CN111180696A - Micro-flower structure TiP2O7/C composite material and preparation method and application thereof - Google Patents

Micro-flower structure TiP2O7/C composite material and preparation method and application thereof Download PDF

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CN111180696A
CN111180696A CN201911420169.1A CN201911420169A CN111180696A CN 111180696 A CN111180696 A CN 111180696A CN 201911420169 A CN201911420169 A CN 201911420169A CN 111180696 A CN111180696 A CN 111180696A
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composite material
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杨剑
潘军
钱逸泰
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Shandong University
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract

The invention relates to a micro-flower structure TiP2O7The invention adopts tetrabutyl titanate (TBOT) and Phytic Acid (PA) to carry out hydrothermal reaction in ethanol, and then calcinates the reaction product at high temperature to successfully synthesize TiP with a micro-flower structure2O7@ C. In this structure, TiP2O7The layers of the popcorn sheet are covered with a thin layer of carbon. The structure is used as a sodium ion battery negative electrodePole material, while achieving high space utilization and long cycle life. At 2.0A g‑1After the current density of the anode material is circulated for 10000 times, the capacity retention rate of the anode material is 88 percent, and the anode material is a cathode material with very excellent performance in titanium-based compound materials.

Description

Micro-flower structure TiP2O7/C composite material and preparation method and application thereof
The technical field is as follows:
the invention provides a micro-flower structure TiP2O7A/C composite material and a preparation method and application thereof belong to the technical field of materials and sodium ion batteries.
Background art:
lithium Ion Batteries (LIBs) have been used in various areas of life as clean energy storage equipment, however, the limited lack of lithium resources has limited the use of LIBs in large energy storage devices. Therefore, it is very important to find a new energy system, and at the same time, sodium ion batteries (NIBs) attract people's attention, theoretically, the NIBs have a similar working principle to LIBs, abundant reserves and low exploitation costs are the basis of research, aluminum foil is directly used as a current collector, assembly costs are reduced, side reactions such as organic electrolyte and the like are reduced due to a low potential, and the defects are that a large ionic radius slows down the diffusion rate of sodium ions in an electrode material and causes a large volume expansion effect, so that the structure collapses, the active substances fall off, and the capacity is rapidly reduced. Therefore, the key to the development of sodium ion batteries is a stable and efficient electrode material. From the commercialization perspective, the LIBs production line is established, NIBs need only to be slightly optimized, and enterprises are reluctant to research lithium-sulfur batteries and lithium-air batteries because they need to invest large manpower and material resources from basic research to production. And sodium ion battery bicycles of Faradion company in UK are on the market at present, and research power is provided for us, but the energy density is still unable to be compared with LIBs, so the development of electrode materials of sodium ion batteries (NIBs) is critical.
The current commercial NIBs cathode material graphite has poor sodium storage capacity
Figure BDA0002352164160000011
And the potential is low, which can cause sodium dendrite growth and cause safety hazards. The materials of the alloy mechanism have large theoretical specific capacity, such as Sb (660mAh g)-1)，Sn(847mAh g-1)，P(2596mAh g-1) However, such materials undergo large volume changes during cycling, resulting in pulverization of the electrode material and capacity fade. Ti-based oxides have several advantages over carbon and alloys, such as high binding affinity to the electrode, excellent thermal stability to carbon and a suitable discharge potential. Therefore, research into composite materials based on Ti-related oxides is essential. TiO 22The materials have attracted a wide range of attentionThe applicant synthesizes the well-defined Sb/TiO through a simple process in the research process2Nanotubes, which repeat 1000 cycles of discharge/charge in lithium ion batteries and sodium ion batteries, have high capacity retention. However, excessive internal voids of the nanotubes will significantly reduce the volumetric energy density. Therefore, in order to improve the energy density, the Sb @ Ti-P-O nanowire with the egg yolk shell structure is developed, wherein the porous Sb nanorod is used as a core, and the amorphous Ti-P-O nanotube is used as a shell. Although the space utilization and reversible capacity are improved, the lifetime is only 0.5Ag-1About 200 cycles. Balancing cycle life and space utilization is therefore a great challenge. The applicant prepares two-phase doped TiO by a simple hydrothermal synthesis method2The material/C is 6000 circles in circulation under high current density, and also has 120mAh g-1However, for a theoretical specific capacity of 335mAh g-1Of TiO 22The specific capacity of the material is not satisfactory.
Therefore, it is required to develop a novel Ti-based oxide electrode material with higher specific capacity and cycle life.
The invention content is as follows:
aiming at the defects of the prior art, the invention provides a micro-flower rice structure TiP2O7a/C composite material, a preparation method and application thereof.
Summary of the invention:
the invention adopts butyl titanate (TBOT) and Phytic Acid (PA) to carry out hydrothermal reaction in ethanol, and then calcinates at high temperature to successfully synthesize the TiP with the structure of the micro-flower rice2O7@ C. In this structure, TiP2O7The layers of the popcorn sheet are covered with a thin layer of carbon. The structure is used as a cathode material of the sodium-ion battery, and high space utilization rate and long cycle life are realized. At 2.0Ag-1After the current density of the anode material is circulated for 10000 times, the capacity retention rate of the anode material is 88 percent, and the anode material is a cathode material with very excellent performance in titanium-based compound materials.
Detailed description of the invention:
the technical scheme of the invention is as follows:
micro-flower structure TiP2O7a/C composite material, wherein the composite material is crystalline TiP2O7The outside is coated with a thin carbon layer, and the thickness of the thin carbon layer is 1-3 nm.
Preferred according to the invention are the micro-flower structures TiP2O7The length of the/C composite material is 2-5 um.
The second purpose of the invention is to provide a micro-popcorn structure TiP2O7A preparation method of the/C composite material.
Micro-flower structure TiP2O7The preparation method of the/C composite material comprises the following steps:
(1) dispersing a titanium source in a solvent, adding a phosphorus source, heating and dissolving, carrying out hydrothermal reaction at 160-200 ℃ for 8-24h, centrifuging a reaction product, sequentially carrying out ethanol washing and water washing, and then carrying out vacuum drying to obtain a precursor;
(2) the precursor is burned at the high temperature of 600-900 ℃ for 2-6h to obtain the TiP with the structure of the micro-flower rice2O7C or TiP2O7A composite material.
According to the invention, the vacuum dried product can obtain the micro-popcorn structure TiP when being burned at high temperature under the protection of inert gas2O7a/C composite material; the vacuum dried product is burnt in the air at high temperature to obtain the TiP with the structure of the micro-flower rice2O7A composite material.
According to the invention, the preferable inert gas is nitrogen, the ignition temperature is 800-900 ℃, and the ignition time is 4-6 h.
Preferably, in step (1), the titanium source is tetrabutyl titanate TBOT.
Preferably, in step (1), the volume ratio of the titanium source to the solvent is (0.1-0.6): 40.
preferably, in step (1), the phosphorus source is Phytic Acid (PA).
According to the invention, in the step (1), the volume ratio of the added titanium source to the phosphorus source is 1 (0.6-1).
Preferably, in step (1), the solvent is ethanol.
According to the invention, in the step (1), the temperature of the hydrothermal reaction is 180-200 ℃ and the reaction time is 10-14 h.
According to the invention, in the step (1), the vacuum drying temperature is 50-70 ℃, and the drying time is 10-14 h.
The above-mentioned micro-flower structure TiP2O7The application of the/C composite material is applied to a sodium ion battery and used as a negative electrode material of the sodium ion battery.
TiP, preferably according to the invention, based on the micro-flower structure2O7The sodium ion battery of the/C composite material comprises a positive plate, a negative plate, a diaphragm, electrolyte and a shell, wherein the positive plate, the negative plate, the diaphragm, the electrolyte and the shell are obtained by respectively mixing an active material, a conductive agent and a binder, then adding a solvent, grinding into slurry and coating on a current collector; the active material in the sodium ion battery negative plate is a micro-popcorn structure TiP2O7the/C composite material and the sodium sheet are used as a counter electrode.
According to the invention, the negative plate is prepared by the following method: making the micro-flower structure TiP2O7Mixing the/C composite material, the conductive agent and the binder according to the mass ratio of 7:2:1, adding water, grinding into slurry, coating on a copper foil, coating, drying in vacuum at 60 ℃, drying, rolling, cutting into pole pieces, wherein the mass of the active material in unit area is 1.0-1.5 mgcm-2。
According to the invention, the electrolyte is preferably NaClO4Soluble in propylene carbonate, NaClO4The concentration of (A) is 1 mol/L; the membrane material was Whatman GF/F glass microfiber.
The principle of the invention is as follows:
the invention obtains Ti (HPO) by hydrothermal reaction by taking tetrabutyl titanate TBOT and Phytic Acid (PA) as raw materials and ethanol as a solvent4)2·xH2O, high-temperature calcination is carried out to obtain the TiP with the structure of the micro-flower rice2O7the/C composite material improves the reversibility of the reaction and the coulombic efficiency by adjusting the kind of anions to obtain the TiP with the micron rice flower structure2O7Application of/C composite material to sodium ionsThe battery negative electrode material has excellent electrochemical performance.
The micro-flower structure TiP of the invention2O7the/C composite material and the application thereof in the sodium battery have the following remarkable characteristics:
1. the synthetic method is simple, and crystalline TiP can be obtained by controlling the hydrothermal synthesis reaction time2O7The outside is coated with a thin carbon layer composite material with a micro-flower rice structure, and Ti, P, O and C elements in the composite material are uniformly distributed.
2. TiP of the invention2O7The @ C composite material is of a micro flower-like structure, the flower-like structure is favorable for permeation of electrolyte, and the composite material shows high electrochemical performance when applied to the field of batteries.
3. TiP of the invention2O7The @ C material is applied to the sodium ion battery, and good cycle and rate performance is obtained. At 2.0Ag -110000 cycles, 88% capacity retention rate and 108mAh g-1High capacity, high cycle life, and high volumetric energy density.
Description of the drawings:
FIG. 1 shows Ti (HPO) obtained in step (3) of example 1 of the present invention4)2·xH2Scanning electron microscope photographs of the O precursor; a is reaction for 3 hours, b is reaction for 6 hours, and c is reaction for 12 hours.
FIG. 2 shows a micro-flower structure TiP prepared in example 1 of the present invention2O7A profile of the/C product; a is an XRD diffraction pattern, b is an X-ray photoelectron spectrum of Ti 2p, C is an X-ray photoelectron spectrum of C1s, d is a scanning electron microscope photograph, e is a transmission electron microscope photograph, f is a high-resolution transmission electron microscope photograph, g is a selected area electron diffraction photograph, and h is a high-angle annular dark-field scanning projection microscope and an element distribution diagram.
FIG. 3 shows a micro-flower structure TiP prepared in example 1 of the present invention2O7Analysis chart of electrochemical reaction mechanism of/C product. a is a charge-discharge curve of the first two circles, b is an in-situ XRD diffraction pattern of the first two circles, c is an in-situ XRD diffraction pattern of the first circle, d is a high-resolution transmission electron microscope which discharges to 0.01V and selectionAnd (e) electron diffraction pictures, wherein e is a high-resolution transmission electron microscope charged to 2.5V and a selected electron diffraction picture.
FIG. 4 shows a micro-flower structure TiP prepared in example 1 of the present invention2O7Electrochemical performance of the/C product. a is the charge-discharge curve of the first three circles, b is the sum of TiP2O7Comparison of the cycle performance of c is with TiP2O7And d is long cycle performance.
FIG. 5 shows a micro-flower structure TiP prepared in example 1 of the present invention2O7Kinetic analysis of the/C composite. a is CV curve of different sweep rates, b is the value of charged and discharged b, and c is 2mV s-1The capacitive contribution of time, d is the capacitive contribution at different sweep speeds.
The specific implementation mode is as follows:
the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings and the embodiments, 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.
The raw materials in the examples are all commercial products.
Example 1
Micro-flower structure TiP2O7The preparation method of the/C composite material comprises the following steps:
(1) 0.5ml of TBOT was dispersed in 40ml of ethanol, 0.4ml of PA was added, and the mixture was decomposed with ultrasound.
(2) Transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 12 hours at 200 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, and drying in vacuum drying oven at 60 deg.C for 12 hr to obtain Ti (HPO)4)2·xH2An O precursor;
(4) the precursor is placed in a vacuum drying oven for drying for 12 hours at the temperature of 60 ℃, and the precursor is reacted for 4 hours at the temperature of 800 ℃ under the nitrogen atmosphere. Obtaining TiP2O7@ C material.
Example 2
Micro-flower structure TiP2O7The preparation of the composite material comprises the following steps:
(1) 0.5ml of TBOT was dispersed in 40ml of ethanol, 0.4ml of PA was added, and the mixture was decomposed with ultrasound.
(2) Transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 12 hours at 200 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, and drying in vacuum drying oven at 60 deg.C for 12 hr to obtain Ti (HPO)4)2·xH2An O precursor;
(4) the precursor is reacted for 4 hours at 800 ℃ in the air to obtain TiP2O7A material.
Experimental example:
mechanism of formation of morphology of matter
For Ti (HPO) in example 14)2·xH2The morphology of the O precursor was studied, and as shown in FIG. 1, it can be seen from FIG. 1(a) that the size of the precursor was irregular particles of 50-200nm when the reaction time was 3 hours, and from FIG. 1(b) that the size of the precursor was particles of 200-400nm when the reaction time was 6 hours. As can be seen from fig. 1(c), the size of the precursor is about 2um of micro-flowers when reacting for 12 h. The principle of forming this structure is-H in PA2PO4The group has strong binding energy with Ti atom in TBOT, forms particles and agglomerates in the solvothermal process, and gradually forms Ti (HPO) with a layered structure as the reaction time increases due to Van der Waals force Wald ripening4)2·xH2O and PA play a great role in generating a nano-sheet structure, and finally, the nano-sheet is self-assembled and grows to form Ti (HPO) with a flower-shaped structure4)2·xH2O。
Structural characterization of substances
By comparing TiP in example 12O7The structure of the material @ C was subjected to a series of structural characterization, and as shown in FIG. 2, it was found from the XRD diffraction pattern in FIG. 2(a) that the crystallinity of the material was very good at 800 degrees calcination, and the diffraction peak was attributed to TiP in the cubic phase2O7(JCPDS card, No. 38-1468). But resulted in the masking of the peaks of carbon and we therefore performed a characterization of the X-ray photoelectron spectrum, two peaks in fig. 2(b) being the binding energy of tetravalent titanium, four peaks fitted in fig. 2(c) being carbon bound to different elements, the material having a 2-5um structure of a microwell as seen from the scan in fig. 2(d), the microwell consisting of thin nanosheets as seen from the projection in fig. 2(e), and further, a layer of carbon coated on top of the high resolution projection in fig. 2(f), each diffraction ring corresponding to TiP as seen from the selective electron diffraction in fig. 2(g)2O7In order to see the distribution of the elements, it can be seen from FIG. 2(h) that the elements Ti, P, O and C are distributed very uniformly.
Exploration of electrochemical mechanism of substance
For TiP in example 12O7The electrochemical properties of the material @ C were investigated, and as shown in FIG. 3, FIG. 3(a) is the charge-discharge curve of the first two cycles, and from FIG. 3(b), it can be seen that TiP2O7The XRD diffraction pattern of (1) gradually disappears with the progress of discharge, and does not reappear in the charging process, which shows that TiP2O7Gradually becomes amorphous during the cycle, the curve is enlarged, and it can be seen from FIG. 3(c) that TiP is generated during the discharge2O7The diffraction peak of (A) is shifted to the left firstly, which shows that the intercalation reaction of sodium ions occurs firstly, when the discharge reaches 0.25V, the peak disappears gradually, which shows that the new transformation reaction occurs along with the gradual intercalation of sodium ions, but no Ti simple substance peak is found, which is probably because the generated Ti metal is less and cannot be observed, so that we use a high-resolution transmission electron microscope and select electron diffraction to illustrate the problem, as can be seen from figure 3(d), when the discharge reaches 0.01V, the lattice fringes and diffraction rings of the Ti simple substance can be observed, as can be seen from figure 3(e), when the charge reaches 2.5V, the TiP is observed again2O7Lattice fringes and diffraction rings.
Electrochemical performance test
To verify TiP in example 12O7@ C materialElectrical properties of (2) in TiP2O7The @ C material is the cathode material, and the sodium piece is reference electrode and counter electrode, assembles the sodium ion half-cell, and the representation electrochemical properties, negative pole preparation: TiP2O7Uniformly dispersing the material of @ C, acetylene black and sodium alginate in a proper amount of water, grinding for 30min by hand to prepare pasty slurry, then uniformly coating the slurry on a copper foil, and then drying in vacuum at 60 ℃; rolling the dried copper foil to obtain a negative electrode, using sodium sheet as reference electrode and counter electrode, using Whatman GF/F glass microfiber as diaphragm, and 1.0M NaClO4Dissolution in Propylene Carbonate (PC) as electrolyte was carried out in an argon-filled glove box (Mikrouna, Super 1220/750/900). The charging and discharging test of the battery is carried out on a blue electricity (Land CT-2001A) test system, and the working range of the battery is 0.01-2.5V.
The test results are shown in FIG. 4, and FIG. 4(a) shows the TiP obtained in example 12O7The charging and discharging curves of the first three circles of the sample @ C, FIG. 4(b) is the TiP obtained in example 12O7Sample of @ C and TiP2O7The cycle performance of the polymer is compared, and whether the capacity or the capacity retention rate is the TiP can be seen2O7@ C is superior to TiP2O7. FIG. 4(c) shows TiP obtained in example 12O7Sample of @ C and TiP2O7The multiplying power performance of the titanium alloy is compared, and whether the titanium alloy is high current or low current, the TiP can be seen2O7The capacity and capacity retention rate of @ C are both superior to TiP2O7. FIG. 4(d) shows that the amount of Ag is 2.0Ag-1Has a circulation curve under a large current density of 10000 cycles, also has a capacity retention rate of 88 percent and 108mAh g-1The capacity of (c).
Electrochemical kinetic analysis
To explore the TiP2O7The kinetics of the @ C material, CV curves at different sweep rates were tested, the results of which are shown in FIG. 5, and it can be seen from FIG. 5(a) that as the rate increases, the CV curves substantially retain shape and profile. The b values of the cathodic peak and anodic peak in the logarithmic plot of peak current versus scan rate are 0.89 and 0.92, respectively (fig. 5(b)), indicating an important role for the surface control process. Estimate the surfaceThe capacity contribution of the control process and the diffusion control process. As a result, the concentration of S was 0.1mV-1The surface control process accounted for 60.7% of the total capacity (fig. 5 (d)). However, as the scan rate increased to 2mV s-1This data increased steadily to 89.6% (fig. 5 (c)). Surface control process in sodium storage makes TiP2O7@ C has a higher rate capability.
Comparative example 1
Ti(HPO4)2·xH2The preparation method of the O particles comprises the following steps:
(1) dissolving 0.5ml of TBOT and 0.4ml of PA in 40ml of ethanol, and dissolving under ultrasonic waves;
(2) transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 3 hours at 200 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, and drying in vacuum drying oven at 60 deg.C for 12 hr to obtain Ti (HPO)4)2·xH2O particles, the particles are about 50-200nm, and the dispersion is uneven and the agglomeration phenomenon exists.
Comparative example 2
Ti(HPO4)2·xH2The preparation method of the O particles comprises the following specific steps:
(1) dissolving 0.5ml of TBOT and 0.4ml of PA in 40ml of ethanol, and dissolving under ultrasonic waves;
(2) transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 6 hours at 200 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, and drying in vacuum drying oven at 60 deg.C for 12 hr to obtain Ti (HPO)4)2·xH2O particles, the particles are about 200-400nm, and the dispersion is uneven and the agglomeration phenomenon exists.
As can be seen from comparative examples 1 and 2, no flower-like structure was obtained with a hydrothermal time of less than 6 hours without the participation of PA.

Claims (10)

1. Micro-flower structure TiP2O7a/C composite material, wherein the composite material is crystalline TiP2O7Coating a thin carbon layer with thickness of 1-3nm and micrometer flower knotForm TiP2O7The length of the/C composite material is 2-5 um.
2. Micro-flower structure TiP2O7The preparation method of the/C composite material comprises the following steps:
(1) dispersing a titanium source in a solvent, adding a phosphorus source, heating and dissolving, carrying out hydrothermal reaction at 160-200 ℃ for 8-24h, centrifuging a reaction product, sequentially carrying out ethanol washing and water washing, and then carrying out vacuum drying to obtain a precursor;
(2) the precursor is burned at the high temperature of 600-900 ℃ for 2-6h to obtain the TiP with the structure of the micro-flower rice2O7C or TiP2O7A composite material.
3. The method according to claim 2, wherein the vacuum-dried product is burned at a high temperature under the protection of inert gas to obtain a micro-popcorn structure TiP2O7a/C composite material; the vacuum dried product is burnt in the air at high temperature to obtain the TiP with the structure of the micro-flower rice2O7A composite material.
4. The process according to claim 3, wherein the inert gas is nitrogen, the ignition temperature is 800-900 ℃ and the ignition time is 4-6 hours.
5. The method according to claim 2, wherein in the step (1), the titanium source is tetrabutyl titanate (TBOT) and the phosphorus source is Phytic Acid (PA).
6. The production method according to claim 2, wherein in the step (1), the volume ratio of the titanium source to the solvent is (0.1 to 0.6): 40, the volume ratio of the added titanium source to the phosphorus source is 1 (0.6-1).
7. The preparation method according to claim 2, wherein in the step (1), the solvent is ethanol, the temperature of the hydrothermal reaction is 180-200 ℃, and the reaction time is 10-14 h.
8. The method according to claim 2, wherein in the step (1), the vacuum drying temperature is 50 to 70 ℃ and the drying time is 10 to 14 hours.
9. The micro-flower structure TiP of claim 12O7The application of the/C composite material is applied to a sodium ion battery and used as a negative electrode material of the sodium ion battery.
10. The micro-flower structure TiP of claim 12O7The sodium ion battery of the/C composite material comprises a positive plate, a negative plate, a diaphragm, electrolyte and a shell, wherein the positive plate, the negative plate, the diaphragm, the electrolyte and the shell are obtained by respectively mixing an active material, a conductive agent and a binder, then adding a solvent, grinding into slurry and coating on a current collector; the active material in the sodium ion battery negative plate is a micro-popcorn structure TiP2O7the/C composite material and the sodium sheet are used as a counter electrode.
CN201911420169.1A 2019-12-31 2019-12-31 Micro-flower structure TiP2O7/C composite material and preparation method and application thereof Pending CN111180696A (en)

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