index prepared by crystal seed is as follows：
1. the TiO in metatitanic acid measuring tank2Concentration：270~290g/l；6.5~7m3 of its volume；Iron≤50ppm
2. the TiO in metatitanic acid measuring tank2Concentration：270~290g/l；Heating-up temperature：60℃
3. the alkali in alkali measuring tank：50%NaOH；Its volume：4.2m3；Heating-up temperature：90℃
4. the reaction temperature in alkali soluble tank：(108~120) DEG C：Boiling temperature：(97~103) DEG C
5. cold water solution meta-titanium perborate temperature：(50~55) DEG C
6. temperature of washing water：(40~55) DEG C
7. one washes rear TiO2Content：220~240g/l
8. the pH value after neutralizing：3.5~4.0
9. the pH value after peptization：≤1.0
10. nucleus reaction temperature：About 101 DEG C
11. crystal seed particle diameter：0.25~0.5 μm.
Wherein step 10：After secondary washing terminates, crystal seed prepares, salt treatment is carried out.
The dosage and addition sequence of salt treatment agent are as follows：
1st, calcining seeds 5%, addition 5%.With TiO2Meter
2nd, zinc oxide (ZnO) is added in salt treatment, addition 0.1%.With TiO2Meter, is stirred 30 minutes after addition.Again plus
After entering ammonium dihydrogen phosphate stirring 15 minutes, KOH0.9% is added, is then stirred for 150 minutes.
Wherein after step 11, salt treatment, squeezing press dry, and injection rotary kiln is calcined,
11.3rd, kiln operation is dried：
(1) when keeping small firepower baking rotary kiln small not less than 12.
(2) dry kiln during should keep " small firepower, the slow-speed of revolution ", with prevent kiln brick be damaged and a large amount of raw material produce.Specifically
Be preceding 4 little Shi high-temperatures area control below 400 DEG C, 8 it is small when temperature control below 600 DEG C, 10 it is small when temperature control exist
800 DEG C, 12 it is small when high-temperature region temperature rise to 900~950 DEG C, kiln end temperature rises to 250~300 DEG C.
(3), should be according to the actual feelings of material calcining in temperature of kiln head, high-temperature region temperature, kiln end temperature, kiln during drying kiln
Condition is appropriate to adjust rotary kiln rotating speed or gas supply amount.
(4) during drying kiln, in the case where ensureing that kiln atmosphere is good, kiln tail negative pressure is maintained at 2000Pa or so tail gas wind
Machine opening degree is as far as possible small, to reduce heat losses in kiln.
(5) when kiln end temperature rises to 250~300 DEG C, the charging of notice kiln tail post.
(6) waste water is in time beaten away according to hot-tub water level conditions in vent gas treatment post.
(7) at the end of drying kiln, gas supply amount should tend towards stability, and rotary kiln reaches regulation kiln speed, each calcining zone temperature, wind
Amount, kiln hood burner gas valve opening degree, inlet amount, offgas outlet valve opening degree should all reach normal condition.Meanwhile
Fall in the range of kiln material performance touches the mark.
11.4, normal operation：
In a normal course of operation, the calcining situation of material in rotary kiln is kept a close eye on, adjusts gas supply accurately and in time
Amount or kiln speed, it is ensured that material calcining is all right.Ordinary circumstance not adjust rotary kiln speed.
B timing samplings, Site Detection fall apparent whiteness, hardness, the pH value of kiln material.Kiln hood, kiln tail, high-temperature region are grasped at any time
Temperature, examines actual size, the calcining situation of high-temperature region material of firepower, it is ensured that appropriate Calcine Strength.
It is stringent to observe high-temperature region calcined material particle situation in c normal course of operation.Guarantee falls kiln material whiteness, reducing power reaches
Mark.
D supervises kiln tail inlet amount in time, makes every effort to feed uniform and stable, and (kiln speed is too low, coal gas is insufficient in case of exceptional circumstances
Deng) timely adjustment input material is answered, avoid kiln tail batch turning, bed of material disconnection, fall the half-cooked phenomenon generation of kiln product.
E keeps a close eye on the ventilation condition in rotary kiln.Offgas outlet valve and exhaust fan are adjusted according to calcining situation in time
Absorbing quantity, it is ensured that kiln atmosphere is good, and kiln end temperature is stablized relatively, and kiln tail negative pressure is maintained at 2000Pa or so.
11.5th, kiln operation is stopped
(1) when needing to stop kiln, charging is first stopped.
(2) after the completion of stopping fill process, kiln speed is turned down, stops coal.
(3) stop working.
A is not when material can turn in kiln, knock down the flame.Stop kiln hood blower fan, close gas valve；Opening accident chimney valve,
Venturi imported valve is closed, termination of pumping, stop exhaust fan, while circular gas stove opens exhaust-valve, stops gas fan, into supporting
Heater stage.
B reduces kiln speed, and rotary kiln keeps slowly rotating state.Treat that temperature of kiln head is down to less than 40 DEG C, shut down.In case of
The emergency cases such as power failure, it is necessary to artificial disc kiln is taken, in case kiln body deforms.It is rapid at the same time to open venturi accident emergency water source dress
Put.
The raw material that c stops being gone out during kiln should be by workshop section's requirement storage, and makes record.
Wherein step 12：After calcining and being cooled down with wind turbine, crushed using Raymond mill machine,
A, anatase titanium dioxide powder fineness (325um screen over-sizes)≤0.10%, enamel type titanium white powder fineness≤0.50%
B, titanium dioxide net content：(25±0.1)kg
C, motor temperature is no more than 70 DEG C.
Wherein step 13：The synthesis of lithium titanate composite material
Titanium dioxide, aluminium salt, carbon source, lithium salts, magnesium salts are mixed, titanium dioxide is beaten first, aluminium salt, magnesium salts, lithium
Salt dissolves, and will be mixed in titanium dioxide, aluminium salt, magnesium salts, lithium salts input dispersant；And it is dried in vacuo and obtains presoma；Wherein titanium,
Aluminium, magnesium, lithium, the molar ratio of carbon are 5: (0.05~0.3): (0.1~0.4): and (4.95~4.7): (2~20), by forerunner
Body puts into the calcining of inert gas heating furnace high temperature, 800~1000 DEG C of temperature, when the time is small more than 8, then by the production after calcining
Thing drops to room temperature and obtains carbon-coated lithium titanate composite material；Antimonic salt, pink salt can also be added when carbon coating is handled,
The molar ratio of antimony, tin and titanium is 5: (0.01~0.1): (0.05~0.2), further puies forward the conductivity after carbon coating；In order into
One step improves carbon-coated effect, can also add graphene when carbon coating is handled；Carbon source uses sucrose or glucose
Deng carbohydrate；Lithium salts is using the one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium chlorate；Aluminium salt
Using the one or more in aluminium hydroxide, aluminium carbonate, aluminum nitrate, aluminum phosphate；Magnesium salts is using magnesium hydroxide, magnesium carbonate, sulfuric acid
One or more in magnesium, phosphatase, magron；Inert gas is using the one or more in argon gas, nitrogen, helium, neon；
Dispersant uses absolute ethyl alcohol.
Wherein step 14：Wash three times
By centrifugal pump a (1403), b (1404), and by on-off valve a (1405), b (1406), will be stirred using pipeline
Lithium titanate composite material is transported to three and washes filter press (1407) in tank a (1401), b (1402)；Three wash on filter press (1407) and set
Central feeding mouth (1408) is put, lithium titanate composite material is washed in filter press (1407) by central feeding mouth (1408) injection three,
Rinse three hours；On central feeding mouth (1408) periphery, four liquid outlet a (1409), b (1410), c (1411), d are set
(1412), four liquid outlet a (1409), b (1410), c (1411), d (1412) connect outlet pipe a, b, c, d respectively, go out liquid
Solenoid valve a (1413), b (1414), c (1415), d (1416) are set on pipeline a, b, c, d；Inlet channel passes through solenoid valve a
(1413), b (1414) is connected with outlet pipe a, b, for washing filter press water filling to three；Pass through connecting tube a (1420) outlet tube
Road a is directly connected with outlet pipe c, is directly connected by connecting tube b (1421) outlet pipe b with outlet pipe d；Outlet pipe
C, the liquid of discharge is transported to wastewater trough by d by solenoid valve c (1415), d (1416).In the bottom that three wash filter press (1407)
Setting connects liquid bucket (1417), further evacuation of liquid to wastewater trough；Set and slip again side by side in the bottom that three wash filter press (1407)
Groove (1418), mashing tank diameter (1419) is transported to by the lithium titanate composite material after processing, and lithium titanate composite material is more preferable
Ground disperses.Three application methods for washing filter press (1407) are：Solenoid valve a (1413) is opened, closes solenoid valve b, c, d, clear water leads to
Liquid outlet a (1413), c (1411) injection three for crossing left side is washed in filter press (1407), after cleaning, closing solenoid valve a (1413),
B (1414), c (1415), open solenoid valve d (1416), waste water are discharged；Solenoid valve b (1414) is opened, closes solenoid valve a
(1413), c (1415), d (1416), clear water are washed in filter press by liquid outlet b (1414), d (1416) injection three on right side, clearly
After washing, solenoid valve a (1413), b (1414), d (1416) are closed, solenoid valve c (1415) is opened, waste water is discharged；Repeat above-mentioned
The step of flushing, flush three times and can reach cleaning performance, and effectively prevents from blocking.
Wherein step 15, press dry：
Scattered lithium titanate composite material is transported to by storage tank a (1501), b (1502) by pipeline；By storage tank a
(1501), the titanium dioxide in b (1502) is transported to diaphragm filter press (1505) and is pressed dry by centrifugal pump c (1503), d (1504)
(there is no water-washing process), one and a half hours time；In diaphragm filter press (1505) lower part, belt conveyor (1506), belt are set
Conveyer (1506) connects spiral transferring pipeline, and flash dryer (1601) is transported to by helical feed pipeline.
Wherein step 16, expansion drying：
Lithium titanate composite material is dried processing in flash dryer (1601).
Wherein step 17, micrometer crusher：
Dried lithium titanate composite material is transported to dry bag hose (1701) by vacuum pipe, lithium titanate is answered
Condensation material and air separation, then the lithium titanate composite material after being separated with air is transported to micron disintegrator (1704) top
Material bin (1702), lithium titanate composite material enter micron disintegrator from material bin (1702) by planet discharge valve (1703)
(1704)；Lithium titanate composite material after micron disintegrator (1704) processing is transported to by vacuum pipe a (1705) selects powder
Grader (1801)；Set on the drying bag hose (1701) on material bin (1702) top on micron disintegrator (1704) top
Vacuum pipe connection negative pressure air exhauster (1702), the air that dry bag hose is isolated is emptied by negative pressure air exhauster (1707).
Vacuum pipe b (1705), vacuum pipe b (1705) are also set up on material bin (1702) top on micron disintegrator (1704) top
The other end set discharge valve (1706), select the lower end of powder grader (1801) to be also connected with vacuum pipe b (1705).
Wherein step 18, select powder to be classified：
Lithium titanate composite material is further screened in powder grader (1801) is selected, and by the lithium titanate of garbled mistake
Composite material is transported to pulse dust collector (1901).
Wherein step 19, pulse dust removal：
Pulse dust collector (1901) side sets centrifugal blower (1902), is set in the lower part of pulse dust collector (1901) defeated
Finished product lithium titanate composite material is transported to finished product bin (2001), finished product material by square auger (1903), conveyor screw (1903) 11
Storehouse (2001) lower part sets planet discharge valve (2002)；Finished product titanium dioxide is transported to finished product bag by planet discharge valve (2002)
Installation, is weighed, is packed, and is finally put into storehouse storage.
The present invention has following technique effect compared with prior art：The present invention using by the preparation of lithium titanate composite material and
Titanium white production is merged；The particle surface of the lithium titanate composite material of preparation is smooth, shape is homogeneous, size tunable；Work
Skill simple possible, cost is low, can industrialize large-scale production.
Brief description of the drawings
Fig. 1 is the total technological process figure in preparation system.
Fig. 2 is step 14 process flow chart in preparation system.
Fig. 3 is the process flow chart of the step 15-19 in preparation system.
Embodiment
With reference to embodiments, more detailed description is done to the above-mentioned technical characteristic and advantage of the present invention.
A kind of preparation system of lithium battery special-purpose nanometer lithium titanate composite material, including：Step 1, crush；Step 2, acid
Solution；Step 3, sedimentation；Step 4, crystallization；Step 5, hydrolysis；Step 6, once wash；Step 7, bleaching；Step 8, secondary washing；
The preparation of step 9, crystal seed；Step 10, salt treatment；Step 11, calcining；Step 12, crush；Step 13, lithium titanate composite material
Synthesis；Step 14, wash three times；Step 15, press dry；Step 16, expansion drying；Step 17, micrometer crusher；Step 18, choosing
Powder is classified；Step 19, pulse dust removal.
Wherein step 5：Processed crystal seed is injected in hydrolytic tank and is hydrolyzed, the titanyl sulfate in titanium liquid is in heating
Under the conditions of, it is hydrolyzed by the induction of active seed, the hydrated titanium dioxide with certain particle diameter is made.
5.1st, the titanium liquid prepared is measured and squeezes into hydrolysis foreheater and crystal seed titanium liquid bath respectively, when liquid level reaches agitating paddle
When, that is, foreheater stirring is opened, the liquid caustic soda for preparing concentration is measured to throw crystal seed lye tank (vat) into spare.
5.2nd, after having broken material, foreheater steam inlet valve to be opened, is heated up to titanium liquid, heating outlet temperature is controlled at 96 DEG C,
Etc. crystal seed to be added.When foreheater titanium liquid temperature degree is raised to 75 DEG C, crystal seed titanium liquid bath steam inlet valve is opened, gives crystal seed titanium liquid liter
Temperature；Then open liquid caustic soda groove steam inlet valve and be warming up to 85 DEG C to liquid caustic soda, and keep this temperature；Treat that crystal seed titanium liquid is warming up to 85 DEG C
When, start crystal seed and make groove stirring, open liquid caustic soda groove baiting valve and liquid caustic soda is quickly put into crystal seed making groove, then open crystal seed titanium
And, continue to heat crystal seed making groove after discharging crystal seed titanium liquid during liquid bath baiting valve makes crystal seed titanium liquid and liquid caustic soda in crystal seed making groove
In material at 96 DEG C stop heating, quickly detect its stability, quickly opened when stability is in 130ml crystal seed make groove
Outlet valve, quickly puts the crystal seed made into and is preheating to 96 DEG C of foreheater titanium liquid.The titanium liquid of foreheater is allowed to be warming up to 96
Crystal seed is waited to carry out DEG C again, it is impossible to allow crystal seed to make and wait titanium liquid to heat up, otherwise crystal seed stability can drastically decline, and influence whole pot matter
Amount.
5.3rd, stirred 10 minutes after adding crystal seed, open hydrolyzer inlet valve, foreheater baiting valve is opened, foreheater
Titanium liquid is put into hydrolyzer, while starts hydrolyzer stirring.
5.4th, after foreheater titanium liquid is put into hydrolyzer, hydrolyzer live (open) steam inlet valve is opened, starts hydrolysis heating.
5.5th, (from time requirement≤28 minute for being warming up to boiling) after Hydrolysis of Titanium liquid once seethes with excitement, turn steam down, prevent
Transition boiling；When hydrolysis, which reaches 1: 1, turns white, stop steam, stop stirring insulation 30 minutes.
5.6th, insulation terminates, then opens stirring and steam progress secondary temperature elevation, and allows Hydrolysis of Titanium liquid to reach two in 20 minutes
Secondary boiling.
5.7th, rinse the foreheater of titanium liquid well and crystal seed makes pot, its flushing liquor is discharged into hydrolyzer when dilution water use, punching
Wash to finish and close valve.
5.8th, turning down live (open) steam valve keeps slight boiling condition (to keep pot inner pressure in 90~120mmH2O) 150 minutes.
5.9th, pressurize terminates, and opens the exhaust-valve of hydrolyzer, adds quantitative dilution water, concentration is reduced to 140~
(add volume 13.5m after water between 155g/l3), it is continuously heating to seethe with excitement, keeps slightly boiling 50 minutes.
5.10th, hydrolysis terminates, steam off valve.
5.11st, quantitative lignocellulosic is added toward the metatitanic acid after hydrolysis, and stirring 10 minutes can blowing.
5.12nd, open the bottom of a pan baiting valve and metatitanic acid after hydrolysis is sent to cooling system.
5.13rd, after blowing, rinse hydrolyzer inner wall to no plain boiled water well and flow out.Flushing finishes, and closes hydrolyzer and puts
Expect valve, wait use next time.
Wherein step 6：After hydrolysis, by graphite heat exchanger, once washed.
Wherein step 7：After once washing, bleached.
7.1st, clay kettle bottom baiting valve is closed, opens pot mouth inlet valve, rear metatitanic acid 45m is washed toward the interior addition one of clay kettle3,
Start stirring；
7.2nd, toward concentrated sulfuric acid measuring tank, accurately metering should add concentrated sulfuric acid volume；
7.3rd, toward titanous measuring tank, accurately metering should add titanous volume；
7.4th, stirring after ten minutes, first adds the concentrated sulfuric acid measured in past clay kettle；
7.5th, again toward adding the trivalent titanium solution that measures in clay kettle；
7.6th, the steam admission valve of clay kettle is opened, slurry is heated to 90 DEG C, when constant temperature insulation 2 is small；
7.7th, insulation terminates, steam off admission valve, inspection by sampling trivalent Ti content and effective acid content, if meeting work
Skill requirement, then bleach work and terminate.
If the 7.8th, Ti3+≤ 0.30g/l, then will add titanous depending on departure, and continue reduction 30 minutes, it is ensured that after bleaching
Slurry Ti3+Between 0.30~0.4g/l；
7.9th, after inspection by sampling bleaching after slurry qualified, slowly plus water is cooled to slurry≤75 DEG C.
Wherein step 8：Secondary washing is carried out after bleaching.
Open metatitanic acid storage tank baiting valve after floating, conveying metatitanic acid to 400m2Filter press.Washed with qualified water, most
Whole metatitanic acid iron-holder≤30ppm after the mashing of inclined titanium scraping blade hollander tub.Qualified metatitanic acid is delivered to two and washes qualified inclined titanium
Sour storage tank.
Wherein step 9：The preparation of crystal seed；
1. drive to prepare
(1), check whether the public work conditions such as compressed air, process water, steam possess.
(2), check whether the equipment such as post storage tank, reactor are intact, and whether debris is cleaned out in all devices, unit
Equipment operation there are the problem of whether rectify and improve and finish, it is unimpeded whether all process pipes have, and either with or without leak point, equipment is pumped and stirred
Whether have oiling, run either with or without abnormal voice if mixing.
(3), the drain valve into this post steam valve and jet chimney is opened.Closed after the drained water of drain valve
(4), the stock situation of NaOH, HCl are checked, whether analyzes its quality index in Con trolling index scope.
2. alkali fusion (the producing reaction of positive sodium titanate)
(1), TiO is checked2Whether metatitanic acid measuring tank drains, and closes outlet valve, starts the blender in the groove.
(2), hollander tub two is washed to the TiO of qualification2Slurries are pumped into metatitanic acid measuring tank (wherein containing Fe≤50mg/l) to rule
Determine liquid level and (realize 270~290g/l of concentration, volume 7m3)。
(3), the first steam valve is opened, the slurries in metatitanic acid groove are heated to 60 DEG C of first steam valves of closing.
(4), check whether NaOH measuring tanks material drains, close groove outlet valve.
(5), open pump exits and entrances valve to alkali measuring tank inlet valve and start pump and blender.It is pumped into liquid caustic soda
4.6m3。
(6), the second steam valve is opened, the NaOH in NaOH measuring tanks closes the second steam valve after being heated to 90 DEG C.
(7), that closes alkali soluble tank drains valve, and starts blender.
(6), the outlet valve of NaOH measuring tanks is opened, NaOH is put into alkali fusion tank.
(9), the outlet valve of metatitanic acid measuring tank is opened, by TiO2Suspension is put into alkali fusion flow container, and (flow is by a diameter of
The orifice plate control of 16mm), 30 minutes blowing time.
(10) while opening the 3rd steam valve makes temperature be kept for 100~105 DEG C, when insulated and stirred boiling 2 is small.
(11), the 3rd steam valve is closed, water valve is opened, adds water 5m3After turn off water valve and make its liquor capacity be 15m3, after
Continuous stirring 10 minutes.
(12), before positive metatitanic acid suspension is put into cooling bath, it must check whether cooling bath has enough rooms, and in blowing
It is preceding first to add 10m3Cold water, opens cooling bath stirring.
(13), alkali fusion tank outlet valve is opened, while opens Cold water tap.By material and cold water (material and water ratio be 1: 2)
Cocurrent is put into cooling bath.
(14), after discharging positive sodium titanate, alkali fusion tank is rinsed, closes soda fusion pot bottom valve.
(15) discharge material and continue stirring 30 minutes, positive sodium titanate is cooled to 50~55 DEG C, if stirring intensity is inadequate,
The groove discharging pump is configured circulating cooling.
(16), after cooling is qualified alkali fusion Special filter press is sent to be washed.◆ filtration washing step：A, alkali is checked
Molten Special filter press and its filter cloth situation, the hydraulic pump for starting alkali fusion Special filter press compress filter plate.B, the special press filtration of alkali fusion is played
The inlet valve of machine, the feed pump for starting alkali fusion Special filter press are fed.When feed pressure reaches setting value, stop its pump and close
Its inlet valve.C, the washing valve of alkali fusion Special filter press is opened, the wash water pump for starting alkali fusion Special filter press is washed.90 points
Clock takes filtrate analysis NaOH, if content is less than 1500ppm, washing finishes.Analysis method is as follows：50ml filtrates are added into taper
Bottle (200ml) simultaneously instills 3 drop methyl oranges again with 0.1mol/l HCl titration untill solution is from yellow to red.If the titration used
Agent HCl dosages are less than 25ml.Then Washing of Filter Cake is qualified, otherwise continues to wash.D, washings detection is qualified.Stop wash water pump, start
Blowpit stirs, and carries out discharging.TiO in hollander tub2Concentration controls (200~220) g/l.
(17), the positive metatitanic acid in hollander tub with being pumped into neutralization reaction groove (being also titanic acid buffering groove), and open
Dashpot stirs, and titanic acid concentration is controlled in (180~200) g/l, volume is 18~20m3。
(18), neutralization reaction；After hydrochloric acid is squeezed into hydrochloric acid measuring tank with pump, termination of pumping, closes exits and entrances valve, opens hydrochloric acid
Measuring tank bottom valve is neutralized, and takes around 30% hydrochloric acid 1.1m3, hydrochloric acid flow is controlled, ensures that neutralizing time control 30 divides
Clock, neutralization terminal are pH value (3.5~4.0), and about hydrochloric acid is put into starts to detect pH value for 20 minutes, surveys once within every 3 minutes later,
When neutralization terminal reaches pH value (3.5~4.0), neutralize and complete.Stirring 15 minutes, send two to wash filter press material with pump.
(19) secondary washing step is filtered：A, alkali fusion Special filter press and its filter cloth situation are checked, starts the special pressure of alkali fusion
The hydraulic pump of filter compresses filter plate.B, the inlet valve of alkali fusion Special filter press is opened, starts the feed pump of alkali fusion Special filter press
Fed.When feed pressure reaches setting value, stop its pump and close its inlet valve.C, the washing of alkali fusion Special filter press is opened
Valve, the wash water pump for starting alkali fusion Special filter press are washed.Washing takes filtrate to detect pH for 40 minutes, until washing filtrate pH value
It is qualification when (being adjusted according to actual conditions) produces more than 7, otherwise continues to wash.D, washings detection is qualified.Stop wash water pump, open
The blowpit stirring of dynamic alkali fusion Special filter press, carries out discharging.TiO in hollander tub2Concentration controls (220~240) g/l, grade
Prepare to be pumped into the molten tank of acid after testing testing result qualification.
3. crystal seed is prepared (reaction of titanium chloride peptization)
(1), check whether the molten tank of crystal seed preparation vessel acid drains, close outlet valve.
(2), two baiting valves for washing hollander tub are opened, will about 7~8m3Positive metatitanic acid with pump add crystal seed preparation vessel acid it is molten
In tank.
(3), start blender, the liquid bulk in two outlet lines for washing hollander tub, then the molten tank of measuring flume acid is rinsed with water
Product, is stirred 15 minutes, and sampling 150ml send laboratory to measure TiO2Concentration.
(4), the terminal valve of hydrochloric acid pump and the inlet valve of HCl measuring tanks are opened, starts pump.
(5), after the charging of hydrochloric acid measuring tank, termination of pumping, closes exits and entrances valve.
(6), TiO is obtained2Slurry dilution to TiO in the molten tank of crystal seed preparation vessel acid after measured value2Content is 200g/l.
(7), the hydrochloric acid that the concentration of metering is about 30% is added in crystal seed preparation vessel and obtained in slurries：Two steps are divided to add；
The first step；According to hydrochloric acid and TiO2Ratio adds for 0.15, and about 30% hydrochloric acid is incorporated as 0.75~0.85m3, add time control
15 minutes, continue stirring after ten minutes constant-speed heating to 60 DEG C (1 DEG C per minute)；Second step is according to hydrochloric acid and TiO2Ratio is
0.25 adds；It is about 1.25~1.35m that 30% hydrochloric acid, which adds,3, add time control 15 minutes, pH value is less than 1.
(8), stir 10 minutes, open steam valve, constant-speed heating then adjusts steam flow to seething with excitement (1 DEG C per minute)
Slurries are kept to seethe with excitement 101 DEG C, 90 minutes, steam off valve.
(9), by slurry dilution to TiO2Content is about 100g/l.Last volume about 17m3, about add water 7m3, open water
Valve, after reaching last volume, closes water valve, takes 100ml samples to send laboratory.Add water to stir 20 minutes and be put into crystal seed storage tank.
(10), check whether crystal seed storage tank has the material of enough molten tanks of room dress crystal seed preparation vessel acid.
(11), the molten tank bottom terminal valve of the molten tank crystal seed preparation vessel acid of acid is opened, after discharging, stops blender, closes outlet valve.
Laboratory is delivered in sampling from crystal seed storage tank.
Wherein step 10：After secondary washing terminates, crystal seed prepares, salt treatment is carried out.
The dosage and addition sequence of salt treatment agent are as follows：
1st, calcining seeds 5%, addition 5%.With TiO2Meter
2nd, zinc oxide (ZnO) is added in salt treatment, addition 0.1%.With TiO2Meter, is stirred 30 minutes after addition.Again plus
After entering ammonium dihydrogen phosphate stirring 15 minutes, KOH0.9% is added, is then stirred for 150 minutes.
After step 11, salt treatment, squeezing press dry, and injection rotary kiln is calcined,
11.3rd, kiln operation is dried：
(1) when keeping small firepower baking rotary kiln small not less than 12.
(2) dry kiln during should keep " small firepower, the slow-speed of revolution ", with prevent kiln brick be damaged and a large amount of raw material produce.Specifically
Be preceding 4 little Shi high-temperatures area control below 400 DEG C, 8 it is small when temperature control below 600 DEG C, 10 it is small when temperature control exist
800 DEG C, 12 it is small when high-temperature region temperature rise to 900~950 DEG C, kiln end temperature rises to 250~300 DEG C.
(3), should be according to the actual feelings of material calcining in temperature of kiln head, high-temperature region temperature, kiln end temperature, kiln during drying kiln
Condition is appropriate to adjust rotary kiln rotating speed or gas supply amount.
(4) during drying kiln, in the case where ensureing that kiln atmosphere is good, kiln tail negative pressure is maintained at 2000Pa or so tail gas wind
Machine opening degree is as far as possible small, to reduce heat losses in kiln.
(5) when kiln end temperature rises to 250~300 DEG C, the charging of notice kiln tail post.
(6) waste water is in time beaten away according to hot-tub water level conditions in vent gas treatment post.
(7) at the end of drying kiln, gas supply amount should tend towards stability, and rotary kiln reaches regulation kiln speed, each calcining zone temperature, wind
Amount, kiln hood burner gas valve opening degree, inlet amount, offgas outlet valve opening degree should all reach normal condition.Meanwhile
Fall in the range of kiln material performance touches the mark.
11.4, normal operation：
In a normal course of operation, the calcining situation of material in rotary kiln is kept a close eye on, adjusts gas supply accurately and in time
Amount or kiln speed, it is ensured that material calcining is all right.Ordinary circumstance not adjust rotary kiln speed.
B timing samplings, Site Detection fall apparent whiteness, hardness, the pH value of kiln material.Kiln hood, kiln tail, high-temperature region are grasped at any time
Temperature, examines actual size, the calcining situation of high-temperature region material of firepower, it is ensured that appropriate Calcine Strength.
It is stringent to observe high-temperature region calcined material particle situation in c normal course of operation.Guarantee falls kiln material whiteness, reducing power reaches
Mark.
D supervises kiln tail inlet amount in time, makes every effort to feed uniform and stable, and (kiln speed is too low, coal gas is insufficient in case of exceptional circumstances
Deng) timely adjustment input material is answered, avoid kiln tail batch turning, bed of material disconnection, fall the half-cooked phenomenon generation of kiln product.
E keeps a close eye on the ventilation condition in rotary kiln.Offgas outlet valve and exhaust fan are adjusted according to calcining situation in time
Absorbing quantity, it is ensured that kiln atmosphere is good, and kiln end temperature is stablized relatively, and kiln tail negative pressure is maintained at 2000Pa or so.
11.5th, kiln operation is stopped
(1) when needing to stop kiln, charging is first stopped.
(2) after the completion of stopping fill process, kiln speed is turned down, stops coal.
(3) stop working.
A is not when material can turn in kiln, knock down the flame.Stop kiln hood blower fan, close gas valve；Opening accident chimney valve,
Venturi imported valve is closed, termination of pumping, stop exhaust fan, while circular gas stove opens exhaust-valve, stops gas fan, into supporting
Heater stage.
B reduces kiln speed, and rotary kiln keeps slowly rotating state.Treat that temperature of kiln head is down to less than 40 DEG C, shut down.In case of
The emergency cases such as power failure, it is necessary to artificial disc kiln is taken, in case kiln body deforms.It is rapid at the same time to open venturi accident emergency water source dress
Put.
The raw material that c stops being gone out during kiln should be by workshop section's requirement storage, and makes record.
Wherein step 12：After calcining and being cooled down with wind turbine, crushed using Raymond mill machine,
12.1st, the preparation before driving
Check elevator, storage bin(hopper), whether Raymond machine works normally, if any bad equipment, could work after should repairing.
12.2nd, it is normal to drive and operate
(1) suction and conveying：Compressed air is first opened, in activation system, then vacuum pump is opened, is fed into feed bin, wherein 1# vacuum
Pump and fed to 1# feed bins, corresponding grinding machine is 1#, 2# Raymond machine, and 3# vacuum pumps are fed to 2# feed bins, and corresponding grinding machine is 3#, 4#
Raymond machine.2# vacuum pumps are spare.Old line crushes enamel grade titanium dioxide now and with omnipotent grinding machine, and suction and conveying principle is similar.
(2) Raymond machine milling is opened：
For a when material is enough in feed bin, airport logistic park starts Raymond machine, drives in order：It is (fully closed to drive the analysis machine → machine that blows in
Close startup, open air door after operating) → host → (" startup " skips to " operating ") → start charging is opened, it is normal to treat that armamentarium starts
Feeding afterwards.
After b drives, fan inlet butterfly valve, lingering remnants of past customs pipe butterfly valve should will should be opened to the optimum position for meeting technological requirement,
Charger electric current relay and control handle are adjusted to host electric current and mill sound optimum state.Keep a close eye on ammeter, voltage
The fluctuation of table and mill sound.
C shuts down, and first closes corresponding vacuum pump and closes system button again, if two at the same time when running, if 1 vacuum pump
Suction and conveying, only closes corresponding vacuum pump, is not related to system.
D material grindings finish, Raymond machine basic no-load running when stop host again, then blowing-out organ air door.Stopping procedure
Should be opposite with driving order.
Check whether each motor temperature and controller, nut etc. are intact after e parkings.
(3) omnipotent mill milling is opened
A first opens cooling water → driving host → and opens bucket charging when material is enough in feed bin.
B pays attention to host curent change situation (＜ 105A) during charging.
C is packed after hopper is full, and when packaging pays attention to preventing material from spraying, and reduces inlet amount or shutdown if necessary.
D is shut down：Stop charging, after material has been ground in grinding machine, close host, then close cooling water.
Wherein step 13：The synthesis of lithium titanate composite material
Titanium dioxide, aluminium salt, carbon source, lithium salts, magnesium salts are mixed, titanium dioxide is beaten first, aluminium salt, magnesium salts, lithium
Salt dissolves, and will be mixed in titanium dioxide, aluminium salt, magnesium salts, lithium salts input dispersant；And it is dried in vacuo and obtains presoma；Wherein titanium,
Aluminium, magnesium, lithium, the molar ratio of carbon are 5: (0.05~0.3): (0.1~0.4): and (4.95~4.7): (2~20), by forerunner
Body puts into the calcining of inert gas heating furnace high temperature, 800~1000 DEG C of temperature, when the time is small more than 8, then by the production after calcining
Thing drops to room temperature and obtains carbon-coated lithium titanate composite material；Antimonic salt, pink salt can also be added when carbon coating is handled,
The molar ratio of antimony, tin and titanium is 5: (0.01~0.1): (0.05~0.2), further puies forward the conductivity after carbon coating；In order into
One step improves carbon-coated effect, can also add graphene when carbon coating is handled；Carbon source uses sucrose or glucose
Deng carbohydrate；Lithium salts is using the one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium chlorate；Aluminium salt
Using the one or more in aluminium hydroxide, aluminium carbonate, aluminum nitrate, aluminum phosphate；Magnesium salts is using magnesium hydroxide, magnesium carbonate, sulfuric acid
One or more in magnesium, phosphatase, magron；Inert gas is using the one or more in argon gas, nitrogen, helium, neon；
Dispersant uses absolute ethyl alcohol.
Wherein step 14：Wash three times
By centrifugal pump a (1403), b (1404), and by on-off valve a (1405), b (1406), will be stirred using pipeline
Lithium titanate composite material is transported to three and washes filter press (1407) in tank a (1401), b (1402)；Three wash on filter press (1407) and set
Central feeding mouth (1408) is put, lithium titanate composite material is washed in filter press (1407) by central feeding mouth (1408) injection three,
Rinse three hours；On central feeding mouth (1408) periphery, four liquid outlet a (1409), b (1410), c (1411), d are set
(1412), four liquid outlet a (1409), b (1410), c (1411), d (1412) connect outlet pipe a, b, c, d respectively, go out liquid
Solenoid valve a (1413), b (1414), c (1415), d (1416) are set on pipeline a, b, c, d；Inlet channel passes through solenoid valve a
(1413), b (1414) is connected with outlet pipe a, b, for washing filter press water filling to three；Pass through connecting tube a (1420) outlet tube
Road a is directly connected with outlet pipe c, is directly connected by connecting tube b (1421) outlet pipe b with outlet pipe d；Outlet pipe
C, the liquid of discharge is transported to wastewater trough by d by solenoid valve c (1415), d (1416).In the bottom that three wash filter press (1407)
Setting connects liquid bucket (1417), further evacuation of liquid to wastewater trough；Set and slip again side by side in the bottom that three wash filter press (1407)
Groove (1418), mashing tank diameter (1419) is transported to by the lithium titanate composite material after processing, and lithium titanate composite material is more preferable
Ground disperses.Three application methods for washing filter press (1407) are；Solenoid valve a (1413) is opened, closes solenoid valve b, c, d, clear water leads to
Liquid outlet a (1413), c (1411) injection three for crossing left side is washed in filter press (1407), after cleaning, closing solenoid valve a (1413),
B (1414), c (1415), open solenoid valve d (1416), waste water are discharged；Solenoid valve b (1414) is opened, closes solenoid valve a
(1413), c (1415), d (1416), clear water are washed in filter press by liquid outlet b (1414), d (1416) injection three on right side, clearly
After washing, solenoid valve a (1413), b (1414), d (1416) are closed, solenoid valve c (1415) is opened, waste water is discharged；Repeat above-mentioned
The step of flushing, flush three times and can reach cleaning performance, and effectively prevents from blocking.
Wherein step 15, press dry：
Scattered lithium titanate composite material is transported to by storage tank a (1501), b (1502) by pipeline；By storage tank a
(1501), the titanium dioxide in b (1502) is transported to diaphragm filter press (1505) and is pressed dry by centrifugal pump c (1503), d (1504)
(there is no water-washing process), one and a half hours time；In diaphragm filter press (1505) lower part, belt conveyor (1506), belt are set
Conveyer (1506) connects spiral transferring pipeline, and flash dryer (1601) is transported to by helical feed pipeline.
Wherein step 16, expansion drying：
Lithium titanate composite material is dried processing in flash dryer (1601).
Wherein step 17, micrometer crusher：
Dried lithium titanate composite material is transported to dry bag hose (1701) by vacuum pipe, lithium titanate is answered
Condensation material and air separation, then the lithium titanate composite material after being separated with air is transported to micron disintegrator (1704) top
Material bin (1702), lithium titanate composite material enter micron disintegrator from material bin (1702) by planet discharge valve (1703)
(1704)；Lithium titanate composite material after micron disintegrator (1704) processing is transported to by vacuum pipe a (1705) selects powder
Grader (1801)；Set on the drying bag hose (1701) on material bin (1702) top on micron disintegrator (1704) top
Vacuum pipe connection negative pressure air exhauster (1702), the air that dry bag hose is isolated is emptied by negative pressure air exhauster (1707).
Vacuum pipe b (1705), vacuum pipe b (1705) are also set up on material bin (1702) top on micron disintegrator (1704) top
The other end set discharge valve (1706), select the lower end of powder grader (1801) to be also connected with vacuum pipe b (1705).
Wherein step 18, select powder to be classified：
Lithium titanate composite material is further screened in powder grader (1801) is selected, and by the lithium titanate of garbled mistake
Composite material is transported to pulse dust collector (1901).
Wherein step 19, pulse dust removal：
Pulse dust collector (1901) side sets centrifugal blower (1902), is set in the lower part of pulse dust collector (1901) defeated
Finished product lithium titanate composite material is transported to finished product bin (2001), finished product material by square auger (1903), conveyor screw (1903) 11
Storehouse (2001) lower part sets planet discharge valve (2002)；Finished product titanium dioxide is transported to finished product bag by planet discharge valve (2002)
Installation, is weighed, is packed, and is finally put into storehouse storage.
Properties of product are tested：
Lithium titanate sample will be prepared, at 900 DEG C, using the charge-discharge magnification of 0.1C：
1) charge-discharge test, is carried out, first charge-discharge capacity is up to 170mAh/g.
2) conclusion of XRD tests, is carried out to lithium titanate sample：Product illustrates with good performance without other impurities phase.
The lithium titanate performance comparison of preparation：
1), chemical property contrasts：
2), volt-ampere charge value and spike potential separation：
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the model of the present invention
Enclose and be defined, on the premise of design spirit of the present invention is not departed from, technical solution of the those skilled in the art to the present invention
The various modifications made and improvement, should all include in the protection domain that claims of the present invention determines.
Claims (7)
1. a kind of preparation system of lithium battery special-purpose nanometer lithium titanate composite material, including：Step 1, crush；Step 2, acidolysis；
Step 3, sedimentation；Step 4, crystallization；Step 5, hydrolysis；Step 6, once wash；Step 7, bleaching；Step 8, secondary washing；Step
Rapid 9, the preparation of crystal seed；Step 10, salt treatment；Step 11, calcining；Step 12, crush；Step 13, lithium titanate composite material
Synthesis；Step 14, wash three times；Step 15, press dry；Step 16, expansion drying；Step 17, micrometer crusher；Step 18, select powder
Classification；Step 19, pulse dust removal.
2. the preparation system of lithium battery special-purpose nanometer lithium titanate composite material according to claim 1, it is characterised in that step
Rapid 13 are：Titanium dioxide, aluminium salt, carbon source, lithium salts, magnesium salts are mixed, titanium dioxide is beaten first, aluminium salt, magnesium salts, lithium salts
Dissolving, will mix in titanium dioxide, aluminium salt, magnesium salts, lithium salts input dispersant；And it is dried in vacuo and obtains presoma；Wherein titanium,
Aluminium, magnesium, lithium, the molar ratio of carbon are 5: (0.05~0.3): (0.1~0.4): and (4.95~4.7): (2~20), by forerunner
Body puts into the calcining of inert gas heating furnace high temperature, 800~1000 DEG C of temperature, when the time is small more than 8, then by the production after calcining
Thing drops to room temperature and obtains carbon-coated lithium titanate composite material.
3. the preparation system of lithium battery special-purpose nanometer lithium titanate composite material according to claim 2, it is characterised in that
Antimonic salt, pink salt are added when carbon coating processing, the molar ratio of antimony, tin and titanium is 5: (0.01~0.1): (0.05~0.2).
4. the preparation system of lithium battery special-purpose nanometer lithium titanate composite material according to claim 2, it is characterised in that carbon
Source uses sucrose or glucose.
5. the preparation system of lithium battery special-purpose nanometer lithium titanate composite material according to claim 2, it is characterised in that lithium
Salt is using the one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium chlorate.
6. the preparation system of lithium battery special-purpose nanometer lithium titanate composite material according to claim 2, it is characterised in that aluminium
Salt is using the one or more in aluminium hydroxide, aluminium carbonate, aluminum nitrate, aluminum phosphate.
7. the preparation system of lithium battery special-purpose nanometer lithium titanate composite material according to claim 2, it is characterised in that magnesium
Salt is using the one or more in magnesium hydroxide, magnesium carbonate, magnesium sulfate, phosphatase, magron.
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| CN108946806A (en) * | 2018-09-05 | 2018-12-07 | 襄阳龙蟒钛业有限公司 | A kind of production method of high covering power titanium dioxide |
| CN109504132A (en) * | 2018-12-14 | 2019-03-22 | 攀枝花东方钛业有限公司 | Titanium dioxide organic process device and method |
| CN109950491A (en) * | 2019-03-22 | 2019-06-28 | 上海昱瓴新能源科技有限公司 | Lithium titanate silicon substrate composite negative pole material and preparation method thereof |
| CN115241461A (en) * | 2022-09-20 | 2022-10-25 | 河北格力钛新能源有限公司 | Method for preparing modified lithium titanate composite material and modified lithium titanate composite material |
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| CN108946806A (en) * | 2018-09-05 | 2018-12-07 | 襄阳龙蟒钛业有限公司 | A kind of production method of high covering power titanium dioxide |
| CN109504132A (en) * | 2018-12-14 | 2019-03-22 | 攀枝花东方钛业有限公司 | Titanium dioxide organic process device and method |
| CN109950491A (en) * | 2019-03-22 | 2019-06-28 | 上海昱瓴新能源科技有限公司 | Lithium titanate silicon substrate composite negative pole material and preparation method thereof |
| CN109950491B (en) * | 2019-03-22 | 2021-11-02 | 上海昱瓴新能源科技有限公司 | Lithium titanate silicon-based composite negative electrode material and preparation method thereof |
| CN115241461A (en) * | 2022-09-20 | 2022-10-25 | 河北格力钛新能源有限公司 | Method for preparing modified lithium titanate composite material and modified lithium titanate composite material |
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