CN108899499B - Sb/Sn phosphate-based negative electrode material, preparation method thereof and application thereof in sodium ion battery - Google Patents
Sb/Sn phosphate-based negative electrode material, preparation method thereof and application thereof in sodium ion battery Download PDFInfo
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Abstract
The invention relates to a cathode material based on Sb/Sn phosphate, a preparation method thereof and application thereof in a sodium ion battery, wherein the Sb-based phosphate cathode material is SbPO4/rGO material, said SbPO4the/rGO material is formed by uniformly growing SbPO on a graphene nano sheet4A nanorod; the negative electrode material based on Sn phosphate is SnP2O7/rGO material, said SnP2O7the/rGO material is formed by uniformly growing SnP on a graphene nano sheet2O7A nanoparticle; the negative electrode material takes the graphene as a substrate material, so that the conductivity is increased, and the charge transmission is facilitated, thereby facilitating the electrochemical property. Has good cycle performance and rate capability. After assembly into a full cell, SbPO4the/rGO material is even at 1.2kW Kg‑1At a power density of up to 99.8Wh Kg‑1The energy density of (1). SnP2O7the/rGO material is 0.049kW Kg‑1The energy density is up to 120.8Wh kg‑1。
Description
The technical field is as follows:
the invention provides a Sb/Sn phosphate-based negative electrode material, a preparation method thereof and application thereof in a sodium ion battery, belonging to the technical field of sodium ion batteries.
Background art:
lithium ion batteries have received much attention as a new type of energy storage equipment. The current commercial lithium ion battery cathode material is graphite, the theoretical specific capacity is low, and the energy density can not meet the requirements of high-power electrical appliances such as electric automobiles and the like. Meanwhile, the lithium resources are deficient and unevenly distributed in the earth, which limits the development of lithium ion batteries in large energy storage devices. In contrast, sodium ion batteries, although having a low energy density, are abundant in nature and chemically similar to lithiumSimilarly, the composition and principle of the sodium ion battery are similar to those of the lithium ion battery, and the sodium ion battery has the advantages of easy purification and the like, and is more and more favored by scientific research workers. But due to the radius of sodium ions
Radius of lithium ion
Large enough to make the deintercalation and transport of sodium ions in the crystal lattice relatively difficult, so that the search for a high-capacity, long-cycle-life, excellent-rate-performance sodium ion anode material remains a challenge at present.
Compared with an anode material (ACS Nano2018,12,1887) of a de-intercalation mechanism, the anode material of an alloy mechanism has higher theoretical specific capacity and safety performance; the anode material of the alloy mechanism has a lower electrochemical potential (nanolett.2012,12,3783) relative to the anode material of the conversion mechanism (Nano Energy 2016,19,279), and thus has a higher Energy density and power density when the full cell is assembled. Is a sodium electric anode material with great application potential. They also have their own drawbacks, such as greater volume expansion during sodium intercalation, resulting in a more collapsible structure and thus poor cycling stability. Modification of the anode material for alloying mechanisms is the focus and difficulty of current research (sci. rep.2015,5,8418).
Compared with cathode materials such as P, Si and the like (adv. energy mater.2017,8,1701827) based on an alloy mechanism, the cathode materials based on Sb and Sn have higher conductivity and small polarization voltage, and therefore, good rate performance can be shown. However, Sb and Sn oxides and sulfides, Na being a product during charge and discharge thereof2O and Na2S is poorly conductive and these intermediates are soluble in the electrolyte, resulting in poor cycling and rate performance (adv. funct. mater.2015,25,214). Thus, phosphate compounds of Sb and Sn have attracted our attention, with the following main advantages: first, they all have good electrochemical activity and are safe and non-toxic green materials (chem. mater.2015,27,6668). Second, during the charging and discharging processIntermediate product Na of (2)3PO4As an ion conductor, can relieve the volume expansion effect and Na in the circulation process+The diffusion resistance of the electrolyte is beneficial to the exertion of the electrochemical performance of the electrolyte (Phys. Rev. B2004, 70, 064302). Third, the phosphate can form three-dimensional electronic channels during the reaction process, greatly improving the reaction efficiency (J.Power Sources 2016,331, 16). In conclusion, the research on Sb and Sn phosphates is very meaningful.
The invention content is as follows:
aiming at the defects of the prior art, the invention provides an Sb/Sn phosphate-based negative electrode material, a preparation method thereof and application thereof in a sodium-ion battery.
SbPO4Is a material with a layered structure, and has a large interlayer spacing
Is favorable to Na+Thereby enhancing the kinetics of the reaction. SnP2O7Is a cubic structure, SbPO4Or SnP2O7The graphene shows excellent electrochemical performance after being compounded with graphene, and has high capacity retention rate no matter after being cycled for 1000 circles or charged and discharged under high current density. The lithium ion battery has stable cycle performance and high energy and power density when applied to a sodium ion battery.
The technical scheme of the invention is as follows:
an Sb/Sn phosphate-based negative electrode material, wherein the Sb-based phosphate negative electrode material is SbPO4/rGO material, said SbPO4the/rGO material is formed by uniformly growing SbPO on a graphene nano sheet4A nanorod; the negative electrode material based on Sn phosphate is SnP2O7/rGO material, said SnP2O7the/rGO material is formed by uniformly growing SnP on a graphene nano sheet2O7A nanoparticle; the content of graphene in the Sb/Sn phosphate-based negative electrode material is 12-18%.
Preferred according to the invention are SbPO4The length of the nano rod is 90-120nm, SnP2O7The particle size of the nano-particles is 40-60 nm.
According to the invention, the preparation method of the Sb/Sn phosphate-based negative electrode material comprises the following steps:
(1) dispersing graphene in a solvent, adding an antimony source or a tin source and a phosphorus source, heating and dissolving, carrying out hydrothermal reaction at the temperature of 100-120 ℃ for 4-6 hours,
(2) and (2) centrifuging the reaction product obtained in the step (1), sequentially washing with ethanol and water, then drying in vacuum, and finally firing at a high temperature of 400-550 ℃ for 4-6h under the protection of inert gas to obtain the Sb/Sn phosphate-based negative electrode material.
Preferably, in step (1), the antimony source is SbCl3The tin source is SnCl4·5H2O。
According to the invention, in step (1), the phosphorus source is NH4H2PO4。
According to the invention, in the step (1), the ratio of the addition amount of the antimony source or the tin source to the molar amount of the phosphorus source is 1 (1-3).
Preferably, in step (1), the solvent is ethylene glycol.
According to the present invention, in step (1), the mass-to-volume ratio of the added amount of graphene to the solvent is: (4-7): (3-5), unit, mg/mL, and the mass ratio of the graphene to the antimony source or the tin source is as follows: 40-70 mg: 0.5-2 mmol.
Preferably, in step (1), the hydrothermal reaction temperature is 110-130 ℃ and the reaction time is 3-6 h.
According to the invention, in the step (2), the vacuum drying temperature is 50-70 ℃, the drying time is 10-14h, the inert gas is a mixed gas of hydrogen and argon, and the volume ratio of the hydrogen to the argon is 95:5
According to the optimization of the invention, in the step (2), the burning temperature is 400 ℃ and the burning time is 2h when the antimony source is used; when the tin source is used, the burning temperature is 550 ℃, and the burning time is 6 hours.
The application of the Sb/Sn phosphate-based negative electrode material is applied to a sodium ion battery and used as a negative electrode material of the sodium ion battery.
According to the preferable sodium ion battery taking the Sb/Sn phosphate-based negative electrode material as the negative electrode material, the sodium ion battery comprises a positive electrode plate, a negative electrode plate, a diaphragm, electrolyte and a shell, wherein the negative electrode plate and the positive electrode plate 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 negative plate of the sodium ion battery is Sb/Sn phosphate, and the active material in the positive plate is Na3V2(PO4)3/C。
According to the invention, the negative plate is prepared by the following method: mixing Sb/Sn phosphate, a conductive agent and a binder according to a mass ratio of 7:2:1, adding azomethylpyrrolidone, grinding into slurry, coating the slurry on a copper foil, drying the slurry in vacuum at 60 ℃, rolling the dried slurry, and cutting the dried slurry into pole pieces, wherein the mass of an active material on a unit area is 1.0-1.5 mg cm-2。
According to the invention, the positive plate is preferably prepared by the following method: mixing Na3V2(PO4)3Mixing the conductive agent and the binder according to the mass ratio of 8:1:1, adding the azomethine pyrrolidone, grinding into slurry, coating on an aluminum foil, drying in vacuum at 60 ℃ after coating, rolling after drying, and cutting to prepare the positive plate.
According to the invention, the mass ratio of the active material in the positive plate to the active material in the negative plate is preferably controlled to be 1: 1.2.
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 respectively obtains SbPO by taking an antimony source or a tin source, a phosphorus source and GO as raw materials and ethylene glycol as a solvent through solvothermal reaction and high-temperature sintering4rGO material, SnP2O7the/rGO material takes graphene as a substrate, so that the conductivity of the material is greatly increased, the transmission of electrons is facilitated, and meanwhile, functional groups on the graphene and SbPO are4Or SnP2O7The interaction between the two can prevent the pulverization of particles in the circulation process, thereby improving the electrochemical performance.
The ionic cell cathode material has the following remarkable characteristics:
(1) the sodium ion negative electrode material SbPO of the invention4rGO material, SnP2O7the/rGO material adopts graphene as a substrate material, improves the conductivity of the material, is favorable for charge transmission, and has functional groups and SbPO on the graphene4Or SnP2O7The interaction between the electrode materials can prevent the pulverization of the electrode material particles, thereby improving the electrochemical performance.
(2) The cathode material SbPO of the invention4/rGO material or SnP2O7SbPO on/rGO material4Or SnP2O7All the nano particles can reduce the diffusion path of sodium ions and improve the reaction kinetics, thereby bringing about good cycle performance and rate capability. For SbPO4/rGO material at 1Ag-1The current density of the current is 100mAh g after 1000 cycles-1Left and right capacity. For SnP2O7/rGO material at 1Ag-1The current density of the current is 150mAh g after 1000 cycles-1Left and right capacity.
(3) SbPO of the invention4/rGO material or SnP2O7on/rGO material, in-situ and ex-situ means are used to separately align SbPO4Expansion mechanism of nano rod in sodium intercalation process and SbPO4/rGO or SnP2O7The electrochemical reaction mechanism of/rGO is deeply researched. SbPO4Is a layered structure, the direction between layers is exactly the radial direction of the nano-rod, so when sodium ions are intercalated, the sodium ions are inserted between the layers, and the expansion of the nano-rod is also carried out along the radial direction. SbPO4The reaction mechanism of/rGO is tested in the voltage range of 0.01-1.5V, and the discharge process is SbPO4Followed by an alloying reaction of Sb and the charging process is a dealloying process of Sb. SnP2O7The reaction mechanism of/rGO is in the voltage range of 0.01-25V test, discharge first SnP2O7Followed by an alloying reaction of Sn, and the charging process is a dealloying of Sn, followed by an oxidation process of Sn. But the whole process is partially reversible and also coincides with the following electrochemical cycle.
(4) SbPO of the invention4/rGO or SnP2O7the/rGO material has good semi-electric performance, and after the material is fully assembled by a battery, the SbPO4the/rGO material is even at 1.2kW Kg-1At a power density of up to 99.8Wh Kg-1The energy density of (1). SnP2O7the/rGO material is 0.049kW Kg-1The energy density is up to 120.8Wh kg-1。
Description of the drawings:
FIG. 1 shows SbPO obtained in example 1 of the present invention4/rGO (a) and SnP2O7XRD diffraction pattern of/rGO (b) material.
FIG. 2 shows SbPO obtained in example 1 of the present invention4/rGO (a) and SnP2O7SEM pictures of/rGO (b) material.
FIG. 3 shows SbPO prepared in example 1 of the present invention4/rGO (a) and SnP2O7Elemental distribution photographs of/rgo (b) material.
FIG. 4 shows SbPO4/rGO (a) and SnP prepared in example 1 of the present invention2O7Graph comparing the cycling performance of/rgo (b) material in a sodium ion half cell.
FIG. 5 shows SbPO prepared in example 1 of the present invention4/rGO (a) and SnP2O7Comparison graph of cycle performance of/rgo (c) material in sodium ion full cell. SbPO4/rGO (b) and SnP2O7(d) power energy density plot.
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
SbPO4Preparation of/rGO material, the steps are as follows:
(1) 50mgGO was dispersed in 40ml of ethylene glycol and 1mmol of SbCl was added32mmol of ammonium dihydrogen phosphate, and dissolving at 70 ℃.
(2) Transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 4 hours at 120 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, drying in a vacuum drying oven at 60 deg.C for 12h, and reacting at 400 deg.C for 2h under argon-hydrogen atmosphere. To obtain SbPO4/rGO。
SnP2O7Preparation of rGO, the steps are as follows:
(1) 50mgGO was dispersed in 40ml of ethylene glycol and 1mmol SnCl was added4·5H2O, 2mmol ammonium dihydrogen phosphate, and dissolving at 70 deg.C.
(2) Transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 4 hours at 120 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, drying in a vacuum drying oven at 60 deg.C for 12h, and reacting at 550 deg.C for 6h under argon-hydrogen atmosphere. Obtaining SnP2O7/rGO。
Performance testing
To SbPO4rGO and SnP2O7The XRD pattern of/rGO is shown in figure 1, and all the diffraction peaks can be seen in figure 1 (a) to correspond to XRD standard card JCPDS No.29-1352, and in figure 1 (b) to correspond to XRD standard card JCPDS No. 35-0829. However, SbPO due to bad crystallinity of rGO4And SnP2O7The peaks of (a) mask the diffraction peaks of rGO. For the SbPO obtained4rGO and SnP2O7the/rGO sample material is analyzed by scanning electron microscope, the scanning electron microscope photo is shown as figure 2, and SbPO can be seen from (a) in figure 24the/rGO samples were grown uniformlySbPO on graphene nanoplatelets4And (4) nanorods. As can be seen in FIG. 2 (b), SnP2O7the/rGO sample is SnP uniformly grown on graphene nanosheets2O7And (3) nanoparticles. For the SbPO obtained4rGO and SnP2O7High resolution transmission electron micrographs of/rGO sample material clearly show very uniform elemental distribution in fig. 3 (a) and fig. 3 (b).
Electrochemical performance test
And (3) testing the performance of the sodium ion half cell:
to verify SbPO4rGO and SnP2O7Electrical properties of/rGO material, in SbPO4/rGO or SnP2O7the/rGO material is a negative electrode material, the sodium sheet is a reference electrode and a counter electrode, a sodium ion half-cell is assembled, the electrochemical performance is represented, and the negative electrode is prepared: SbPO4rGO and SnP2O7Uniformly dispersing the rGO material, acetylene black and sodium alginate in a proper amount of water, grinding for 30min by hand to prepare paste 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 an 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 0.01-1.5V and 0.01-2.5V. FIG. 4 (a) shows SbPO obtained in example 14the/rGO sample and the comparative material SbPO4 are 1Ag-1The cycle curve at a large current density of (A), and (b) in FIG. 4 is SnP obtained in example 12O7the/rGO sample is 1Ag-1And 2Ag-1The cycle curve at a high current density. As can be seen in FIG. 4, SbPO4rGO and SnP2O7the/rGO samples all showed good cycling performance.
And (3) testing the performance of the sodium ion full battery:
FIG. 5 is a graph of full electrical performance, SbPO4/rGO (a) and SnP2O7Cycle profile after assembly of a full cell. From the figure, SbPO can be seen4rGO and SnP2O7the/rGO has a smooth cycling behavior after assembly of the full cell. SbPO4/rGO (b) and SnP2O7/rgo (d) is the power density and energy density plot. SbPO4the/rGO material is even at 1.2kW Kg-1At a power density of up to 99.8Wh Kg-1The energy density of (1). SnP2O7the/rGO material is 0.049kW Kg-1The energy density is up to 120.8Wh kg-1。
Comparative example 1
SbPO4The preparation method of the material comprises the following steps:
(1) dissolving 1mmol of antimony potassium tartrate and 2mmol of ammonium dihydrogen phosphate at 70 ℃;
(2) transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 4 hours at 120 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, drying in a vacuum drying oven at 60 deg.C for 12h, and reacting at 400 deg.C under argon-hydrogen atmosphere for 2h to obtain SbPO4The microspheres have the size, are not uniformly dispersed and have slight agglomeration. Adversely affecting its electrochemical properties.
Comparative example 2
SbPO4The preparation method of/rGO comprises the following specific steps:
(1) dispersing 50mgGO in 40ml of ethylene glycol, adding 1mmol of antimony potassium tartrate and 2mmol of ammonium dihydrogen phosphate, and dissolving at 70 ℃;
(2) transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 4 hours at 120 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, drying in a vacuum drying oven at 60 deg.C for 12h, and reacting at 400 deg.C under argon-hydrogen atmosphere for 2h to obtain SbPO4(ii)/rGO; the comparative example is obtained by taking potassium antimony tartrate as an antimony source and ammonium dihydrogen phosphate as raw materials and ethylene glycol as a solvent through solvothermal reaction and high-temperature sintering, the obtained material has an irregular micron composite, the antimony phosphate and the graphene are not well compounded together, the conductivity is poor,is not favorable for the transmission of electrons, thereby exhibiting poor cycle performance.
Comparative example 3
SbPO4The preparation method of/rGO comprises the following specific steps:
(1) 50mgGO was dispersed in 40ml of ethylene glycol and 1mmol of SbCl was added32mmol of ammonium dihydrogen phosphate, and dissolving at 70 ℃;
(2) transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 4 hours at 120 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, drying in a vacuum drying oven at 60 deg.C for 12h, and reacting at 400 deg.C under argon atmosphere for 2h to obtain SbPO4/rGO。
The comparative example is that the graphene is burned in an argon atmosphere, and the reduction degree of the graphene is directly influenced by the burning atmosphere, so that the electrochemical property is directly influenced.
Comparative example 4
SnP2O7The preparation method of/rGO comprises the following specific steps:
(1) 50mgGO was dispersed in 40ml of ethylene glycol and 1mmol SnCl was added4·5H2O, 2mmol ammonium dihydrogen phosphate, and dissolving at 70 deg.C;
(2) transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 4 hours at 120 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, drying in a vacuum drying oven at 60 deg.C for 12h, and reacting at 400 deg.C for 2h under argon-hydrogen atmosphere.
The comparative example is SnP obtained by burning at 400 DEG C2O7/rGO，SnP2O7the/rGO crystallinity is very poor and thus shows poor cyclability and rate capability in electrochemical properties.
Claims (7)
1. An Sb/Sn phosphate-based negative electrode material, wherein the Sb-based phosphate negative electrode material is SbPO4/rGO material, said SbPO4the/rGO material is formed by uniformly growing SbPO on a graphene nano sheet4A nanorod; the negative electrode material based on Sn phosphate is SnP2O7/rGO material, saidSnP2O7the/rGO material is formed by uniformly growing SnP on a graphene nano sheet2O7A nanoparticle; the content of graphene in the Sb/Sn phosphate-based negative electrode material is 12-18%; SbPO4The length of the nano rod is 90-120nm, SnP2O7The particle size of the nano particles is 40-60 nm;
the preparation method of the Sb/Sn phosphate-based negative electrode material comprises the following steps:
(1) dispersing graphene in a solvent, adding an antimony source or a tin source and a phosphorus source, heating and dissolving, and carrying out hydrothermal reaction at the temperature of 110-130 ℃ for 3-6 hours, wherein the ratio of the addition amount of the antimony source or the tin source to the molar amount of the phosphorus source is 1 (1-3), and the solvent is ethylene glycol; the mass-volume ratio of the added amount of the graphene to the solvent is as follows: (4-7): (3-5), unit, mg/mL, and the mass ratio of the graphene to the antimony source or the tin source is as follows: 40-70 mg: 0.5-2 mmol;
(2) and (2) centrifuging the reaction product obtained in the step (1), sequentially washing with ethanol and water, then drying in vacuum, and finally firing at a high temperature of 400-550 ℃ for 4-6h under the protection of inert gas to obtain the Sb/Sn phosphate-based negative electrode material.
2. The Sb/Sn phosphate-based negative electrode material of claim 1, wherein in the step (1), the antimony source is SbCl3The tin source is SnCl4∙5H2O; the phosphorus source is NH4H2PO4。
3. The Sb/Sn phosphate-based negative electrode material according to claim 1, wherein in the step (2), the vacuum drying temperature is 50-70 ℃ and the drying time is 10-14 h.
4. The Sb/Sn phosphate-based negative electrode material of claim 1, wherein in the step (2), the burning temperature of the antimony source is 400 ℃ and the burning time is 2 h; when the tin source is used, the burning temperature is 550 ℃, and the burning time is 6 hours.
5. The use of the Sb/Sn phosphate-based negative electrode material of claim 1 in a sodium ion battery as a negative electrode material for a sodium ion battery.
6. The application of the sodium-ion battery as claimed in claim 5, wherein the sodium-ion battery comprises a positive plate, a negative plate, a diaphragm, electrolyte and a shell, wherein the negative plate and the positive plate 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 negative plate of the sodium ion battery is Sb/Sn phosphate, and the active material in the positive plate is Na3V2(PO4)3/C。
7. The use according to claim 6, wherein the mass ratio of the active material in the positive electrode sheet to the active material in the negative electrode sheet is controlled to be 1: 1.2.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810687557.5A CN108899499B (en) | 2018-06-28 | 2018-06-28 | Sb/Sn phosphate-based negative electrode material, preparation method thereof and application thereof in sodium ion battery |
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| Publication Number | Publication Date |
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| CN104183848A (en) * | 2014-08-26 | 2014-12-03 | 南昌航空大学 | Graphene/nickel sulphide nano composite electrode material and preparation method thereof |
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| CN104183848A (en) * | 2014-08-26 | 2014-12-03 | 南昌航空大学 | Graphene/nickel sulphide nano composite electrode material and preparation method thereof |
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| CN106185858A (en) * | 2016-07-26 | 2016-12-07 | 南京信息工程大学 | The simple method for preparing of a kind of uniform phosphoric acid antimony micron bar and photocatalysis performance thereof |
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