CN113851638B - SnO (stannic oxide) 2-x Preparation method and application thereof, and composite electrode - Google Patents
SnO (stannic oxide) 2-x Preparation method and application thereof, and composite electrode Download PDFInfo
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Abstract
The invention discloses SnO 2‑x A preparation method and application thereof, and a composite electrode. The SnO 2‑x The preparation method comprises the following steps: spraying and pyrolyzing the mixed solution by flame to obtain the composite material; wherein the mixed solution comprises a tin source, a surfactant, an organic solvent and water. SnO of the present invention 2‑x The preparation method has short reaction time, and the obtained SnO 2‑x The oxygen vacancy concentration is higher and controllable within a certain range, and is made of SnO 2‑x The prepared electrode has excellent electrical properties and SnO 2‑x The composite electrode prepared by the additive has excellent electrical properties.
Description
Technical Field
The invention relates to SnO 2-x A preparation method and application thereof, and a composite electrode.
Background
The negative electrode of the lithium ion battery material is mainly made of graphite material, and the most successful reason is the stable lithium storage mechanism and performance, but the low reversible capacity of the graphite material becomes a main factor for limiting the development of the lithium ion battery due to the requirement on the energy density of the lithium ion battery. SnO 2 The material becomes one of the candidates of the next generation of negative electrode material due to its ultra-high reversible lithium storage reaction. But has poor cycle performance due to its low electrical conductivity and near 300% volume expansion by the conversion and alloying reaction mechanisms. Recently, materials rich in oxygen vacancies have brought a huge improvement in electrical properties due to their effects on intrinsic conductivity, snO 2-x A new material that becomes a high-capacity negative electrode material having excellent stability is one of strong competitors to further improve the energy density of lithium ion batteries. On the other hand, nanocrystallization has the ability to buffer large stress strain, thereby reducing the influence of volume expansion and shortening the transmission path of lithium ions and electrons, and has become a research hotspot in recent years.
Patent document CN106268750A discloses a visible light-responsive photoreduction-active SnO 2-x Method for preparing nanoparticles, snO obtained by the preparation thereof 2-x However, the concentration of oxygen vacancies obtained by preparing the nano particles is low, the prepared electrode cannot achieve good effect, the reaction time needs 20 to 27 hours, and the reaction time is too long, so that the industrial production is not facilitated.
In the prior art, most of the research has focused on SnO 2-x Prepared into cathode materials without containing SnO 2-x The composite electrode of (4) was studied.
The above studies indicate that SnO with higher oxygen vacancy concentration can be rapidly prepared 2-x Nanoparticles have a profound impact on the development of lithium ion batteries.
Disclosure of Invention
The technical problem to be solved by the invention is SnO in the prior art 2-x The preparation method has the defects of low oxygen vacancy concentration and low reaction rate, and provides SnO 2-x A preparation method and application thereof, and a composite electrode. SnO of the present invention 2-x The preparation method has short reaction time, and the obtained SnO 2-x The oxygen vacancy concentration is higher and is controllable within a certain range, and is made of SnO 2-x The prepared electrode has excellent electrical properties and SnO 2-x The composite electrode prepared by the additive has excellent electrical properties.
The invention solves the technical problems through the following technical scheme.
The invention provides SnO 2-x Said SnO 2-x 3d of medium Sn element 3/2 The bonding energy of the orbitals is 486.3-486.8eV, and the bonding energy of Sn element is 3d 5/2 The binding energy of the orbitals is 494.7-495.2 eV.
The invention also provides SnO 2-x The preparation method comprises the following steps:
spraying and pyrolyzing the mixed solution by flame to obtain the composite material;
wherein the mixed solution comprises a tin source, a surfactant, an organic solvent and water.
In the flame spray pyrolysis, after the mixed solution is atomized and undergoes a series of reactions such as combustion, explosion, hydrolysis, sintering and the like, a vacuum pump brings product particles to a glass fiber filter membrane of a collector along with airflow, and the product particles are deposited to obtain SnO 2-x And (3) nanoparticles.
In the present invention, preferably, the flame spray pyrolysis includes atomizing the mixed solution to obtain liquid droplets.
Wherein, preferably, the size of the liquid drop is 5-20 microns.
Wherein, preferably, the liquid drops are obtained by subjecting the mixed solution to gas shearing.
Preferably, the gas is O 2 。
Preferably, the shearing pressure generated by the gas is 0.1-0.3 MPa.
Preferably, the feeding speed of the mixed solution during the atomization is 2-10 mL/min, such as 5mL/min.
Preferably, the mixed solution is fed by a syringe pump or a continuous syringe pump during atomization, for example, a peristaltic syringe pump can be used.
In the present invention, the flame for flame spray pyrolysis is generally obtained by burning an oxygen-containing gas.
Wherein, preferably, the oxygen-containing gas is H 2 And O 2 The mixed gas of (3); more preferably, in the oxygen-containing gas, H 2 The flow rate of (A) is 0.08-2 m 3 H, e.g. 0.15m 3 /h，O 2 The flow rate of (A) is 0.5 to 1.2m 3 H is, for example, 1m 3 /h。
In the present invention, preferably, in the flame spray pyrolysis, the temperature of the combustion flame region is 800 to 1500 ℃.
In the present invention, the tin source may be an organic and/or inorganic substance capable of providing tin element, which is conventional in the art, preferably one or more of tin tetrachloride, stannous octoate, tetrabutyltin and tin dichloride, and more preferably tin tetrachloride.
In the present invention, preferably, the surfactant is one or more of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone and tween.
In the present invention, the molar ratio of the tin source to the surfactant is 3 to 10, for example, 2.
In the present invention, the organic solvent may be an organic solvent conventional in the art, and preferably one or more of ethanol, toluene, xylene, and propionic acid.
In the present invention, the volume ratio of the organic solvent to the water is preferably 1.
In the present invention, preferably, the mixed solution is obtained by mixing and stirring the tin source, the surfactant, the organic solvent, and the water, and the stirring time is preferably 3 to 6 hours, for example, 5 hours.
In the present invention, preferably, in the mixed solution, a ratio of the total number of moles of the tin source and the surfactant to the volume of the organic solvent is 0.1 to 1mol/L, for example, 0.43mol/L, 0.67mol/L, or 0.83mol/L.
The invention also provides SnO 2-x Consisting of SnO as previously described 2-x The preparation method.
In the present invention, preferably, the SnO 2-x The particle diameter of (A) is 5-20 nm.
In the present invention, preferably, the SnO 2-x Has a specific surface area of 100 to 130m 2 /g。
In the present invention, preferably, the SnO 2-x Is in rutile phase.
In the present invention, preferably, the SnO 2-x The intensity of the electron paramagnetic resonance spectrum (EPR) of (1) is 2000 or more, preferably 2014.8 to 3464.8. The SnO can be judged by electron paramagnetic resonance spectrum (EPR) intensity 2-x The concentration of oxygen vacancies. As will be appreciated by those skilled in the art, the higher the EPR peak intensity, the SnO 2-x The higher the oxygen vacancy concentration of (a). Those skilled in the art also know that when judging the oxygen vacancy intensity from the EPR map, it is generally necessary to make a judgment based on the test results of the same inspection machine.
In the present invention, preferably, the SnO 2-x 3d of medium Sn element 3/2 The bonding energy of the orbitals is 486.3-486.8eV, and the bonding energy of Sn element is 3d 5/2 The binding energy of the orbit is 494.7-495.2 eV. As known to those skilled in the art, the SnO 2-x The binding energy of the 3d orbital in the medium Sn element can be obtained by X-ray photoelectron spectroscopy (XPS) test, and the SnO can be 2-x X-ray photoelectron spectroscopy (XPS) and SnO 2 Comparing the XPS spectra, and judging the deviation amount of the peak position, wherein the more the deviation amount is, the SnO 2-x The higher the oxygen vacancy concentration in (b). It is also known to those skilled in the art that when judging the oxygen vacancy concentration from the XPS spectrum, it is generally necessary to make a judgment based on the test results of the same detection machine.
The invention also provides SnO 2-x A method of making an electrode comprising the steps of:
coating the first mixed slurry on the surface of a substrate material and then heating;
wherein the first mixed slurry comprisesSnO as previously described 2-x Conductive agent, binder and solvent;
the SnO 2-x Said SnO 2-x The total amount of the conductive agent and the binder is 70% by mass or more and not 100%.
In the present invention, the substrate may be an electrode substrate conventional in the art, and preferably, is a copper foil or an aluminum foil.
In the present invention, preferably, the SnO 2-x Said SnO 2-x The total amount of the conductive agent and the binder is 70 to 80 mass%, and more preferably 70 mass%.
In the present invention, the kind of the conductive agent may be conventional in the art, and preferably one or more of ketjen black, conductive carbon black and acetylene black.
In the present invention, preferably, the conductive agent is in the SnO 2-x The total amount of the conductive agent and the binder is 30% by mass or less and is not 0, more preferably 20% by mass or less, and still more preferably 20% by mass.
In the present invention, the kind of the binder may be conventional in the art, and preferably polyvinylidene fluoride (PVDF) and/or carboxymethyl cellulose.
In the present invention, the binder is in the SnO 2-x The total amount of the conductive agent and the binder is 20% by mass or less and is not 0, more preferably 10% by mass or less, and still more preferably 10% by mass.
In the present invention, the kind of the solvent may be conventional in the art, and preferably N-methylpyrrolidone (NMP).
In the present invention, preferably, the SnO 2-x The mass ratio to the solvent is 1 to 7, for example, 7.
In the present invention, preferably, the SnO 2-x : the conductive agent: the mass ratio of the binder is 7.
In the present invention, the operation and parameters of the heating may be conventional in the art, and the heating is generally continued until the first mixed slurry is dried.
Wherein, the heating temperature is preferably 130-150 ℃, for example 120 ℃.
Among them, the heating time is preferably 10 to 15 hours, for example, 12 hours.
Wherein, preferably, the heating is performed under vacuum condition.
The invention also provides SnO 2-x Electrodes made of SnO as described previously 2-x The preparation method of the electrode.
The invention also provides a preparation method of the composite electrode, which comprises the following steps:
coating the second mixed slurry on the surface of the substrate material and then heating;
wherein the second mixed slurry comprises SnO as described above 2-x Graphite, a conductive agent, a binder and a solvent;
the SnO 2-x Said SnO 2-x And the total amount of the graphite, the conductive agent, and the binder is 32% by mass or less and is not 0.
In the present invention, the substrate may be an electrode substrate conventional in the art, and preferably, is a copper foil or an aluminum foil.
In the present invention, preferably, the SnO 2-x Said SnO 2-x 16 to 32 percent of the total amount of the graphite, the conductive agent and the binder.
In the present invention, the graphite may be commercially available graphite.
In the present invention, preferably, the graphite occupies the SnO 2-x The total amount of the graphite, the conductive agent and the binder is 64% by mass or more and is not 100%, and more preferably 48% to 64%.
In the present invention, the kind of the conductive agent may be conventional in the art, and preferably one or more of ketjen black, conductive carbon black and acetylene black.
In the present invention, preferably, the conductive agent is in the SnO 2-x The total amount of the graphite, the conductive agent and the binder is in mass percentThe ratio is 20% or less, is not 0, is more preferably 10% or less, for example, 10%.
In the present invention, the binder may be of a kind conventional in the art, and preferably polyvinylidene fluoride and/or carboxymethyl cellulose.
In the present invention, the binder is in the SnO 2-x The total amount of the graphite, the conductive agent, and the binder is 20% by mass or less and is not 0, more preferably 10% by mass or less, and still more preferably 10% by mass.
In the present invention, the kind of the solvent may be conventional in the art, and preferably N-methylpyrrolidone (NMP).
In the present invention, preferably, the SnO 2-x The mass ratio to the solvent is 1 to 7, for example, 7.
In the present invention, preferably, the SnO 2-x : the graphite: the conductive agent: the mass ratio of the binder is 16.
In the present invention, the operation and parameters of the heating may be conventional in the art, and the heating is generally continued until the first mixed slurry is dried.
Wherein, the heating temperature is preferably 130-150 ℃, for example, 120 ℃.
Among them, the heating time is preferably 10 to 15 hours, for example, 12 hours.
Wherein, preferably, the heating is performed under vacuum condition.
The invention also provides a composite electrode, which is prepared by the preparation method of the composite electrode.
The invention also provides SnO as mentioned above 2-x Use of an electrode or a composite electrode as hereinbefore described in a lithium ion battery.
The invention also provides a lithium ion battery which comprises the SnO 2-x An electrode or a composite electrode as previously described.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
SnO of the present invention 2-x The preparation method has short reaction time, and the obtained SnO 2-x The oxygen vacancy concentration is higher and is controllable within a certain range, and is made of SnO 2-x The prepared electrode has excellent rate performance and SnO 2-x The composite electrode prepared by the additive has excellent rate capability, reversible capacity and cycle performance.
Drawings
FIG. 1 is SnO of example 1 2-x Transmission electron micrograph (c).
FIG. 2 is SnO of examples 1 to 3 2-x XRD profile of (a).
FIG. 3 shows SnO of examples 1 to 3 2-x EPR curve of (1).
FIG. 4 is SnO of examples 1 to 3 2-x XPS curve of (2).
FIG. 5 is a graph of rate capability of the electrodes of example 3-1, example 3-2, and comparative example 1.
Fig. 6 is a graph of rate performance of the electrodes of examples 1 to 3 and comparative example 2.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples and comparative examples, polyethylene glycol was obtained from Shanghai Linfeng Chemicals, inc., and Ketjen Black and PVDF were obtained from Synfei Kejing materials, inc.
Example 1
(1) Preparing a mixed solution: weighing 0.02mol of stannic chloride, dissolving in a mixed solvent of 35mL of ethanol and 25mL of deionized water, adding 0.006mol of polyethylene glycol, mixing, and stirring for 5 hours to obtain a mixed solution for later use;
(2) The mixed solution is mixed by a peristaltic injection pump according to the volume of 5mL/minThe feed rate of (a) is such that fine droplets of about 13 microns are formed by the atomizing burner and fed into the spray combustion reactor with a shear gas of O 2 The resulting shear pressure was 0.1MPa. Atomized droplets in H 2 /O 2 Mixed gas (H) of (2) 2 At a flow rate of 0.15m 3 /h，O 2 Has a flow rate of 1m 3 With the assistance of/h), after a series of reactions such as combustion, explosion, hydrolysis, sintering and the like occur in flame at about 1200 ℃, a vacuum pump drives airflow to drive particles, and SnO is obtained by deposition on a glass fiber filter membrane of a collector 2-x ，SnO 2-x Has an average particle diameter of 13nm and a specific surface area of 104.8m 2 /g；
(3)SnO 2-x Preparing an electrode: snO is treated 2-x Grinding with Ketjen black, adding into slurry containing PVDF and NMP, snO 2-x : ketjen black: the mass ratio of PVDF is 7 2-x The mass ratio of (1) to (9) is 7. Pouring the first mixed slurry on a copper foil, and drying the copper foil in a vacuum oven at 120 ℃ for 12h to obtain SnO 2-x And an electrode.
SnO of example 1 2-x Transmission electron microscopy was performed with a ThermoFisher Talos F200X transmission electron microscopy, the results are shown in FIG. 1.
Example 2
(1) Preparing a mixed solution: weighing 0.02mol of stannic chloride, dissolving the stannic chloride in a mixed solvent of 30mL of ethanol and 30mL of deionized water, adding 0.02mol of polyethylene glycol, mixing, and stirring for 5 hours to obtain a mixed solution for later use;
(2) Feeding the mixed solution into a spray combustion reactor at a feeding rate of 5mL/min by using a peristaltic injection pump, forming fine liquid drops with the size of 13 microns by using an atomizing burner, and feeding the liquid drops into the spray combustion reactor with a shearing gas of O 2 The resulting shear pressure was 0.1MPa. Atomized droplets in H 2 /O 2 Mixed gas (H) of (2) 2 Has a flow rate of 0.15m 3 /h，O 2 Has a flow rate of 1m 3 With the assistance of/h), after a series of reactions such as combustion, explosion, hydrolysis, sintering and the like occur in flame at about 1200 ℃, the vacuum pump drives the airflow to drive particles, and the glass fiber of the collectorDeposition on a filter to obtain SnO 2-x ，SnO 2-x Has an average particle diameter of 18nm and a specific surface area of 120.3m 2 /g；
(3)SnO 2-x Preparing an electrode: snO 2-x Grinding with Ketjen black, adding into slurry containing PVDF and NMP, snO 2-x : keqin black: the mass ratio of PVDF is 7 2-x The mass ratio of (1) to (2) is 7. Pouring the first mixed slurry on a copper foil, and drying the copper foil in a vacuum oven at 120 ℃ for 12h to obtain SnO 2-x And an electrode.
Example 3
(1) Preparing a mixed solution: weighing 0.02mol of stannic chloride, dissolving in a mixed solvent of 40mL of ethanol and 25mL of deionized water, adding 0.03mol of polyethylene glycol, mixing, and stirring for 5 hours to obtain a mixed solution for later use;
(2) Feeding the mixed solution into a spray combustion reactor at a feeding rate of 5mL/min by using a peristaltic injection pump, forming fine liquid drops with the size of 13 microns by using an atomizing burner, and feeding the liquid drops into the spray combustion reactor with a shearing gas of O 2 The resulting shear pressure was 0.1MPa. Atomized droplets in H 2 /O 2 Mixed gas (H) of (2) 2 At a flow rate of 0.15m 3 /h，O 2 Has a flow rate of 1m 3 With the assistance of/h), after a series of reactions such as combustion, explosion, hydrolysis, sintering and the like occur in flame at about 1200 ℃, a vacuum pump drives airflow to drive particles, and SnO is obtained by deposition on a glass fiber filter membrane of a collector 2-x ，SnO 2-x Has an average particle diameter of 10nm and a specific surface area of 123.3m 2 /g。
(3)SnO 2-x Preparing an electrode: snO is treated 2-x Grinding with Ketjen black, adding into slurry containing PVDF and NMP, snO 2-x : ketjen black: the mass ratio of PVDF is 7 2-x The mass ratio of (1) to (2) is 7. Pouring the first mixed slurry on a copper foil, and drying the copper foil in a vacuum oven at 120 ℃ for 12h to obtain SnO 2-x And an electrode.
SnO of examples 1 to 3 2-x Performing X-ray diffraction (XRD) test with X-ray polycrystalline diffractionThe results of the shooter (polycrystal/D8 Advance DaVinci, bruke AXS, germany) are shown in FIG. 2. SnO of examples 1 to 3 2-x All are rutile phase.
SnO of examples 1 to 3 2-x Electron paramagnetic resonance spectroscopy (EPR) was performed using an electron paramagnetic resonance spectrometer (bruker a 300) and the results are shown in fig. 3. The EPR intensities of examples 1 to 3 were 2014.8, 2591.1 and 3464.8, respectively.
SnO of examples 1 to 3 2-x An X-ray photoelectron spectroscopy (XPS) test was performed using a Thermo ESCALAB 250Xi (semer feishal) test apparatus, and the results are shown in fig. 4. 3d of Sn element in examples 1 to 3 3/2 Binding energy of track and 3d 5/2 The binding energy results for the tracks are shown in table 1.
TABLE 13 d of Sn element in examples 1 to 3 3/2 Binding energy of track and 3d 5/2 Binding energy of rail
| 3d 3/2 Binding energy of track (eV) | 3d 5/2 Binding energy of track (eV) | |
| Example 1 | 486.8 | 495.2 |
| Example 2 | 486.6 | 495 |
| Example 3 | 486.3 | 494.7 |
The shift of the Sn 3d peak in XPS indicates SnO 2-x Formation of mesooxygen vacancies. As can be seen from Table 1, the peak shifts (3 d) of example 2 and example 1 relative to example 3 are shown 3/2 Orbital binding energy) were 0.2eV and 0.5eV, respectively.
Combining the EPR and XPS results, example 3 has a greater concentration of oxygen vacancies than example 2 than example 1.
Example 3-1
(1) Preparing a composite electrode: snO prepared in step (2) of example 3 2-x Grinding with Ketjen black, adding into slurry containing graphite, PVDF and NMP, snO 2-x : graphite: keqin black: the mass ratio of PVDF is 16 2-x The mass ratio of (1) to (2) is 7. And pouring the second mixed slurry on the copper foil, and drying for 12 hours in a vacuum oven at 120 ℃ to obtain the composite electrode.
Examples 3 to 2
(1) Preparing a composite electrode: snO prepared in step (2) of example 3 2-x Grinding with Ketjen black, adding into slurry containing graphite, PVDF and NMP, snO 2-x : graphite: ketjen black: mass ratio of PVDF 32 2-x The mass ratio of (1) to (2) is 7. And pouring the second mixed slurry on the copper foil, and drying for 12h in a vacuum oven at 120 ℃ to obtain the composite electrode.
Comparative example 1
Mixing graphite and ketjen black, and adding the mixture into a slurry containing PVDF and NMP, wherein the ratio of graphite: keqin black: the mass ratio of PVDF to graphite was 8. And pouring the third mixed slurry on a copper foil, and drying for 12 hours in a vacuum oven at 120 ℃ to obtain the graphite electrode.
The electrodes of example 3-1, example 3-2 and comparative example 1 were subjected to a rate capability test as shown in fig. 5 and table 2.
TABLE 2 specific capacities (mAh. G) of examples 3-1, 3-2 and comparative example 1 at different current densities -1 )
| Current density | 0.1Ag -1 | 0.2Ag -1 | 0.5Ag -1 | 1Ag -1 | 2Ag -1 | 5Ag -1 | 10Ag -1 |
| Example 3-1 | 441.9 | 444.6 | 416.5 | 358.1 | 280.8 | 179.7 | 133.6 |
| Examples 3 to 2 | 777.6 | 712.8 | 662.7 | 593.9 | 503.7 | 398.2 | 338.9 |
| Comparative example 1 | 387.3 | 314 | 154.6 | 51.6 | 29 | 11.6 | 51 |
When SnO prepared in step (2) of example 3 is reacted 2-x Example 3-1 and example 3-2 were at 0.1 ag for preparing composite electrodes with graphite as an additive -1 After circulating for 100 circles under the current density of (1), 589.4mAh g is kept -1 And 851.9 mAh. G -1 The specific capacity of (a).
In a laboratory assembled button full cell, the electrodes of example 3-1 and example 3-2 still had 279mAh g, respectively, after 100 cycles of stable cycling -1 And 387mAh · g -1 The reversible specific capacity of (a). Wherein, the full cell assembly process is as follows: mixing a commercial ternary material NCM811 serving as a positive electrode material with Ketjen black and PVDF in a mass ratio of 8. The test instrument was model LAND-2001A.
Comparative example 2
(1) Preparing a mixed solution: weighing 0.02mol of stannic chloride, dissolving in 60mL of ethanol, mixing, and stirring for 5 hours to obtain a mixed solution for later use;
(2) Forming the mixed solution into fine powder by an atomizing burner at a feeding rate of 5mL/min by using a peristaltic injection pumpDroplets, 13 microns in size, are fed to a spray combustion reactor with a shear gas of O 2 The resulting shear pressure was 0.1MPa. Atomized droplets in H 2 /O 2 Mixed gas (H) of (2) 2 At a flow rate of 0.15m 3 /h，O 2 Has a flow rate of 1m 3 With the assistance of/h), after a series of reactions such as combustion, explosion, hydrolysis, sintering and the like occur in flame at about 1200 ℃, a vacuum pump drives airflow to drive particles, and SnO is obtained by deposition on a glass fiber filter membrane of a collector 2 ，SnO 2 Has an average particle diameter of 60nm;
(3)SnO 2 preparing an electrode: snO 2 Grinding with Ketjen black, adding into slurry containing PVDF and NMP, snO 2 : keqin black: the mass ratio of PVDF is 7 2 The mass ratio of (1) to (9) is 7. Pouring the first mixed slurry on a copper foil, and drying the copper foil in a vacuum oven at 120 ℃ for 12h to obtain SnO 2 And an electrode.
The electrodes of examples 1 to 3 and comparative example 2 were subjected to 1Ag -1 Cycling performance at current density was tested as shown in fig. 6 and table 3.
Table 3 specific capacity (mAh · g) at different cycle numbers for examples 1 to 3 and comparative example 1 -1 )
| Number of |
100 | 200 |
| Example 1 | 612.4 | 419.2 |
| Example 2 | 703.4 | 602 |
| Example 3 | 738.6 | 742.6 |
| Comparative example 2 | 480.5 | 313.9 |
As mentioned above, the only preferred SnO of the present invention with adjustable vacancy concentration 2-x The scope of the present invention is not limited thereto, and any person skilled in the art to which the present invention pertains, who may make equivalent substitutions or changes according to the preparation scheme of the present invention, should be covered by the scope of the present invention.
Claims (16)
1. SnO (stannic oxide) 2-x The preparation method is characterized by comprising the following steps:
performing flame spray pyrolysis on the mixed solution to obtain the composite material;
wherein the mixed solution comprises a tin source, a surfactant, an organic solvent and water;
the flame spray pyrolysis comprises atomizing the mixed solution to obtain liquid drops; the size of the liquid drop is 5 to 20 micrometers; the liquid drops are obtained by shearing the mixed solution through gas; the gas is O 2 The shearing pressure generated by the gas is 0.1 to 0.3Mpa; during atomization, the feeding speed of the mixed solution is 2-10mL/min;
during atomization, the mixed solution is fed by adopting an injection pump or a continuous injection pump;
the flame of the flame spray pyrolysis is obtained by combusting an oxygen-containing gas;
the oxygen-containing gas is H 2 And O 2 The mixed gas of (3);
the above-mentionedIn an oxygen-containing gas, H 2 The flow rate of (2) is 0.08 to 2m 3 /h，O 2 The flow rate of (2) is 0.5 to 1.2m 3 /h；
In the flame spray pyrolysis, the temperature of a combustion flame area is 800-1500 ℃;
the tin source is one or more of stannic chloride, stannous octoate, tetrabutyltin and stannic chloride;
the surfactant is one or more of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone and tween;
the molar ratio of the tin source to the surfactant is 3 to 10;
the organic solvent is one or more of ethanol, toluene, xylene and propionic acid;
the volume ratio of the organic solvent to the water is 1 to 1;
the mixed solution is obtained by mixing and stirring the tin source, the surfactant, the organic solvent and the water; the stirring time is 3 to 6 hours;
in the mixed solution, the ratio of the total mole number of the tin source and the surfactant to the volume of the organic solvent is 0.1 to 1mol/L;
the SnO 2-x Is in a rutile phase;
the SnO 2-x The intensity of the electron paramagnetic resonance spectrum of (2) is 2000 or more;
the SnO 2-x 3d of medium Sn element 3/2 The bonding energy of the orbit is 494.7 to 495.2eV, the bonding energy of the Sn element is 3d 5/2 The binding energy of the orbit is 486.3 to 486.8eV.
2. The SnO of claim 1 2-x Characterized in that said SnO 2-x The preparation method of (a) satisfies one or more of the following conditions:
(1) During atomization, the feeding speed of the mixed solution is 5mL/min;
(2) The molar ratio of the tin source to the surfactant is 2;
(3) The volume ratio of the organic solvent to the water is 1.4 or 1.6;
(4) The stirring time is 5h;
(5) In the mixed solution, the ratio of the total molar number of the tin source and the surfactant to the volume of the organic solvent is 0.43mol/L, 0.67mol/L or 0.83mol/L.
3. SnO (stannic oxide) 2-x Characterized in that it consists of the SnO according to claim 1 or 2 2-x The preparation method.
4. The SnO of claim 3 2-x Characterized in that said SnO 2-x The particle size of the nano-particles is 5 to 20nm;
and/or, said SnO 2-x The specific surface area of (b) is 100 to 130m 2 /g；
And/or, said SnO 2-x The intensity of the electron paramagnetic resonance spectrum (E) is 2014.8 to 3464.8.
5. SnO (stannic oxide) 2-x The preparation method of the electrode is characterized by comprising the following steps:
coating the first mixed slurry on the surface of a substrate material and then heating;
wherein the first mixed slurry comprises the SnO of claim 3 or 4 2-x A conductive agent, a binder and a solvent;
the SnO 2-x Said SnO 2-x The total amount of the conductive agent and the binder is 70% by mass or more and not 100%.
6. The SnO of claim 5 2-x A method for producing an electrode, characterized in that said SnO 2-x The preparation method of the electrode meets one or more of the following conditions:
(1) The substrate material is copper foil or aluminum foil;
(2) The SnO 2-x Said SnO 2-x The mass percentage of the total amount of the conductive agent and the binder is 70% -80%;
(3) The conductive agent is one or more of Ketjen black, conductive carbon black and acetylene black;
(4) The conductive agent is in the SnO 2-x The total amount of the conductive agent and the binder is 30% by mass or less and is not 0;
(5) The binder is polyvinylidene fluoride and/or carboxymethyl cellulose;
(6) The binder is in the SnO 2-x The total amount of the conductive agent and the binder is 20% by mass or less and is not 0;
(7) The solvent is N-methyl pyrrolidone;
(8) The SnO 2-x The mass ratio of the solvent to the solvent is 1 to 7;
(9) The SnO 2-x : the conductive agent: the mass ratio of the binder is 7;
(10) The heating temperature is 130 to 150 ℃;
(11) The heating time is 10 to 15h;
(12) The heating is performed under vacuum.
7. The SnO of claim 5 2-x A method for producing an electrode, characterized in that said SnO 2-x Said SnO 2-x The total amount of the conductive agent and the binder is 70% by mass;
and/or, the conductive agent accounts for the SnO 2-x The total amount of the conductive agent and the binder is 20% by mass or less;
and/or, said binder comprises said SnO 2-x The total amount of the conductive agent and the binder is 10% by mass or less;
and/or, said SnO 2-x The mass ratio of the solvent to the solvent is 7;
and/or the heating temperature is 120 ℃;
and/or the heating time is 12h.
8. The SnO of claim 5 2-x A method for producing an electrode, characterized in that the conductive agent is contained in the SnO 2-x The mass percentage of the total amount of the conductive agent and the binder is 20%;
and/or, said binder comprises said SnO 2-x And the total amount of the conductive agent and the binder is 10% by mass.
9. SnO (stannic oxide) 2-x An electrode made of the SnO according to any of claims 5 to 8 2-x The preparation method of the electrode.
10. The preparation method of the composite electrode is characterized by comprising the following steps of:
coating the second mixed slurry on the surface of a substrate material and then heating;
wherein the second mixed slurry comprises the SnO of claim 3 or 4 2-x Graphite, a conductive agent, a binder and a solvent;
the SnO 2-x Said SnO 2-x The total amount of the graphite, the conductive agent, and the binder is 32% by mass or less and is not 0;
the graphite occupies the SnO 2-x The mass percentage of the total amount of the graphite, the conductive agent and the binder is 48-64%.
11. A method of making a composite electrode according to claim 10, wherein the method of making the composite electrode satisfies one or more of the following conditions:
(1) The substrate material is copper foil or aluminum foil;
(2) The SnO 2-x Said SnO 2-x 16-32% by mass of the total amount of the graphite, the conductive agent and the binder;
(3) The conductive agent is one or more of Ketjen black, conductive carbon black and acetylene black;
(4) The conductive agent isThe SnO 2-x The total amount of the graphite, the conductive agent, and the binder is 20% by mass or less and is not 0;
(5) The binder is polyvinylidene fluoride and/or carboxymethyl cellulose;
(6) The binder is in the SnO 2-x The total amount of the graphite, the conductive agent, and the binder is 20% by mass or less and is not 0;
(7) The solvent is N-methyl pyrrolidone;
(8) The SnO 2-x The mass ratio of the solvent to the solvent is 1 to 7;
(9) The SnO 2-x : the graphite: the conductive agent: the mass ratio of the binder is 16;
(10) The heating temperature is 130 to 150 ℃;
(11) The heating time is 10 to 15h;
(12) The heating is performed under vacuum conditions.
12. The method of making a composite electrode of claim 10, wherein said conductive agent comprises said SnO 2-x The total amount of the graphite, the conductive agent and the binder is 10% by mass or less;
and/or, the binder comprises the SnO 2-x The total amount of the graphite, the conductive agent and the binder is 10% by mass or less
And/or, said SnO 2-x The mass ratio of the solvent to the solvent is 7;
and/or the heating temperature is 120 ℃;
and/or the heating time is 12h.
13. The method of making a composite electrode of claim 10, wherein said conductive agent comprises said SnO 2-x The total amount of the graphite, the conductive agent and the binder is 10% by mass;
and/or, the binder comprises the SnO 2-x And the total amount of the graphite, the conductive agent and the binder is 10% by mass.
14. A composite electrode produced by the method of producing a composite electrode according to any one of claims 10 to 13.
15. The SnO of claim 9 2-x Use of an electrode or a composite electrode according to claim 14 in a lithium ion battery.
16. A lithium ion battery comprising the SnO of claim 9 2-x An electrode or a composite electrode as claimed in claim 14.
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