CN110589791B - Preparation method of tin-doped titanium pyrophosphate - Google Patents
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- 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
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Abstract
A preparation method of tin-doped titanium pyrophosphate comprises the steps of carrying out hydrothermal reaction on a titanium source, a tin source and a phosphorus source serving as raw materials to prepare a titanium pyrophosphate precursor, and then placing the titanium pyrophosphate precursor in a non-oxidizing atmosphere for sintering to prepare the tin-doped titanium pyrophosphate Ti1‑ xSnxP2O7(ii) a Furthermore, the preparation method can also add a carbon source while adding a phosphorus source to prepare the carbon-containing tin-doped titanium pyrophosphate, so that the conductivity of the titanium pyrophosphate is improved, and the electrochemical activity of the titanium pyrophosphate is further improved; the cathode material prepared by mixing the tin-doped titanium pyrophosphate, the acetylene black and the binder has excellent electrochemical performance, and the first charge-discharge specific capacity reaches 900mAh g‑1After 150 cycles of charging and discharging, it can still maintain 400mAh g‑1The specific capacity of (A).
Description
Technical Field
The invention relates to the field of preparation of battery cathode materials, in particular to a preparation method of tin-doped titanium pyrophosphate.
Background
The lithium ion battery has the advantages of high working voltage, high energy density, high stability, long service life and the like, and is widely applied to the fields of portable electronic products, electric automobiles and the like. However, the performance of the lithium ion battery depends on the electrode material to a great extent, and the negative electrode material is a key electrode material of the lithium ion battery, so that research and development of the negative electrode material with excellent performance are the concerns of many researchers. The capacity of the traditional graphite cathode is low, and the requirement of high capacity of a modern battery cannot be met; the graphene material is limited in further popularization and use due to high preparation cost and high process requirement; the metal oxide material has volume expansion effect in the process of lithium ion desorption and insertion, and the rate capability of the battery is influenced. Therefore, the research and development of the novel lithium ion battery anode material have important practical significance.
Titanium pyrophosphate has a chemical formula of TiP2O7Is a polyanionic compound prepared from TiO6Octahedron and P2O7The double tetrahedrons are connected through the top corners, and the structure is very stable, so that the titanium pyrophosphate material has excellent thermal stability; in addition, the open three-dimensional network structure is beneficial to the rapid migration of lithium ions, so that the material has good electrochemical activity. At present, reports about titanium pyrophosphate as a negative electrode material of a lithium ion battery are rare, and the electrochemical performance is poor.
CN108574093A discloses a preparation method of a carbon/titanium pyrophosphate composite material, the method is characterized in that the carbon/titanium pyrophosphate composite material is prepared through three steps of stirring and mixing, hydrothermal reaction and high-temperature calcination, and the specific discharge capacity of the composite material can reach 68.7mAh/g under the current density of 100 mA/g. But its electrochemical performance still needs to be further improved.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects in the prior art are overcome, and the preparation method of the tin-doped titanium pyrophosphate is provided.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of tin-doped titanium pyrophosphate comprises the following steps: taking a titanium source, a tin source and a phosphorus source asCarrying out hydrothermal reaction on the raw materials to prepare a titanium pyrophosphate precursor, and then sintering the titanium pyrophosphate precursor in a non-oxidizing atmosphere to prepare the tin-doped titanium pyrophosphate Ti1-xSnxP2O7Wherein x is more than or equal to 0 and less than or equal to 0.05.
Preferably, the preparation method comprises the following specific steps:
(1) uniformly dispersing a titanium source, a tin source and a phosphorus source into a solvent I to obtain a reaction solution, heating the reaction solution to 140-180 ℃, carrying out hydrothermal reaction for 2-6 h, cooling to room temperature, carrying out solid-liquid separation, washing, and drying to obtain a titanium pyrophosphate precursor;
(2) heating the titanium pyrophosphate precursor to 500-900 ℃ in a non-oxidizing atmosphere, sintering for 2-5 h, and cooling to room temperature to obtain the tin-doped titanium pyrophosphate Ti1-xSnxP2O7（0≤x≤0.05）。
Preferably, a carbon source is further dispersed in the reaction solution.
Preferably, the carbon source is graphene or/and glucose.
Preferably, the titanium source is selected from one or more of titanium trichloride, titanium tetrachloride, titanium dioxide, titanium hydroxide and tetrabutyl titanate.
Preferably, the tin source is selected from one or more of tin dioxide, stannous oxide, tin tetrachloride and stannous chloride dihydrate.
Preferably, the phosphorus source is selected from one or more of phosphoric acid, pyrophosphoric acid, sodium pyrophosphate or potassium pyrophosphate.
Preferably, the solvent I is water or/and alcohol; preferably, the solvent I is an alcohol solvent, and more preferably, the solvent I is one or more selected from methanol, ethanol, ethylene glycol and isopropanol.
Preferably, in the reaction liquid, the mass ratio of the titanium element in the titanium source, the tin element in the tin source and the phosphorus element in the phosphorus source is 1-0.95: 0-0.05: 2.
Preferably, in the reaction solution, the mass ratio of the titanium element in the titanium source to the carbon source is 9-4: 1.
Preferably, the concentration of titanium element in the reaction solution is 0.025 to 0.040 mol/L.
Preferably, the temperature of the hydrothermal reaction is 160 ℃, and the time of the hydrothermal reaction is 3 h.
Preferably, the sintering temperature is 600-700 ℃, and the sintering time is 2 hours.
Preferably, the gas in the non-oxidizing atmosphere is one or more selected from argon, nitrogen, helium, hydrogen and carbon monoxide.
Preferably, the solid-liquid separation mode is centrifugal separation, and more preferably, the rotating speed of the centrifugal separation is 3000-7000 r/min.
Preferably, the washing liquid is one or more of water, ethanol or glycol; preferably, the drying temperature is 70-110 ℃, and the drying time is 3-12 h.
The invention has the beneficial effects that:
(1) the preparation method takes a plurality of titanium compounds as a titanium source, uses phosphoric acid as a phosphorus source for the first time, and combines hydrothermal reaction and high-temperature calcination to prepare the tin-doped titanium pyrophosphate with higher specific capacity;
(2) the tin-doped titanium pyrophosphate prepared by the preparation method has a uniform spherical shape, the particle size range is 200-300 nm, the negative electrode material prepared by mixing the tin-doped titanium pyrophosphate with acetylene black and a binder has excellent electrochemical performance, and the first charge-discharge specific capacity reaches 900mAhg-1After 150 cycles of charging and discharging, it can also maintain 400mAhg-1The specific capacity of (A).
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern in which (a) is Ti prepared in comparative example 11-xSnxP2O7XRD patterns of (0. ltoreq. x. ltoreq.0.05)/rGO composite material, and (b) is Ti prepared in example 11-xSnxP2O7(x is more than or equal to 0 and less than or equal to 0.05) XRD pattern of the composite material;
FIG. 2 is Ti prepared in example 31-xSnxP2O7(x is more than or equal to 0 and less than or equal to 0.05)/C composite material;
FIG. 3 is a graph of electrochemical properties in which (a) is Ti prepared in comparative example 11-xSnxP2O7(x is not less than 0 and not more than 0.05)/rGO composite material electrochemical performance diagram, (b) is Ti prepared in example 11-xSnxP2O7(x is more than or equal to 0 and less than or equal to 0.05) electrochemical performance diagram of the composite material.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
Adding 16mL of graphene oxide dispersion liquid into 40mL of ethylene glycol solution, uniformly stirring, and carrying out ultrasonic treatment for 2 h; then adding 16mL of phosphoric acid into the solution, stirring for 10min at the speed of 60 r/min, adding 0.0156g of stannic chloride and 0.68g of tetrabutyl titanate into the mixed solution after uniform mixing, and stirring for 12h at the speed of 60 r/min; then transferring the solution into a 100mL reaction kettle, and carrying out hydrothermal reaction at 160 ℃ for 3 hours; carrying out suction filtration on the solution after reaction and washing for 3 times by pure water; carrying out cold drying treatment on the precursor for 24 h; finally, calcining the precursor at 600 ℃ in an argon atmosphere for 2h to obtain Ti1-xSnxP2O7 (x is more than or equal to 0 and less than or equal to 0.05)/rGO composite material.
Ti prepared in this example1-xSnxXRD scanning is carried out on the P2O7 (x is more than or equal to 0 and less than or equal to 0.05)/rGO composite material, the peak of the composite material is correspondingly consistent with that of a standard card, the target product is a pure phase, and compared with the product without the carbon source, the purity and crystallinity of the product are not influenced after the graphene is added.
Ti prepared in this example1-xSnxP2O7Fully grinding rGO (x is more than or equal to 0 and less than or equal to 0.05) with acetylene black and PVDF according to the mass ratio of 7:2:1, and then dripping a proper amount of NMP and uniformly stirring to form slurry; then coating the slurry on an aluminum foil current collector, and drying for 6 hours at 90 ℃; cutting the large pole piece into diameter by a sheet punching machineWeighing a small circular pole piece of 1cm, and drying in a 120 ℃ oven; then transferred into a glove box, a lithium sheet is taken as a counter electrode, and 1mol/L LiPF is added6(EC: DEC =1:1, volume) as electrolyte, and assembling into 2032 button cell; and finally, carrying out constant current charge and discharge test on the button cell to research important electrochemical parameters of the material, such as charge and discharge specific capacity, cycle performance, rate performance and the like. The results are shown in b) of FIG. 3, which shows Ti after addition of a carbon source1-xSnxP2O7The first charge-discharge specific capacity of the/rGO composite material can reach 900mAhg-1After 150 cycles of charging and discharging, it can still maintain 400mAhg-1The specific discharge capacity and the capacity retention rate are high, which shows that the conductivity of the material can be improved by adding the carbon source, and the electrochemical performance of the material is greatly improved.
Comparative example 1
Adding 16mL of phosphoric acid into 40mL of glycol solution, stirring for 10min at the speed of 60 r/min, respectively adding 0.0156g of stannic chloride and 0.68g of tetrabutyl titanate into the mixed solution after the two are uniformly mixed, and stirring for 12h at the speed of 60 r/min; then transferring the solution into a 100mL reaction kettle, and carrying out hydrothermal reaction at 160 ℃ for 3 hours; centrifuging the solution after reaction at the rotating speed of 5000 r/min, and washing for 3 times by pure water; drying the centrifuged precursor in a drying oven at 90 ℃ for 3 h; finally, calcining the precursor at 600 ℃ in an argon atmosphere for 2h to obtain Ti1-xSnxP2O7（0≤x≤0.05）。
Ti prepared in this example1-xSnxP2O7XRD scanning was performed, and the result is shown in (a) of FIG. 1, and the peak of the prepared titanium pyrophosphate corresponds to that of the standard card, indicating that the target product is pure phase. The tin source was not shown in the XRD characterization results due to the addition of a very small amount of tin source.
Ti prepared in this example1-xSnxP2O7(x is more than or equal to 0 and less than or equal to 0.05), acetylene black and PVDF are fully ground according to the mass ratio of 7:2:1, and then a proper amount of NMP is dropped into the mixture to be uniformly stirred to form slurry; then coating the slurry on an aluminum foil current collectorDrying at 90 deg.C for 6 h; cutting the large pole piece into small round pole pieces with the diameter of 1cm by using a sheet punching machine, weighing the small round pole pieces, and drying the small round pole pieces in a 120 ℃ drying oven; then transferred into a glove box, a lithium sheet is taken as a counter electrode, and 1mol/L LiPF is added6(EC: DEC =1:1, volume) as electrolyte, and assembling into 2032 button cell; and finally, carrying out constant current charge and discharge test on the button cell to research important electrochemical parameters of the material, such as charge and discharge specific capacity, cycle performance, rate performance and the like. The results are shown in FIG. 3 (a), pure phase Ti1- xSnxP2O7The first charge-discharge specific capacity is 700mAh g-1But the capacity attenuation is serious, and after 150 cycles of charge and discharge, the specific capacity is less than 200mAhg-1。
Example 2
Adding 16mL of phosphoric acid into 40mL of glycol solution, stirring for 10min at the speed of 60 r/min, respectively adding 0.0156g of stannic chloride and 0.68g of tetrabutyl titanate into the mixed solution after the two are uniformly mixed, and stirring for 12h at the speed of 60 r/min; then transferring the solution into a 100mL reaction kettle, and carrying out hydrothermal reaction at 160 ℃ for 3 hours; centrifuging the solution after reaction at the rotating speed of 5000 r/min, and washing for 3 times by pure water; drying the centrifuged precursor in a drying oven at 90 ℃ for 3 h; finally, calcining the precursor at 700 ℃ for 2h in argon atmosphere to obtain Ti1-xSnxP2O7（0≤x≤0.05）。
Ti prepared in this example1-xSnxP2O7(x is more than or equal to 0 and less than or equal to 0.05), acetylene black and PVDF are fully ground according to the mass ratio of 7:2:1, and then a proper amount of NMP is dropped into the mixture to be uniformly stirred to form slurry; then coating the slurry on an aluminum foil current collector, and drying for 6 hours at 90 ℃; cutting the large pole piece into small round pole pieces with the diameter of 1cm by using a sheet punching machine, weighing the small round pole pieces, and drying the small round pole pieces in a 120 ℃ drying oven; then transferred into a glove box, a lithium sheet is taken as a counter electrode, and 1mol/L LiPF is added6(EC: DEC =1:1, volume) as electrolyte, and assembling into 2032 button cell; finally, constant current charging and discharging tests are carried out on the button cell to research the important charge and discharge specific capacity, the cycle performance, the rate performance and the like of the materialAnd (4) electrochemical parameters. Ti prepared in this example1-xSnxP2O7(x is more than or equal to 0 and less than or equal to 0.05) the first charge-discharge specific capacity of the material can reach 600mAh g-1The first charge-discharge efficiency is 59.7 percent, and after 500 cycles, the specific capacity can still keep 200mAh g-1。
Example 3
Firstly, 0.2218g of glucose is added into 40mL of glycol solution, and the mixture is stirred until the glucose is completely dissolved; adding 16mL of phosphoric acid into the solution, stirring for 10min at the speed of 60 r/min, adding 0.0156g of stannic chloride and 0.68g of tetrabutyl titanate into the mixed solution after uniform mixing, and stirring for 12h at the speed of 60 r/min; then transferring the solution into a 100mL reaction kettle, and carrying out hydrothermal reaction at 160 ℃ for 3 hours; centrifuging the solution after reaction at the rotating speed of 5000 r/min, and washing for 3 times by pure water; drying the centrifuged precursor in a drying oven at 90 ℃ for 3 h; finally, calcining the precursor at 600 ℃ in an argon atmosphere for 2h to obtain Ti1-xSnxP2O7 (x is more than or equal to 0 and less than or equal to 0.05)/C composite material.
Scanning Electron microscope was used for Ti of this example1-xSnxThe P2O7 (x is more than or equal to 0 and less than or equal to 0.05)/C composite material is scanned, the result is shown in figure 2, and the figure shows that the composite material is spherical particles which are uniformly distributed and have regular shapes.
Ti prepared in this example1-xSnxP2O7Fully grinding the/C (x is more than or equal to 0 and less than or equal to 0.05), acetylene black and PVDF according to the mass ratio of 7:2:1, and then dripping a proper amount of NMP and uniformly stirring to form slurry; then coating the slurry on an aluminum foil current collector, and drying for 6 hours at 90 ℃; cutting the large pole piece into small round pole pieces with the diameter of 1cm by using a sheet punching machine, weighing the small round pole pieces, and drying the small round pole pieces in a 120 ℃ drying oven; then transferred into a glove box, a lithium sheet is taken as a counter electrode, and 1mol/L LiPF is added6(EC: DEC =1:1, volume) as electrolyte, and assembling into 2032 button cell; and finally, carrying out constant current charge and discharge test on the button cell to research important electrochemical parameters of the material, such as charge and discharge specific capacity, cycle performance, rate performance and the like. Ti prepared in this example1-xSnxP2O7/C（0≤x≤005) the first charge-discharge specific capacity of the composite material can reach 850mAh g-1The first charge-discharge efficiency is 53.5 percent, and after 300 cycles, the specific capacity can still keep 300 mAh g-1。
Claims (23)
1. A preparation method of tin-doped titanium pyrophosphate is characterized by comprising the following steps: carrying out hydrothermal reaction on a titanium source, a tin source and a phosphorus source serving as raw materials to prepare a titanium pyrophosphate precursor, and then sintering the titanium pyrophosphate precursor in a non-oxidizing atmosphere to prepare the tin-doped titanium pyrophosphate Ti1-xSnxP2O7Wherein x is more than or equal to 0 and less than or equal to 0.05;
the preparation method of the tin-doped titanium pyrophosphate comprises the following specific steps:
(1) uniformly dispersing a titanium source, a tin source and a phosphorus source into a solvent I to obtain a reaction solution, heating the reaction solution to 140-180 ℃, carrying out hydrothermal reaction for 2-6 h, cooling to room temperature, carrying out solid-liquid separation, washing, and drying to obtain a titanium pyrophosphate precursor;
(2) heating the titanium pyrophosphate precursor to 500-900 ℃ in a non-oxidizing atmosphere, sintering for 2-5 h, and cooling to room temperature to obtain the tin-doped titanium pyrophosphate Ti1-xSnxP2O7Wherein x is more than or equal to 0 and less than or equal to 0.05;
a carbon source is also dispersed in the reaction solution;
the titanium source is selected from one or more of titanium trichloride, titanium tetrachloride, titanium dioxide, titanium hydroxide and tetrabutyl titanate; the tin source is selected from one or more of tin dioxide, stannous oxide, stannic chloride tetrahydrate and stannous chloride dihydrate;
the phosphorus source is selected from one or more of phosphoric acid, pyrophosphoric acid, sodium pyrophosphate and potassium pyrophosphate;
the solvent I is an alcohol solvent;
in the reaction liquid, the mass ratio of the titanium element in the titanium source to the carbon source is 9-4: 1.
2. The method of claim 1, wherein the carbon source is graphene or/and glucose.
3. The method of claim 1 or 2, wherein the solvent I is selected from one or more of methanol, ethanol, ethylene glycol, and isopropanol.
4. The method of producing tin-doped titanium pyrophosphate according to claim 1 or 2, wherein the mass ratio of the titanium element in the titanium source, the tin element in the tin source, and the phosphorus element in the phosphorus source in the reaction solution is 1 to 0.95:0 to 0.05: 2.
5. The method of producing tin-doped titanium pyrophosphate according to claim 3 wherein the mass ratio of the titanium element in the titanium source, the tin element in the tin source, and the phosphorus element in the phosphorus source in the reaction solution is 1 to 0.95:0 to 0.05: 2.
6. The method of producing tin-doped titanium pyrophosphate according to claim 1 or 2, wherein the concentration of titanium element in the reaction solution is 0.025 to 0.040 mol/L; the solid-liquid separation mode is centrifugal separation; the rotating speed of the centrifugal separation is 3000-7000 r/min; the washing liquid is one or more of water, ethanol or glycol; the drying temperature is 70-110 ℃, and the drying time is 3-12 h.
7. The method of claim 3, wherein the concentration of titanium in the reaction solution is 0.025 to 0.040 mol/L; the solid-liquid separation mode is centrifugal separation; the rotating speed of the centrifugal separation is 3000-7000 r/min; the washing liquid is one or more of water, ethanol or glycol; the drying temperature is 70-110 ℃, and the drying time is 3-12 h.
8. The method of claim 4, wherein the concentration of titanium in the reaction solution is 0.025 to 0.040 mol/L; the solid-liquid separation mode is centrifugal separation; the rotating speed of the centrifugal separation is 3000-7000 r/min; the washing liquid is one or more of water, ethanol or glycol; the drying temperature is 70-110 ℃, and the drying time is 3-12 h.
9. The method of claim 1 or 2, wherein the hydrothermal reaction is carried out at a temperature of 160 ℃ for a time of 3 hours.
10. The method of claim 3, wherein the hydrothermal reaction is carried out at a temperature of 160 ℃ for a period of 3 hours.
11. The method of claim 4, wherein the hydrothermal reaction is carried out at a temperature of 160 ℃ for a time of 3 hours.
12. The method of claim 6, wherein the hydrothermal reaction is carried out at a temperature of 160 ℃ for a period of 3 hours.
13. The method for preparing tin-doped titanium pyrophosphate according to claim 1 or 2, wherein the sintering temperature is 600 to 700 ℃ and the sintering time is 2 hours.
14. The method for preparing tin-doped titanium pyrophosphate according to claim 3 wherein the sintering temperature is 600 to 700 ℃ and the sintering time is 2 hours.
15. The method for preparing tin-doped titanium pyrophosphate according to claim 4 wherein the sintering temperature is 600 to 700 ℃ and the sintering time is 2 hours.
16. The method for preparing tin-doped titanium pyrophosphate according to claim 6 wherein the sintering temperature is 600 to 700 ℃ and the sintering time is 2 hours.
17. The method for preparing tin-doped titanium pyrophosphate according to claim 9 wherein the sintering temperature is 600 to 700 ℃ and the sintering time is 2 hours.
18. The method of claim 1 or 2, wherein the gas in the non-oxidizing atmosphere is selected from one or more of argon, nitrogen, helium, hydrogen, and carbon monoxide.
19. The method of claim 3, wherein the gas in the non-oxidizing atmosphere is selected from one or more of argon, nitrogen, helium, hydrogen, and carbon monoxide.
20. The method of claim 4, wherein the gas in the non-oxidizing atmosphere is selected from one or more of argon, nitrogen, helium, hydrogen, and carbon monoxide.
21. The method of claim 6, wherein the gas in the non-oxidizing atmosphere is selected from one or more of argon, nitrogen, helium, hydrogen, and carbon monoxide.
22. The method of claim 9, wherein the gas in the non-oxidizing atmosphere is selected from one or more of argon, nitrogen, helium, hydrogen, and carbon monoxide.
23. The method of claim 13, wherein the gas in the non-oxidizing atmosphere is selected from one or more of argon, nitrogen, helium, hydrogen, and carbon monoxide.
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| CN107311137A (en) * | 2017-08-04 | 2017-11-03 | 武汉理工大学 | A kind of method of utilization titanium tetrachloride solvent-thermally synthesizing nano Titanium pyrophosphate |
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