CN113991103A - Aqueous lithium ion battery NaTi2(PO4)3Preparation method of/C negative electrode material - Google Patents

Aqueous lithium ion battery NaTi2(PO4)3Preparation method of/C negative electrode material Download PDF

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CN113991103A
CN113991103A CN202111105710.7A CN202111105710A CN113991103A CN 113991103 A CN113991103 A CN 113991103A CN 202111105710 A CN202111105710 A CN 202111105710A CN 113991103 A CN113991103 A CN 113991103A
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nati
negative electrode
electrode material
lithium ion
ion battery
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张靖佳
卢典虹
玉富达
王振波
王红霞
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Harbin Normal University
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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
    • H01M4/58—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
    • H01M4/5805—Phosphides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Abstract

The invention discloses a water system lithium ion battery NaTi2(PO4)3The preparation method of the/C negative electrode material specifically comprises the following steps: step one, preparing NaTi by adopting a coprecipitation or hydrothermal treatment method2(PO4)3a/C anode material precursor; step two, drying the NaTi2(PO4)3the/C cathode material precursor is calcined at high temperature in a tubular furnace filled with different gases to obtain NaTi2(PO4)3a/C negative electrode material. The invention belongs to the technical field of material synthesis, and provides a water system lithium ion battery NaTi with more complete chemical reaction, stable material structure and less impurity generation2(PO4)3A preparation method of the/C negative electrode material; the preparation method has simple preparation process, the capacity retention rate of the electrode material is obviously improved, and the prepared NaTi2(PO4)3the/C negative electrode material has good cycle performance in the electrochemical reaction process.

Description

Aqueous lithium ion battery NaTi2(PO4)3Preparation method of/C negative electrode material
Technical Field
The invention belongs to the technical field of material synthesis, relates to a cathode of a water system lithium ion battery and a preparation method thereof, and particularly relates to a NaTi of the water system lithium ion battery2(PO4)3A preparation method of the/C negative electrode material.
Background
Compared with lead-acid batteries, nickel-cadmium batteries and the like, the lithium ion batteries have the advantages of high energy density, high working voltage and the like. The lithium ion battery electrolyte mainly comprises electrolyte salts such as lithium hexafluorophosphate and lithium hexafluoroarsenate, organic solvents such as carbonic ester and carboxylic ester, additives such as film forming and flame retarding. The organic electrolyte has low conductivity, certain volatility and combustibility and higher cost, and the lithium ion battery has higher assembly process requirement and expensive battery components. The traditional lithium ion battery has higher requirements on large-scale practical application. In 1994, the first report of LiMn by Dahn team in Canada2O4As cathode material, VO2As anode material, LiNO3An aqueous lithium ion battery as an electrolyte. Since then, more and more researchers are continuously developing new materials to study aqueous lithium ion battery systems. The aqueous lithium ion battery adopts inorganic salt aqueous solution such as lithium sulfate, lithium nitrate and the like with higher safety performance and lower cost as electrolyte, and the battery assembly process is simple. The ionic conductivity of the organic electrolyte is lower than that of the water system electrolyte by 2 orders of magnitude, and the water system battery has better cycle performance and rate performance due to higher ionic conductivity.
The electrochemical window of the water-based electrolyte is 1.23V, and the narrow electrochemical window limits the practical application of a plurality of anode and cathode materials in a water-based battery. Oxidation-reduction potential of 3 to 4V (VsLi)+The material of/Li) can be used for the anode of the water-based ion battery. Lithium manganate, lithium iron phosphate, lithium cobaltate, and the like are the most widely studied positive electrode materials for aqueous lithium ion batteries. Oxidation-reduction potential of 2-3V (Vs Li)+The material of/Li) can be used for the cathode of the water-based ion battery. VO (vacuum vapor volume)2、V2O5、LiV3O8An aqueous battery using vanadium oxide as a negative electrode, since vanadium is contained in the aqueous batteryDissolution in an aqueous electrolyte leads to poor cycle stability of the battery and rapid capacity fade. In the Chenpu subject group of the Canadian smooth iron Lu university, a water-based battery is assembled by using Zn metal as an anode, lithium manganate as a cathode and a lithium sulfate and zinc sulfate mixed aqueous solution, and a great deal of research work is carried out. It has been found that zinc anodes inevitably corrode in aqueous solution and produce zinc dendrites during the electrochemical process, thereby reducing the stability of the electrode material and accelerating capacity fade. Compared with the cathode materials, the titanium sodium phosphate with the sodium super-ion conductor structure has a three-dimensional framework structure which allows reversible intercalation and deintercalation of sodium ions, and has small volume change and better thermodynamic stability in the reaction process. The electron conductivity of the battery is improved by in-situ carbon coating, so that the electron transmission in the charge and discharge process is accelerated, and the electrochemical performance of the battery is improved. The improvement of the stability and specific capacity of the electrode material in the aqueous electrolyte is the key to solve the problem of improving the possibility of practical application of the aqueous battery.
Disclosure of Invention
Aiming at the situation, in order to solve the problem that the capacity of the cathode material of the water-system lithium ion battery is rapidly attenuated in the aqueous solution, the invention provides NaTi of the water-system lithium ion battery2(PO4)3Preparation method of/C negative electrode material, and preparation of NaTi by sol-gel method, solid phase method and the like2(PO4)3Compared with the precursor of the C material, the NaTi provided by the invention2(PO4)3The preparation method of the/C precursor is simple and the experimental process is easy to operate.
The invention provides the following technical scheme: the invention provides a water system lithium ion battery NaTi2(PO4)3The preparation method of the/C negative electrode material specifically comprises the following steps:
step one, preparing NaTi by adopting a coprecipitation or hydrothermal treatment method2(PO4)3a/C anode material precursor;
step two, drying the NaTi2(PO4)3the/C cathode material precursor is calcined at high temperature in a tubular furnace filled with different gases to obtain NaTi2(PO4)3a/C negative electrode material.
Further, in the step one, a coprecipitation method is adopted to prepare NaTi2(PO4)3the/C anode material precursor specifically comprises the following steps:
(1) respectively weighing 70% phytic acid solution, sodium hydroxide and tetrabutyl titanate according to the mol ratio of 1:2:4, dropwise adding 70% phytic acid solution and sodium hydroxide mixed aqueous solution into tetrabutyl titanate alcoholic solution, and stirring for 5 hours at room temperature;
(2) centrifuging the suspension obtained after stirring, repeatedly washing the precipitate with distilled water and absolute ethyl alcohol, and drying the precipitate in a vacuum drying oven to obtain NaTi2(PO4)3and/C, a precursor of the negative electrode material.
Further, the method of coprecipitation is adopted to prepare NaTi2(PO4)3Under the condition of a/C anode material precursor, the high-temperature calcination of NaTi is adopted in the step two2(PO4)3a/C cathode material precursor to obtain NaTi2(PO4)3The method of the/C negative electrode material is as follows: the NaTi obtained in the step one2(PO4)3Placing the/C cathode material precursor in a tube furnace filled with argon or hydrogen-argon mixed gas for heat treatment, pre-burning for 1h at 550 ℃, and calcining for 5h at 750 ℃ to obtain the NaTi2(PO4)3a/C negative electrode material.
Further, in the step one, a hydrothermal treatment method is adopted to prepare NaTi2(PO4)3the/C anode material precursor specifically comprises the following steps:
(1) respectively weighing 70% phytic acid solution, sodium hydroxide and tetrabutyl titanate according to the mol ratio of 1:2:4, dropwise adding 70% phytic acid solution and sodium hydroxide mixed aqueous solution into tetrabutyl titanate alcoholic solution, and uniformly stirring at room temperature;
(2) transferring the mixed solution into a hydrothermal kettle with a 100mL polytetrafluoroethylene lining, placing the hydrothermal kettle in an air-blowing drying box, carrying out hydrothermal treatment, centrifuging, washing, and drying in a drying ovenDrying in a vacuum drying oven to obtain NaTi2(PO4)3and/C, a precursor of the negative electrode material.
Wherein the hydrothermal treatment temperature is 160-180 ℃, and the treatment time is 12-24 h.
Further, the method of hydrothermal treatment is adopted to prepare NaTi2(PO4)3Under the condition of a/C anode material precursor, the high-temperature calcination of NaTi is adopted in the step two2(PO4)3a/C cathode material precursor to obtain NaTi2(PO4)3The method of the/C negative electrode material is as follows: the NaTi obtained in the step one2(PO4)3Placing the/C cathode material precursor in a tube furnace filled with hydrogen and argon mixed gas for heat treatment, presintering for 1h at 550 ℃, calcining for 5h at 750 ℃ to obtain NaTi2(PO4)3a/C negative electrode material.
Further, the 70% phytic acid solution is NaTi2(PO4)3the/C negative electrode material provides a phosphorus source and a carbon source.
Further, the drying condition in the vacuum drying oven is 80 ℃, and the drying time is 10 h.
Further, the volume ratio of hydrogen to argon in the hydrogen-argon mixed gas is 10: 90.
the invention with the structure has the following beneficial effects: the invention relates to a water system lithium ion battery NaTi2(PO4)3The preparation method of the/C cathode material is simple and easy to operate, the chemical reaction is more complete, the material structure is stable, and the generation of impurities is less; the preparation method has the advantages of simple preparation process, low cost, obviously improved capacity retention rate of the electrode material, and prepared NaTi2(PO4)3the/C negative electrode material has good cycle performance in the electrochemical reaction process.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an example1 NaTi prepared under argon atmosphere2(PO4)3TEM image of/C negative electrode material.
FIG. 2 is NaTi prepared in example 1 under argon atmosphere2(PO4)3And the/C negative electrode material cycle performance diagram.
FIG. 3 shows NaTi prepared in example 2 under an atmosphere of mixed hydrogen and argon2(PO4)3TEM image of/C negative electrode material.
FIG. 4 shows NaTi prepared in example 2 under an atmosphere of mixed hydrogen and argon2(PO4)3And the/C negative electrode material cycle performance diagram.
FIG. 5 shows an aqueous all-cell (NaTi) of example 32(PO4)3/C)/LiMn2O4And (4) a charge-discharge curve diagram.
FIG. 6 is NaTi prepared in example 42(PO4)3And the/C negative electrode material cycle performance diagram.
FIG. 7 shows NaTi obtained after calcination of precursors prepared in different ways in examples 2 and 42(PO4)3XRD pattern of/C.
FIG. 8 is NaTi prepared in example 52(PO4)3And the/C negative electrode material cycle performance diagram.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "front," "back," "left," "right," "upper" and "lower" used in the following description refer to directions in the drawings, and the terms "inner" and "outer" refer to directions toward and away from, respectively, the geometric center of a particular component.
Example 1
Weighing 70% phytic acid solution, sodium hydroxide and tetrabutyl titanate according to the molar ratio of 1:2: 4; dissolving the phytic acid solution (70%) and sodium hydroxide in 10mL of distilled water, and stirring on a magnetic stirrer until the solid is completely dissolved to obtain a solution A; adding 25mL of n-butyl alcohol and 25mL of absolute ethyl alcohol into the tetrabutyl titanate, and uniformly stirring the mixture on a magnetic stirrer to obtain a solution B; continuously stirring, dropwise adding the solution A into the solution B, and stirring for 5 hours at room temperature; centrifuging and washing the obtained suspension at 8000 rpm for 10 min, repeatedly washing with distilled water and anhydrous ethanol to remove impurities, and centrifuging for 5 times; collecting the precipitate, and drying the precipitate in a vacuum drying oven at 80 ℃ for 10h to obtain the white precursor of the sodium titanium phosphate material.
And (3) grinding the white precursor in an agate mortar for 10 minutes, putting a certain amount of white powder in a tube furnace in an argon atmosphere, heating from 20 ℃ to 550 ℃ at a heating rate of 5 ℃/min for pre-sintering for 1 hour, and heating to 750 ℃ at the same heating rate for calcining for 5 hours to obtain the carbon-coated sodium titanium phosphate cathode material.
As shown in fig. 1, which is a transmission electron microscope image of the sodium titanium phosphate anode material prepared in this embodiment, it can be seen that the sodium titanium phosphate anode material prepared in this embodiment has a uniform carbon layer at the edge.
The obtained NaTi2(PO4)3the/C negative electrode material is used for assembling a three-electrode system of the water-based battery and takes 1M Na2SO4The aqueous solution is used as electrolyte, electrochemical performance test is carried out in a voltage range of-1.0 to-0.3V, the first discharge specific capacity of the battery is 99.2mAh/g under 1C multiplying power, and after 100 charge-discharge cycles, the capacity retention rate is 83.3 percent, as shown in figure 2.
Example 2
Weighing 70% phytic acid solution, sodium hydroxide and tetrabutyl titanate according to the molar ratio of 1:2: 4; dissolving the phytic acid solution (70%) and sodium hydroxide in 10mL of distilled water, and stirring on a magnetic stirrer until the solid is completely dissolved to obtain a solution A; adding 25mL of n-butyl alcohol and 25mL of absolute ethyl alcohol into the tetrabutyl titanate, and uniformly stirring the mixture on a magnetic stirrer to obtain a solution B; continuously stirring, dropwise adding the solution A into the solution B, and stirring for 5 hours at room temperature; centrifuging and washing the obtained suspension at 8000 rpm for 10 min, repeatedly washing with distilled water and anhydrous ethanol to remove impurities, and centrifuging for 5 times; collecting the precipitate, and drying the precipitate in a vacuum drying oven at 80 ℃ for 10h to obtain the white precursor of the sodium titanium phosphate material.
And (2) grinding the white precursor in an agate mortar for 10 minutes, putting a certain amount of white powder in a tubular furnace hydrogen-argon mixing (H2/Ar is 10:90) atmosphere, heating from 20 ℃ to 550 ℃ at a heating rate of 5 ℃/min for presintering for 1H, and then heating to 750 ℃ at the same heating rate for calcining for 5H to obtain the carbon-coated sodium titanium phosphate cathode material.
As shown in fig. 3, which is a transmission electron microscope image of the sodium titanium phosphate anode material prepared in this embodiment, it can be seen that the sodium titanium phosphate anode material prepared in this embodiment has a uniform carbon layer at the edge.
The obtained NaTi2(PO4)3the/C negative electrode material is used for assembling a three-electrode system of the water-based battery and takes 1M Na2SO4The aqueous solution is used as electrolyte, electrochemical performance test is carried out in a voltage range of-1.0 to-0.3V, the first discharge specific capacity of the battery is 101.9mAh/g under 1C multiplying power, and after 100 charge-discharge cycles, the capacity retention rate is 83.3 percent, as shown in figure 4.
The comparison between example 1 and example 2 shows that: compared with the electrochemical stability of a sample calcined in argon, the material calcined in the hydrogen-argon mixed atmosphere has relatively small material capacity change fluctuation in the cycle process, namely the material has small structure change in the charge-discharge cycle process.
Example 3
NaTi was synthesized according to the preparation method of example 22(PO4)3C: with synthetic NaTi2(PO4)3the/C is a negative electrode material, the commercial lithium manganate is a positive electrode material, and the Li2SO4And Na2SO4The mixed aqueous solution is used as electrolyte, and the whole battery is assembled and electrochemically processed within the voltage range of 0.1-1.85VAnd (3) performance testing, wherein the first charging specific capacity of the battery is 103mAh/g, as shown in figure 5.
Example 4
Weighing 70% phytic acid solution, sodium hydroxide and tetrabutyl titanate according to the molar ratio of 1:2: 4; dissolving the phytic acid solution (70%) and sodium hydroxide in 10mL of distilled water, and stirring on a magnetic stirrer until the solid is completely dissolved to obtain a solution A; adding 25mL of n-butyl alcohol and 25mL of absolute ethyl alcohol into the tetrabutyl titanate, and uniformly stirring the mixture on a magnetic stirrer to obtain a solution B; adding the solution A into the solution B drop by drop under continuous stirring; stirring for 30 minutes, transferring the mixed solution into a 100mL hydrothermal kettle with a polytetrafluoroethylene lining, placing the hydrothermal kettle in an air-blowing drying oven, setting the temperature to be 160 ℃, and reacting for 24 hours; after the reaction is finished, after the hydrothermal kettle is naturally cooled to room temperature, taking out the inner liner, centrifugally washing the obtained suspension at the centrifugal speed of 8000 rpm for 5 minutes each time, repeatedly washing with distilled water and absolute ethyl alcohol to remove impurities, and centrifuging for 5 times; collecting the precipitate, and drying the precipitate in a vacuum drying oven at 80 ℃ for 10h to obtain the white precursor of the sodium titanium phosphate material.
Putting the precursor into an agate mortar for manual grinding, putting a certain amount of powder into a tube furnace hydrogen-argon mixing (H2/Ar is 10:90) atmosphere, heating from 20 ℃ to 550 ℃ at the heating rate of 5 ℃/min for presintering for 1H, heating to 750 ℃ at the same heating rate, and calcining for 5H to obtain the NaTi2(PO4)3a/C negative electrode material.
The obtained NaTi2(PO4)3the/C negative electrode material is used for assembling a three-electrode system of the water-based battery and takes 1M Na2SO4The aqueous solution was used as an electrolyte, and an electrochemical performance test was performed at a rate of 1C, and after 200 charge-discharge cycles, the capacity retention rate was 94.3%, as shown in fig. 6.
FIG. 7 shows NaTi obtained after high-temperature calcination of hydrothermal and non-hydrothermal precursors2(PO4)3XRD contrast diagram of/C cathode material. XRD pattern shows that NaTi is not prepared by hydrothermal method2(PO4)3the/C material is between 25 and 30 DEGNaTi prepared after hydrothermal synthesis with an unknown impurity peak2(PO4)3No peak was observed between 25 ℃ and 30 ℃ for the/C material. On the basis of coprecipitation, hydrothermal is carried out in the process of preparing a precursor, so that chemical reaction is more complete through hydrothermal, the generation of impurities is reduced, and the material structure is stable.
Example 5
Weighing 70% phytic acid solution, sodium hydroxide and tetrabutyl titanate according to the molar ratio of 1:2: 4; dissolving the phytic acid solution (70%) and sodium hydroxide in 10mL of distilled water, and stirring on a magnetic stirrer until the solid is completely dissolved to obtain a solution A; adding 25mL of n-butyl alcohol and 25mL of absolute ethyl alcohol into the tetrabutyl titanate, and uniformly stirring the mixture on a magnetic stirrer to obtain a solution B; adding the solution A into the solution B drop by drop under continuous stirring; stirring for 30 minutes, transferring the mixed solution into a 100mL hydrothermal kettle with a polytetrafluoroethylene lining, placing the hydrothermal kettle in a forced air drying oven, setting the temperature to be 180 ℃, and reacting for 12 hours; after the reaction is finished, after the hydrothermal kettle is naturally cooled to room temperature, taking out the inner liner, centrifugally washing the obtained suspension at the centrifugal speed of 8000 rpm for 5 minutes each time, repeatedly washing with distilled water and absolute ethyl alcohol to remove impurities, and centrifuging for 5 times; collecting the precipitate, and drying the precipitate in a vacuum drying oven at 80 ℃ for 10h to obtain the white precursor of the sodium titanium phosphate material.
Putting the precursor into an agate mortar for manual grinding, putting a certain amount of powder into a tube furnace hydrogen-argon mixing (H2/Ar is 10:90) atmosphere, heating from 20 ℃ to 550 ℃ at the heating rate of 5 ℃/min for presintering for 1H, heating to 750 ℃ at the same heating rate, and calcining for 5H to obtain the NaTi2(PO4)3a/C negative electrode material.
The obtained NaTi2(PO4)3/C negative electrode material is assembled into a three-electrode system of an aqueous battery, and 1M Na is added2SO4The aqueous solution was used as an electrolyte, and an electrochemical performance test was performed at a rate of 1C, and after 200 charge-discharge cycles, the capacity retention rate was 96.2%, as shown in fig. 8.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (9)

1. Aqueous lithium ion battery NaTi2(PO4)3The preparation method of the/C negative electrode material is characterized by comprising the following steps:
step one, preparing NaTi by adopting a coprecipitation or hydrothermal treatment method2(PO4)3a/C anode material precursor;
step two, drying the NaTi2(PO4)3the/C cathode material precursor is calcined at high temperature in a tubular furnace filled with different gases to obtain NaTi2(PO4)3a/C negative electrode material.
2. An aqueous lithium ion battery, NaTi, as claimed in claim 12(PO4)3The preparation method of the/C cathode material is characterized in that a coprecipitation method is adopted in the step one to prepare NaTi2(PO4)3the/C anode material precursor specifically comprises the following steps:
(1) respectively weighing 70% phytic acid solution, sodium hydroxide and tetrabutyl titanate according to the mol ratio of 1:2:4, dropwise adding 70% phytic acid solution and sodium hydroxide mixed aqueous solution into tetrabutyl titanate alcoholic solution, and stirring for 5 hours at room temperature;
(2) centrifuging the suspension obtained after stirring, repeatedly washing the precipitate with distilled water and absolute ethyl alcohol, and drying the precipitate in a vacuum drying oven to obtain NaTi2(PO4)3and/C, a precursor of the negative electrode material.
3. An aqueous lithium ion battery, NaTi, as claimed in claim 22(PO4)3The preparation method of the/C cathode material is characterized in that the coprecipitation method is adopted to prepare the NaTi2(PO4)3Under the condition of a/C anode material precursor, the high-temperature calcination of NaTi is adopted in the step two2(PO4)3a/C cathode material precursor to obtain NaTi2(PO4)3The method of the/C negative electrode material is as follows: the NaTi obtained in the step one2(PO4)3Placing the/C cathode material precursor in a tube furnace filled with argon or hydrogen-argon mixed gas for heat treatment, pre-burning for 1h at 550 ℃, and calcining for 5h at 750 ℃ to obtain the NaTi2(PO4)3a/C negative electrode material.
4. An aqueous lithium ion battery, NaTi, as claimed in claim 12(PO4)3The preparation method of the/C cathode material is characterized in that in the step one, a hydrothermal treatment method is adopted to prepare NaTi2(PO4)3the/C anode material precursor specifically comprises the following steps:
(1) respectively weighing 70% phytic acid solution, sodium hydroxide and tetrabutyl titanate according to the mol ratio of 1:2:4, dropwise adding 70% phytic acid solution and sodium hydroxide mixed aqueous solution into tetrabutyl titanate alcoholic solution, and uniformly stirring at room temperature;
(2) transferring the mixed solution into a hydrothermal kettle with a 100mL polytetrafluoroethylene lining, placing the hydrothermal kettle in an air-blowing drying box, carrying out hydrothermal treatment, centrifuging, washing, and drying in a drying ovenDrying in a vacuum drying oven to obtain NaTi2(PO4)3and/C, a precursor of the negative electrode material.
5. The aqueous lithium ion battery NaTi of claim 42(PO4)3The preparation method of the/C cathode material is characterized in that the hydrothermal treatment temperature is 160-180 ℃, and the treatment time is 12-24 hours.
6. An aqueous lithium ion battery NaTi as claimed in claim 52(PO4)3The preparation method of the/C cathode material is characterized in that the NaTi is prepared by adopting a hydrothermal treatment method2(PO4)3Under the condition of a/C anode material precursor, the high-temperature calcination of NaTi is adopted in the step two2(PO4)3a/C cathode material precursor to obtain NaTi2(PO4)3The method of the/C negative electrode material is as follows: the NaTi obtained in the step one2(PO4)3Placing the/C cathode material precursor in a tube furnace filled with hydrogen and argon mixed gas for heat treatment, presintering for 1h at 550 ℃, calcining for 5h at 750 ℃ to obtain NaTi2(PO4)3a/C negative electrode material.
7. An aqueous lithium ion battery, NaTi, according to claim 2 or 42(PO4)3The preparation method of the/C negative electrode material is characterized in that the 70% phytic acid solution is NaTi2(PO4)3the/C negative electrode material provides a phosphorus source and a carbon source.
8. An aqueous lithium ion battery, NaTi, according to claim 2 or 42(PO4)3The preparation method of the/C negative electrode material is characterized in that the drying condition in the vacuum drying oven is 80 ℃, and the drying time is 10 hours.
9. An aqueous lithium ion battery, NaTi, according to claim 3 or 62(PO4)3The preparation method of the/C negative electrode material is characterized in that the volume ratio of hydrogen to argon in the hydrogen-argon mixed gas is 10: 90.
CN202111105710.7A 2021-09-22 2021-09-22 Aqueous lithium ion battery NaTi2(PO4)3Preparation method of/C negative electrode material Withdrawn CN113991103A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114873573A (en) * 2022-04-19 2022-08-09 江苏理工学院 NaTi 2 (PO4) 3 @ C micro-nano composite material and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114873573A (en) * 2022-04-19 2022-08-09 江苏理工学院 NaTi 2 (PO4) 3 @ C micro-nano composite material and preparation method and application thereof
CN114873573B (en) * 2022-04-19 2023-09-22 江苏理工学院 NaTi (sodium silicate) 2 (PO 4 ) 3 @C micro-nano composite material and preparation method and application thereof

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