CN104600276A - Micro-spherical titanium phosphorus oxide and preparation method thereof - Google Patents

Micro-spherical titanium phosphorus oxide and preparation method thereof Download PDF

Info

Publication number
CN104600276A
CN104600276A CN201510044089.6A CN201510044089A CN104600276A CN 104600276 A CN104600276 A CN 104600276A CN 201510044089 A CN201510044089 A CN 201510044089A CN 104600276 A CN104600276 A CN 104600276A
Authority
CN
China
Prior art keywords
solution
preparation
phosphorous oxides
titanium
precursor liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510044089.6A
Other languages
Chinese (zh)
Other versions
CN104600276B (en
Inventor
刘宇
吕仙月
贺诗阳
夏骥
贺健
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Benan Energy Technology Shanghai Co ltd
Original Assignee
Shanghai Institute of Ceramics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Ceramics of CAS filed Critical Shanghai Institute of Ceramics of CAS
Priority to CN201510044089.6A priority Critical patent/CN104600276B/en
Publication of CN104600276A publication Critical patent/CN104600276A/en
Application granted granted Critical
Publication of CN104600276B publication Critical patent/CN104600276B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a micro-spherical titanium phosphorus oxide and a preparation method thereof. The preparation method comprises the following steps: (a) preparing a solution A containing a titanium source, and a solution B containing a phosphorus source; (b) mixing the solution A and the solution B to obtain a precursor solution, wherein the molar ratio of Ti<2+> to PO4<3-> in the precursor solution is between 0.2-2.5; (c) adding an alkaline substance to the precursor solution prepared in the step (b), adjusting the pH value of the precursor solution to be 5-10, preferably adjusting the pH value to be 7-8, heating to 80-200 DEG C by a microwave, reacting for 2-6 hours, ending the reaction and filtering to obtain sediments; and (d) washing the sediments obtained from the step (c), drying, and roasting at 600-900 DEG C, so as to obtain the micro-spherical titanium phosphorus oxide.

Description

A kind of microspheroidal titanium phosphorous oxides and preparation method thereof
Technical field
The invention belongs to battery electrode material preparation method field, relate generally to the method for a kind of microwave-hydrothermal method synthesis microspheroidal titanium phosphorous oxides.
Background technology
Lithium ion battery has larger capacity due to it, good cycle life and fail safe, be widely used in field of portable electronic apparatus, especially in recent years along with the development of electric automobile and large-scale energy storage device, the application and research of lithium ion battery obtains the growth of explosion type.But lithium resource is limited, material cost is higher, and these limit the further large-scale application of lithium ion battery to a certain extent, also in the urgent need to developing a kind of battery system that can be close with performance of lithium ion battery.Sodium element and elemental lithium are in same main group, and have similar chemical property, electrode potential is close, and sodium aboundresources, and the cost of refinement is lower, is expected to for lithium-ion battery system.Therefore, the common concern that the anode material of lithium-ion battery with Large Copacity and excellent cycle performance has caused industrial quarters and academia is developed.
Negative active core-shell material has material impact to the security performance of sodium-ion battery, high rate performance, and the negative electrode active material plastidomes such as titanium phosphate sodium, sodium lithium titanate and titanium oxygen compound are the study hotspots of current sodium-ion battery.The people such as Jun-ichi Yamakiden have studied NaTi 2(PO 4) 3as anode material of lithium-ion battery, have the voltage platform of 2.1V and the capacity of 130mAh/g, 30 circulation volumes are not almost decayed (Journal of Electrochemical Society, 2011,158 (10), A1067-A1070).The people such as Yuesheng Wang have studied P2-Na 0.66[Li 0.22ti 0.78] O 2as anode material of lithium-ion battery, this material and lithium titanate structural similarity, belong to " zero strain " material, can avoid the capacity attenuation that change in volume causes in cyclic process, and circulate 1200 times, capacity is almost undamped.But there is larger limitation in such electrode material preparation method of existing report, high temperature is needed admittedly to sinter in materials synthesis, there is process control complexity, energy consumption and cost in batch production comparatively large, and the product particle pattern prepared is uncontrollable, limits the performance of material.Therefore, how to develop a kind of novel electrode material, the anode material of lithium-ion battery simultaneously having comparatively ideal capacity and cycle performance by simple step synthesis is one of emphasis research direction of those skilled in the art.
Summary of the invention
The present invention is intended to overcome the defect of existing anode material of lithium-ion battery in performance and preparation method, the invention provides a kind of microspheroidal titanium phosphorous oxides and preparation method thereof.
The invention provides a kind of preparation method of microspheroidal titanium phosphorous oxides, comprising:
A) solution A of preparation containing titanium source and the solution B containing phosphorus source;
B) precursor liquid is obtained, Ti in precursor liquid after measuring solution A and solution B mixing 2+: PO 4 3-mol ratio between 0.2-2.5;
C) to step b) add alkaline matter in the precursor liquid prepared, regulate the pH value of precursor liquid to 5-10, preferred adjust ph is to 7-8, and then microwave heating is to 80-200 DEG C, and the microwave reaction time is 2-6h, after completion of the reaction, filters and is precipitated thing;
D) by step c) washing of the sediment that obtains, after drying, roasting at 600-900 DEG C, obtains described microspheroidal titanium phosphorous oxides.
Preferably, titanium source comprises TiCl 4, TiBr 4, Ti (SO 4) 2, C 16h 36o 4at least one in Ti, phosphorus source comprises NaH 2pO 4, Na 2hPO 4, NH 4h 2pO 4, (NH 4) 2hPO 4in at least one.
Preferably, in solution A, Ti 2+concentration is 0.05mol/L-2mol/L; In solution B, PO 4 3-concentration is 0.05mol/L-2mol/L.
Preferably, the solvent in solution A and solution B comprises at least one in water, ethanol, PEG-400.
Preferably, alkaline matter comprises at least one in ammoniacal liquor, sodium carbonate, sodium acetate, and working concentration is that the alkaline substance solution of 0.05mol/L-2mol/L regulates precursor liquid pH value.
Preferably, the reaction time at 80-200 DEG C of temperature is 1-24 hour, and reaction is carried out in a kettle., and reactor filling is than controlling as 40%-50%.
Preferably, with the ramp of 1-10 DEG C/min to 600-900 DEG C of roasting 2-12 hour.
Present invention also offers microspheroidal titanium phosphorous oxides prepared by a kind of said method, the constitutional chemistry formula of described microspheroidal titanium phosphorous oxides is (TiO) xPyOz (z=x+2.5y), 0<x<3,0<y<3,0<x<12, the particle diameter of microspheroidal titanium phosphorous oxides is 1-10 micron.
Preferably, in microspheroidal titanium phosphorous oxides titanium, phosphorus mol ratio between 0.5-3.0.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates preparing (TiO) xPyOz in one embodiment of the present invention;
Fig. 2 is the SEM collection of illustrative plates preparing (TiO) xPyOz material in one embodiment of the present invention.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following execution mode, should be understood that accompanying drawing and following execution mode are only for illustration of the present invention, and unrestricted the present invention.
Present disclosure provides the method for a kind of microwave-hydrothermal method synthesis microspheroidal titanium phosphorous oxides, described material preparation method is simple, and production cost is low, with short production cycle, stable performance.Present invention employs the titanium phosphorous oxides negative pole that a kind of simple preparation method has synthesized a kind of microspheroidal, material particle size easily realizes Optimal Distribution, have higher electrode packing density, the sodium-ion battery in order to preparation has the advantages such as stable cycle performance, high power characteristic and high-energy-density.
The invention discloses the method for a kind of microwave-hydrothermal method synthesis microspheroidal titanium phosphorous oxides.Comprise:
1) take titanium source respectively, phosphorus comes from beaker, add a certain amount of solvent, compound concentration is the solution A of 0.05mol/L-2mol/L respectively, and concentration is the solution B of 0.05mol/L-2mol/L;
2) by Ti 2+: PO 4 3-mol ratio between 0.5-3, the solution A of measured amounts and B, be dropwise added drop-wise to solution A in solution B, obtain precursor liquid after mixing;
3) to step 2) in mixed liquor in add a certain amount of weak base or weak base salt, by precursor liquid pH range regulation to 5-10;
4) filled in by precursor liquid and be lined with in the reactor of polytetrafluoroethylene, microwave heating is to 80-200 DEG C, and microwave reaction 2h, naturally cools to room temperature by reactor after terminating reaction, obtain product;
5) product is used deionized water and washes of absolute alcohol successively, then that product is dry, obtain titanium phosphorous oxides presoma;
6) by step 5) in presoma be placed in Muffle furnace with the ramp of 2 DEG C/min to 600-900 DEG C of roasting 2-12h, cooling, obtain (TiO) xPyOz spheric granules.
Described titanium source can be TiCl 4, TiBr 4, Ti (SO 4) 2, C 16h 36o 4at least one in Ti, described phosphorus source can be NaH 2pO 4, Na 2hPO 4, NH 4h 2pO 4, (NH 4) 2hPO 4in at least one.
The solvent of described solution A and solution B can be distilled water, ethanol, at least one in PEG-400.
Step 3) in use weak base or weak base salt can be ammoniacal liquor, sodium carbonate, sodium acetate etc.
Step 3) in working concentration be that the weak base of 0.05mol/L-2mol/L or weak base salt solution regulate precursor liquid pH value.
Reactor filling is than controlling as 40%-50%.
Step 4) in reaction time at 80-200 DEG C of temperature be 1-24h.
This titanium phosphorous oxides material has following general formula: (TiO) xPyOz (z=x+2.5y).
0<x<3,0<y<3,0<x<12。
The present invention adopts microwave-hydrothermal method easily effectively to prepare to have the titanium phosphorous oxides material of microspheroidal, and first Application is in anode material of lithium-ion battery, the present invention adopts the mode of microwave heating, take deionized water as reaction medium, form the special state of HTHP, then high-temperature process, thus prepared (TiO) xPyOz, microwave-hydrothermal method have be swift in response, the time is short, purity is high advantage, course of reaction of the present invention is efficiently controlled, has good operability; And the microspheroidal titanium phosphorous oxides scantling that the present invention prepares distribution is homogeneous, characteristic parameter is given prominence to, and being applied to anode material of lithium-ion battery, to have capacity high, the advantage of good cycle.The titanium phosphorous oxides particle size distribution that the present invention prepares is homogeneous, and pattern is microspheroidal, is conducive to the structural stability of better reinforcing material, and being applied to anode material of lithium-ion battery, to have capacity high.
Exemplify embodiment below further to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The technological parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1:
The invention provides the method for a kind of microwave-hydrothermal method synthesis microspheroidal titanium phosphorous oxides, comprise the following steps:
1) appropriate Ti (SO is taken respectively 4) 2and NH 4h 2pO 4being placed in beaker, take deionized water as solvent, and compound concentration is the Ti (SO of 0.1mol/L respectively 4) 2solution A and concentration are the NH of 0.1mol/L 4h 2pO 4solution B;
2) by Ti 2+: PO 4 3-mol ratio be 1, the solution A of measured amounts and B, be dropwise added drop-wise to solution A in solution B with the speed of 10mL per minute, obtain precursor liquid after mixing;
3) to step 2) in mixed liquor in add the ammonia spirit that a certain amount of concentration is 0.1mol/L, the pH value of precursor liquid is adjusted to 8, continues to use magnetic stirring apparatus stir about 4h;
4) fill in reactor by precursor liquid, loading than control is 40%, microwave heating to 120 DEG C, and microwave reaction 2h, slowly cools to room temperature condition after having reacted, and obtains product;
5) product is transferred to centrifuge tube, centrifugal 15min under slow-speed of revolution condition, next uses washed with de-ionized water twice successively to centrifugal material, uses washes of absolute alcohol twice, at 70 DEG C of vacuum drying chamber inner drying 6h, namely obtain titanium phosphorous oxides persursor material;
6) by step 5) in preparation persursor material transfer be placed in Muffle furnace with the ramp to 900 of 2 DEG C/min DEG C roasting 5h, cooling, obtain (TiO) xPyOz, as shown in Figure 1, the SEM collection of illustrative plates of (TiO) xPyOz material as shown in Figure 2 for prepared (TiO) xPyOz characteristic XRD.
Embodiment 2:
The invention provides the method for a kind of microwave-hydrothermal method synthesis microspheroidal titanium phosphorous oxides, comprise the following steps:
1) appropriate TiCl is taken respectively 4(NH 4) 2hPO 4being placed in beaker, take ethanol as solvent, and compound concentration is the TiCl of 0.05mol/L respectively 4solution A and concentration are the NH of 0.05mol/L 4h 2pO 4solution B;
2) by Ti 2+: PO 4 3-mol ratio be 0.5, the solution A of measured amounts and B, be dropwise added drop-wise to solution A in solution B with the speed of 10mL per minute, obtain precursor liquid after mixing;
3) to step 2) in mixed liquor in add the Na that a certain amount of concentration is 0.05mol/L 2cO 3solution, is adjusted to 7.5 by the pH value of precursor liquid, continues to use magnetic stirring apparatus stir about 4h;
4) fill in reactor by precursor liquid, loading than control is 40%, microwave heating to 120 DEG C, and microwave reaction 2h, slowly cools to room temperature condition after having reacted, and obtains product;
5) product is transferred to centrifuge tube, centrifugal 15min under slow-speed of revolution condition, next uses washed with de-ionized water four times successively to centrifugal material, uses washes of absolute alcohol three times, at 80 DEG C of vacuum drying chamber inner drying 8h, namely obtain titanium phosphorous oxides persursor material;
6) by step 5) in preparation persursor material transfer be placed in Muffle furnace with the ramp to 800 of 2 DEG C/min DEG C roasting 5h, cooling, obtain (TiO) xPyOz.
Embodiment 3:
The invention provides the method for a kind of microwave-hydrothermal method synthesis microspheroidal titanium phosphorous oxides, comprise the following steps:
1) appropriate C is taken respectively 16h 36o 4ti and NH 4h 2pO 4being placed in beaker, take ethanol as solvent, and compound concentration is the C of 0.2mol/L respectively 16h 36o 4ti solution A and concentration are the NH of 0.2mol/L 4h 2pO 4solution B;
2) by Ti 2+: PO 4 3-mol ratio be 0.5, the solution A of measured amounts and B, under magnetic agitation condition, be dropwise added drop-wise to solution A in solution B with the speed of 10mL per minute, obtain precursor liquid after mixing;
3) to step 2) in mixed liquor in add the sodium acetate solution that a certain amount of concentration is 0.2mol/L, the pH value of precursor liquid is adjusted to 7.0, continues to use magnetic stirring apparatus stir about 2h;
4) fill in reactor by precursor liquid, loading than control is 50%, microwave heating to 150 DEG C, microwave reaction 2h, slowly cool to room temperature condition after having reacted, obtain product;
5) product is transferred to centrifuge tube, centrifugal 15min under slow-speed of revolution condition, next uses washed with de-ionized water twice successively to centrifugal material, uses washes of absolute alcohol three times, at 70 DEG C of vacuum drying chamber inner drying 8h, namely obtain titanium phosphorous oxides persursor material;
6) by step 5) in preparation persursor material transfer be placed in Muffle furnace with the ramp to 700 of 2 DEG C/min DEG C roasting 5h, cooling, obtain (TiO) xPyOz.
Embodiment 4:
The invention provides the method for a kind of microwave-hydrothermal method synthesis microspheroidal titanium phosphorous oxides, comprise the following steps:
1) appropriate Ti (SO is taken respectively 4) 2and NaH 2pO 4being placed in beaker, take deionized water as solvent, and compound concentration is the Ti (SO of 1mol/L respectively 4) 2solution A and concentration are the NaH of 1mol/L 2pO 4solution B;
2) by Ti 2+: PO 4 3-mol ratio be 2.0, the solution A of measured amounts and B, under magnetic agitation condition, be dropwise added drop-wise to solution A in solution B with the speed of 10mL per minute, obtain precursor liquid after mixing;
3) to step 2) in mixed liquor in add the ammonia spirit that a certain amount of concentration is 0.1mol/L, the pH value of precursor liquid is adjusted to 8.0, continues to use magnetic stirring apparatus stir about 2h;
4) fill in reactor by precursor liquid, loading than control is 50%, microwave heating to 150 DEG C, and microwave reaction 2h, slowly cools to room temperature condition after having reacted, and obtains product;
5) product is transferred to centrifuge tube, centrifugal 15min under slow-speed of revolution condition, next uses washed with de-ionized water twice successively to centrifugal material, uses washes of absolute alcohol three times, at 70 DEG C of vacuum drying chamber inner drying 8h, namely obtain titanium phosphorous oxides persursor material;
6) by step 5) in preparation persursor material transfer be placed in Muffle furnace with the ramp to 600 of 2 DEG C/min DEG C roasting 5h, cooling, obtain (TiO) xPyOz.
Embodiment 5:
The invention provides the method for a kind of microwave-hydrothermal method synthesis microspheroidal titanium phosphorous oxides, comprise the following steps:
1) appropriate C is taken respectively 16h 36o 4ti and NH 4h 2pO 4being placed in beaker, take ethanol as solvent, and compound concentration is the C of 1.5mol/L respectively 16h 36o 4ti solution A and concentration are the NH of 1.5mol/L 4h 2pO 4solution B;
2) by Ti 2+: PO 4 3-mol ratio be 0.8, the solution A of measured amounts and B, under magnetic agitation condition, be dropwise added drop-wise to solution A in solution B with the speed of 10mL per minute, obtain precursor liquid after mixing;
3) to step 2) in mixed liquor in add the Na that a certain amount of concentration is 1mol/L 2cO 3solution, is adjusted to 8.0 by the pH value of precursor liquid, continues to use magnetic stirring apparatus stir about 2h;
4) fill in reactor by precursor liquid, loading than control is 50%, microwave heating to 160 DEG C, and microwave reaction 2h, slowly cools to room temperature condition after having reacted, and obtains product;
5) product is transferred to centrifuge tube, centrifugal 15min under slow-speed of revolution condition, next uses washed with de-ionized water twice successively to centrifugal material, uses washes of absolute alcohol three times, at 70 DEG C of vacuum drying chamber inner drying 8h, namely obtain titanium phosphorous oxides persursor material;
6) by step 5) in preparation persursor material transfer be placed in Muffle furnace with the ramp to 900 of 2 DEG C/min DEG C roasting 5h, cooling, obtain (TiO) xPyOz.
Embodiment 6:
The invention provides the method for a kind of microwave-hydrothermal method synthesis microspheroidal titanium phosphorous oxides, comprise the following steps:
1) appropriate Ti (SO is taken respectively 4) 2and Na 2hPO 4being placed in beaker, take deionized water as solvent, and compound concentration is the Ti (SO of 0.5mol/L respectively 4) 2solution A and concentration are the NH of 0.5mol/L 4h 2pO 4solution B;
2) by Ti 2+: PO 4 3-mol ratio be 1, the solution A of measured amounts and B, under magnetic agitation condition, be dropwise added drop-wise to solution A in solution B with the speed of 10mL per minute, obtain precursor liquid after mixing;
3) to step 2) in mixed liquor in add the ammonia spirit that a certain amount of concentration is 0.5mol/L, the pH value of precursor liquid is adjusted to 7.5, continues to use magnetic stirring apparatus stir about 2h;
4) fill in reactor by precursor liquid, loading than control is 50%, microwave heating to 180 DEG C, and microwave reaction 2h, slowly cools to room temperature condition after having reacted, and obtains product;
5) product is transferred to centrifuge tube, centrifugal 15min under slow-speed of revolution condition, next uses washed with de-ionized water twice successively to centrifugal material, uses washes of absolute alcohol three times, at 70 DEG C of vacuum drying chamber inner drying 8h, namely obtain titanium phosphorous oxides persursor material;
6) by step 5) in preparation persursor material transfer be placed in Muffle furnace with the ramp to 800 of 2 DEG C/min DEG C roasting 5h, cooling, obtain (TiO) xPyOz.
Embodiment 7:
The invention provides the method for a kind of microwave-hydrothermal method synthesis microspheroidal titanium phosphorous oxides, comprise the following steps:
1) appropriate C is taken respectively 16h 36o 4ti and NH 4h 2pO 4being placed in beaker, take ethanol as solvent, and compound concentration is the C of 0.8mol/L respectively 16h 36o 4ti solution A and concentration are the NH of 0.8mol/L 4h 2pO 4solution B;
2) by Ti 2+: PO 4 3-mol ratio be 1.8, the solution A of measured amounts and B, under magnetic agitation condition, be dropwise added drop-wise to solution A in solution B with the speed of 10mL per minute, obtain precursor liquid after mixing;
3) to step 2) in mixed liquor in add the sodium acetate solution that a certain amount of concentration is 0.8mol/L, the pH value of precursor liquid is adjusted to 8.5, continues to use magnetic stirring apparatus stir about 2h;
4) fill in reactor by precursor liquid, loading than control is 50%, microwave heating to 160 DEG C, and microwave reaction 2h, slowly cools to room temperature condition after having reacted, and obtains product;
5) product is transferred to centrifuge tube, centrifugal 15min under slow-speed of revolution condition, next uses washed with de-ionized water twice successively to centrifugal material, uses washes of absolute alcohol three times, at 70 DEG C of vacuum drying chamber inner drying 8h, namely obtain titanium phosphorous oxides persursor material;
6) by step 5) in preparation persursor material transfer be placed in Muffle furnace with the ramp to 900 of 2 DEG C/min DEG C roasting 5h, cooling, obtain (TiO) xPyOz.

Claims (9)

1. a preparation method for microspheroidal titanium phosphorous oxides, is characterized in that, comprising:
A) solution A of preparation containing titanium source and the solution B containing phosphorus source;
B) precursor liquid is obtained, Ti in precursor liquid after measuring solution A and solution B mixing 2+: PO 4 3-mol ratio between 0.2-2.5;
C) add alkaline matter in the precursor liquid prepared to step b), regulate the pH value of precursor liquid to 5-10, preferred adjust ph is to 7-8, and then microwave heating is to 80-200 DEG C, and the reaction time is 2-6h, after completion of the reaction, filters and is precipitated thing;
D), after sediment washing step c) obtained, drying, roasting at 600-900 DEG C, obtains described microspheroidal titanium phosphorous oxides.
2. preparation method according to claim 1, is characterized in that, titanium source comprises TiCl 4, TiBr 4, Ti (SO 4) 2, C 16h 36o 4at least one in Ti, phosphorus source comprises NaH 2pO 4, Na 2hPO 4, NH 4h 2pO 4, (NH 4) 2hPO 4in at least one.
3. preparation method according to claim 1 and 2, is characterized in that, in solution A, and Ti 2+concentration is 0.05mol/L-2mol/L; In solution B, PO 4 3-concentration is 0.05mol/L-2mol/L.
4. according to described preparation method arbitrary in claim 1-3, it is characterized in that, the solvent in solution A and solution B comprises at least one in water, ethanol, PEG-400.
5. according to described preparation method arbitrary in claim 1-4, it is characterized in that, alkaline matter comprises at least one in ammoniacal liquor, sodium carbonate, sodium acetate, and working concentration is that the alkaline substance solution of 0.05mol/L-2mol/L regulates precursor liquid pH value.
6. according to described preparation method arbitrary in claim 1-5, it is characterized in that, the reaction time at 80-200 DEG C of temperature is 1-24 hour, and reaction is carried out in a kettle., and reactor filling is than controlling as 40%-50%.
7., according to described preparation method arbitrary in claim 1-6, it is characterized in that, with the ramp of 1-10 DEG C/min to 600-900 DEG C of roasting 2-12 hour.
8. the microspheroidal titanium phosphorous oxides that in a claim 1-7 prepared by arbitrary described method, it is characterized in that, the constitutional chemistry formula of described microspheroidal titanium phosphorous oxides is (TiO) xPyOz, z=x+2.5y, 0<x<3,0<y<3,0<x<12, the particle diameter of microspheroidal titanium phosphorous oxides is 1-10 micron.
9. microspheroidal titanium phosphorous oxides according to claim 8, is characterized in that, in microspheroidal titanium phosphorous oxides, titanium, phosphorus mol ratio are between 0.5-3.0.
CN201510044089.6A 2015-01-28 2015-01-28 A kind of microspheroidal titanium phosphorous oxides and preparation method thereof Active CN104600276B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510044089.6A CN104600276B (en) 2015-01-28 2015-01-28 A kind of microspheroidal titanium phosphorous oxides and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510044089.6A CN104600276B (en) 2015-01-28 2015-01-28 A kind of microspheroidal titanium phosphorous oxides and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104600276A true CN104600276A (en) 2015-05-06
CN104600276B CN104600276B (en) 2017-09-22

Family

ID=53125911

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510044089.6A Active CN104600276B (en) 2015-01-28 2015-01-28 A kind of microspheroidal titanium phosphorous oxides and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104600276B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111994888A (en) * 2017-03-30 2020-11-27 福吉米株式会社 Titanium phosphate powder, method for producing same, and white pigment for cosmetics
CN115064681A (en) * 2022-07-05 2022-09-16 深圳为方能源科技有限公司 Preparation method of carbon-coated sodium titanium phosphate material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090026413A1 (en) * 2006-03-27 2009-01-29 Commissariat A L'energie Atomique Compound Based on Titanium Diphosphate and Carbon, Preparation Process, and Use as an Active Material of an Electrode for a Lithium Storage Battery
CN103495429A (en) * 2013-07-19 2014-01-08 西安理工大学 Microwave hydrothermal synthetic method of phosphorus-doped titanium dioxide powder photocatalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090026413A1 (en) * 2006-03-27 2009-01-29 Commissariat A L'energie Atomique Compound Based on Titanium Diphosphate and Carbon, Preparation Process, and Use as an Active Material of an Electrode for a Lithium Storage Battery
CN103495429A (en) * 2013-07-19 2014-01-08 西安理工大学 Microwave hydrothermal synthetic method of phosphorus-doped titanium dioxide powder photocatalyst

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
卜凡晴等: "磷酸钛的研究进展", 《山东轻工业学院学报》 *
周艳: "锂电池电极材料TiP2O7和LiTi2(PO4）3的制备及其电化学性能", 《中国优秀硕士学位论文全文数据库（工程科技II辑）》 *
李旭影等: "微波辅助水热法快速合成介孔磷酸镍", 《无机材料学报》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111994888A (en) * 2017-03-30 2020-11-27 福吉米株式会社 Titanium phosphate powder, method for producing same, and white pigment for cosmetics
CN111994888B (en) * 2017-03-30 2023-11-17 福吉米株式会社 Titanium phosphate powder, process for producing the same, and white pigment for cosmetics
CN115064681A (en) * 2022-07-05 2022-09-16 深圳为方能源科技有限公司 Preparation method of carbon-coated sodium titanium phosphate material
CN115064681B (en) * 2022-07-05 2023-11-17 深圳为方能源科技有限公司 Preparation method of carbon-coated sodium titanium phosphate material

Also Published As

Publication number Publication date
CN104600276B (en) 2017-09-22

Similar Documents

Publication Publication Date Title
CN104710302B (en) Oxalic acid ferrimanganic presoma of grade doping and preparation method thereof
CN105355879B (en) Composite carbon coated metal oxide and preparation method thereof
CN106920964A (en) A kind of prussian blue sodium-ion battery positive material and preparation method thereof
CN103896339B (en) A kind of preparation method of sodium manganese oxide
CN103594693B (en) A kind of titanium dioxide/niobium-titanium oxide composite material and Synthesis and applications thereof
CN105185975B (en) A kind of preparation method of Coated With Hydroxyapatite lithium titanate
CN104201361B (en) The preparation method of multilevel hierarchy carbon coating zinc oxide quantum dot negative material
CN102956880B (en) A kind of for the preparation of Li 4ti 5o 12-TiO 2method of nano composite material and products thereof
CN104037413A (en) Preparation method of positive electrode material (carbon-coated iron-manganese-lithium phosphate) of lithium ion battery
CN102249297A (en) Method for preparing lithium titanate powder
CN101891180A (en) Method for preparing sub-micrometer lithium iron phosphate (LiFePO4)
CN104701527A (en) Preparation method for lithium ion battery anode material Li(Ni1-x-yCoxAly)O2
CN105489874A (en) Stannic oxide nanoparticles with high electrical property and preparation method therefor
CN107204426A (en) A kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property
CN104993116A (en) Preparation method of self-assembled lithium ion battery positive material V2O5
CN105129758B (en) A kind of porous calcium phosphate manganese vanadium lithium composite positive pole and preparation method thereof
CN103833083A (en) Preparation method of precursor of lithium iron phosphate-lithium vanadium phosphate composite
CN107215902A (en) A kind of preparation method of lithium ion battery negative material niobic acid iron
CN107681134A (en) The preparation method of High-performance lithium manganate anode material
CN104600276B (en) A kind of microspheroidal titanium phosphorous oxides and preparation method thereof
CN100483809C (en) Method for producing ultra-fine LiFePO4/C of lithium ion battery anode material
CN103985870B (en) The method of the coated ferrous pyrophosphate lithium of a kind of hydrothermal synthesis of carbon
CN105098155A (en) Silicon dioxide-coated fluorinated lithium cobalt phosphate and preparation method thereof
CN102157725A (en) Method for synthesizing positive electrode material of nickel-cobalt-manganese polybasic lithium ion battery by microwave sintering
CN102009998A (en) Method for preparing lithium ion battery cathode material lithium titanate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20230105

Address after: Room 198, 1st Floor, Building 15, No. 42, Jibang Old Street, Zhongxing Town, Chongming District, Shanghai 202163

Patentee after: BenAn energy technology (Shanghai) Co.,Ltd.

Address before: 200050 No. 1295 Dingxi Road, Shanghai, Changning District

Patentee before: SHANGHAI INSTITUTE OF CERAMICS, CHINESE ACADEMY OF SCIENCES

TR01 Transfer of patent right