CN114804118B - Modified silicon oxide material, preparation method thereof and lithium ion battery - Google Patents
Modified silicon oxide material, preparation method thereof and lithium ion battery Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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Abstract
The invention provides a modified silicon oxide material, a preparation method thereof and a lithium ion battery. The invention firstly combines alkali metal and silicon oxide (SiO) x X is approximately equal to 1) is mixed in nitrogen-based liquid (namely liquid ammonia and/or liquid amine) and is subjected to heating treatment, so that the coating of amino salt is realized, and then the obtained material is subjected to molten salt thermal reaction to induce the separation of inert silicon-oxygen compounds, so that the active silicon-oxygen ratio is regulated, the first coulomb efficiency of the obtained modified silicon oxide material is obviously improved, and the modified silicon oxide material has good air stability.
Description
Technical Field
The invention relates to the field of battery materials, in particular to a modified silicon oxide material, a preparation method thereof and a lithium ion battery.
Background
The main challenge faced by lithium ion batteries is the lower theoretical capacity (372 mAh g) of conventional carbonaceous electrodes (hard carbon and graphite) -1 ) But cannot meet the currently required energy density requirements. Silicon oxide (also known as silicon monoxide, siO) x X.apprxeq.1) has a suitable working potential<0.4V vs. Li+/Li) high reversible specific capacity>1300mAh g -1 ) The lithium ion battery is a cathode material of the next generation of the lithium ion battery with the prospect, and is rich in reserves and has stronger cycling stability compared with a silicon electrode. SiO (SiO) x The electrochemical mechanism of (a) is summarized as follows: siO (SiO) x +Li++e-→Li x Si+Li y SiO z +Li 2 O, while lithium silicate (Li y SiO z ) And Li (lithium) 2 O plays the role of double-edged sword. Li (Li) 2 O and Li y SiO z Can act as buffers to mitigate the volume change of active silicon, but their electrochemical inertness also results in lower first-order coulombic efficiency (ICE) (-)<65%) greatly hampers its practical application. The addition of excess positive electrode material in current practice counteracts the loss of active Li, but this simultaneously limits the available energy density of the full cell.
To solve the above problems, researchers have focused on SiO x The (X is approximately equal to 1) cathode is developed, and the higher first coulomb efficiency is realized on the premise of not sacrificing the energy density. Methods for improving the first coulombic efficiency are generally by using pre-lithiation techniques, including lithium metal pre-lithiation, active lithium alloy pre-lithiation, chemical pre-lithiation, and the like. And these pre-formsLithiation operation and prepared pre-lithiated SiO x The cathode is extremely sensitive to air and is difficult to realize industrialized mass production, so that SiO with high first effect and stable air is prepared x The negative pole is urgent.
Disclosure of Invention
In view of the above, the present invention aims to provide a modified silica material, a preparation method thereof, and a lithium ion battery. The modified silicon oxide material provided by the invention can improve the first coulomb efficiency of the lithium ion battery and is stable to air.
The invention provides a preparation method of a modified silicon oxide material, which comprises the following steps:
a) Mixing alkali metal and silicon oxide in nitrogen-based liquid, and then heating to obtain an amino salt coated silicon oxide composite material;
b) Mixing the amino salt coated silica composite material with molten salt, and performing heat treatment to obtain a modified silica material;
the nitrogen-based liquid is liquid ammonia and/or liquid amine;
the molten salt is an alkali halide.
Preferably, the amine compound in the liquid amine is methylamine and/or ethylamine.
Preferably, in the step a), the temperature of the heating treatment is 20-80 ℃ and the heat preservation time is 10 min-2 h.
Preferably, in the step a), the molar ratio of the alkali metal to the silicon oxide is 1: (5-20);
the molar ratio of the silicon oxide to the nitrogen-based compound in the nitrogen-based liquid is preferably (5-20) to 1.
Preferably, the step a) specifically includes:
after mixing alkali metal and silicon oxide, charging nitrogen-based gas into the system, and converting the nitrogen-based gas into nitrogen-based liquid by cooling; then carrying out heat treatment to volatilize the nitrogen-based liquid to obtain an amino salt coated silica composite material;
the nitrogen-based gas is ammonia gas and/or amine gas.
Preferably, in the step b), the temperature of the heat treatment is 500-900 ℃ and the time is 3-24 hours;
the heat treatment is performed under a protective atmosphere.
Preferably, the molten salt is selected from one or more of lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide and potassium bromide.
Preferably, in the step b), the mass ratio of the amino salt coated silica composite material to the molten salt is 1:5-20.
The invention also provides a modified silicon oxide material prepared by the preparation method in the technical scheme.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode and a diaphragm; the negative electrode active material in the negative electrode is the modified silicon oxide material in the technical scheme.
The invention firstly combines alkali metal and silicon oxide (SiO) x Mixing and heating in nitrogen-based liquid to realize coating of amino salt, and then carrying out molten salt thermal reaction on the obtained material to induce the separation of inert silicon-oxygen compound so as to adjust the active silicon-oxygen ratio, thereby obtaining the modified SiO x The material significantly improves the first coulombic efficiency and exhibits good air stability.
Experimental results show that the modified silicon oxide material prepared by the invention can improve the lithium ion battery, has a first reversible charging capacity of more than 1300mAh/g under the current density of 0.2A/g, has a first coulomb efficiency of more than 85%, and shows good air stability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the color change from raw materials to final product in example 1;
FIG. 2 is a graph of the microtopography from feedstock to final product in example 1; wherein FIG. 2a is an SEM image of the raw material, and FIG. 2b is an intermediate product lithium amide coated SiO x FIG. 2c is an SEM of the final product;
FIG. 3 shows the modified SiO obtained in example 1 x An X-ray diffraction pattern of the material;
FIG. 4 shows the modified SiO obtained in example 1 x Raman spectrum of the material;
FIG. 5 shows the modified SiO obtained in example 1 x Photoelectron spectrum of the material;
FIG. 6 shows the modified SiO obtained in example 1 x NMR spectrum of the material;
FIG. 7 shows the modified SiO obtained in example 1 x A lithium storage performance diagram of the material;
FIG. 8 is a raw material SiO x A lithium storage performance graph of a control sample;
FIG. 9 shows the modified SiO obtained in example 1 x Cycling performance graph of the material.
Detailed Description
The invention provides a preparation method of a modified silicon oxide material, which comprises the following steps:
a) Mixing alkali metal and silicon oxide in nitrogen-based liquid, and then heating to obtain an amino salt coated silicon oxide composite material;
b) Mixing the amino salt coated silica composite material with molten salt, and performing heat treatment to obtain a modified silica material;
the nitrogen-based liquid is liquid ammonia and/or liquid amine;
the molten salt is an alkali halide.
The invention firstly combines alkali metal and silicon oxide (SiO) x Mixing and heating in nitrogen-based liquid (liquid ammonia and/or liquid amine) to coat amino salt, and performing molten salt thermal reaction on the obtained material to induce the separation of inert silicon-oxygen compound, thereby regulating active silicon-oxygen ratio and modifying SiO x The first warehouse of materials is obviously improvedThe efficiency of the system is improved, and the system has good air stability.
Regarding step a): mixing alkali metal and silicon oxide in nitrogen-based liquid, and then heating to obtain the amino salt coated silicon oxide composite material.
In the present invention, the alkali metal is preferably one or more of lithium, sodium and potassium. The source of the alkali metal is not particularly limited, and the alkali metal may be a general commercial product.
In the present invention, the silicon oxide (also called SiO, siO x X is about 1) is a conventional silicon oxide anode material in the prior art, and the source of the silicon oxide anode material is not particularly limited, so that the silicon oxide anode material is a common commercial product. The particle size of the silica is preferably 1 to 8 microns.
In the present invention, the molar ratio of the alkali metal to the silica is preferably 1:5 to 20.
In the invention, the nitrogen-based liquid is liquid ammonia and/or liquid amine. Wherein the liquid amine is preferably methylamine and/or ethylamine. In the present invention, the nitrogen-based liquid is preferably formed by introducing a nitrogen-based gas into the system and then cooling the gas to convert the gas into a nitrogen-based liquid. Wherein, the nitrogen gas is preferably ammonia gas and/or amine gas. The amine gas is preferably methylamine and/or ethylamine.
In the present invention, the molar ratio of the silicon oxide to the nitrogen-based compound in the nitrogen-based liquid is preferably (5 to 20) to 1.
In the present invention, the step a) preferably specifically includes: after mixing alkali metal and silicon oxide, charging nitrogen-based gas into the system, and converting the nitrogen-based gas into nitrogen-based liquid by cooling; and then carrying out heat treatment to volatilize the nitrogen-based liquid to obtain the amino salt coated silica composite material.
Namely, first, the nitrogen-based gas is converted into the nitrogen-based liquid by low-temperature liquefaction to perform liquid-phase coating. Wherein the temperature of the coolant used for cooling is preferably-100 to-20 ℃. The coolant preferably comprises one or more of liquid nitrogen, dry ice-acetone mixture, dry ice-ethanol mixture. Specifically, the container containing the raw materials is placed in a cooling bath for cooling. The cooling time is preferably 0.5 to 2 hours.
After the nitrogen-based gas is converted into nitrogen-based liquid through the cooling, the nitrogen-based liquid is coated, an air outlet of a raw material container is opened, and the system is subjected to heat treatment to volatilize the nitrogen-based liquid. In the invention, the temperature of the heat treatment is preferably 20-80 ℃; the heat treatment time is preferably 10 minutes to 2 hours, specifically, until the nitrogen-based liquid is completely volatilized. Then taking out the sample, namely the amino salt coated SiO x Is a composite material of (a).
In the invention, the process of the step a) and the sampling process are preferably carried out under protective atmosphere, specifically, an experimental device is assembled in a glove box, after reactants are filled in, an air valve is closed, a balloon protection device is arranged, and ammonia gas is introduced outside the glove box for carrying out the next reaction. The reacted system was transferred to a glove box filled with a protective gas, and a sample was taken out. The kind of the protective gas is not particularly limited in the present invention, and may be a conventional inert gas such as nitrogen, argon or helium, etc., which are well known to those skilled in the art.
Regarding step b): and mixing the amino salt coated silica composite material with molten salt, and performing heat treatment to obtain the modified silica material.
The molten salt refers to a molten mass formed after melting of salts, which is solid at standard temperature and atmospheric pressure, and salts which exist in a liquid phase after the temperature is raised. In the invention, the molten salt is an alkali metal halide, preferably one or more of lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide and potassium bromide. In the present invention, it is preferable that the metal in the molten salt used in the step b) is the same kind as the alkali metal used in the step a).
In the invention, the mass ratio of the amino salt coated silica composite material to the molten salt is preferably 1:5-20; in some embodiments of the invention, the mass ratio is 1:10, 1:15, or 1:18.
In the invention, the temperature of the heat treatment is preferably 500-900 ℃; in some embodiments of the invention, the temperature of the heat treatment is 620 ℃, 650 ℃, or 700 ℃. In the present invention, the heating rate of the heat treatment is preferably 1 to 10 ℃/min. In the invention, the heat preservation time of the heat treatment is preferably 3-24 hours; in some embodiments of the invention, the incubation time is 5 hours, 8 hours, or 10 hours. In the present invention, it is preferable to further wash and dry the modified silica material after the above heat treatment.
In the preparation process of the invention, the SiO coated by amino salt is obtained in the first step x In particular to SiO coated by ammonia/amino salt formed by dissolving alkali metal in liquid ammonia/liquid amine and then reacting liquid ammonia molecules/amine molecules with alkali metal x After this coating is completed, the temperature is raised and the liquid ammonia/liquid amine is completely volatilized. And secondly, after molten salt is added, the externally coated ammonia/amino salt reacts with the silicon oxide in a molten salt medium to generate the lithium silicate composite modified silicon oxide.
The invention also provides a modified silicon oxide material prepared by the preparation method in the technical scheme. The preparation method of the invention adjusts the silicon oxide SiO through molten salt and amino salt x The proportion of the medium-activity silica to lead the obtained modified silica SiO x The material significantly improves the first coulombic efficiency and exhibits good air stability.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode and a diaphragm; the negative electrode active material in the negative electrode is the modified silicon oxide material in the technical scheme.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention. In the following examples, raw material silicon oxide (SiO x X.apprxeq.1) particle size of 1-8 microns.
Example 1
30mg of metallic lithium, 2g of SiO x The materials were mixed in a Schlenk tube (alkali metal lithium and silica SiO) x The molar ratio of (1:10), the upper outlet of the tube was sealed with a balloon, the air inlet was filled with ammonia gas, and the mixture was kept in a dry ice-acetone bath for 1 hour with rotary stirring. Placing the Schlenk tube in 25 deg.C ethanol bath, opening air outlet, rotating and stirring to volatilize liquid ammonia, transferring into a glove box filled with argon after volatilization is completed, and taking out sample (i.e. SiO coated with lithium amide x ). Uniformly mixing the mixture with anhydrous lithium chloride according to the mass ratio of 1:10, heating to 700 ℃ in a tubular furnace under the protection of argon, and preserving heat for 10 hours to obtain a product. Then washing, centrifuging and drying to obtain modified silicon oxide SiO x A material.
SiO coated by lithium amide as the product obtained from raw material-step 1 x The final obtained modified SiO x Materials (i.e. high first-effect SiO x ) Referring to fig. 1, fig. 1 is a graph showing the change in color from raw material to final product in example 1.
SiO coated with lithium amide obtained in step 1 from the raw material in example 1 was subjected to scanning electron microscopy x The final obtained modified SiO x Materials (i.e. high first-effect SiO x ) As a result of analysis of the microstructure of (2), see fig. 2, fig. 2 is a graph showing the microstructure from the raw material to the final product in example 1; wherein FIG. 2a is an SEM image of the raw material, and FIG. 2b is an intermediate product lithium amide coated SiO x Figure 2c is an SEM image of the final product. The result shows that the silicon oxide forms a layer of rough and fluffy substance on the surface after coating, and is converted into pomegranate-shaped cluster particles after molten salt thermal reaction.
The modified SiO obtained in example 1 was subjected to X-ray powder diffractometer x The X-ray diffraction analysis of the material is shown in FIG. 3, and FIG. 3 shows the modified SiO obtained in example 1 x X-ray diffraction pattern of the material. As can be seen from FIG. 3, the 2 theta in the X-ray diffraction pattern has clearly visible diffraction peaks in the range of 10 DEG to 80 DEG, accompanied by Li 2 SiO 3 And the formation of small amounts of crystalline silicon.
The modified SiO obtained in example 1 was subjected to a Raman spectrometer x The material was subjected to Raman spectrum analysis, the result is shown in FIG. 4, and FIG. 4 shows the modified SiO obtained in example 1 x Raman spectrum of the material. Showing the co-presence of crystalline silicon and amorphous silicon oxide.
The modified SiO obtained in example 1 was subjected to an X-ray spectrometer x Material feedThe results of the photoelectron spectroscopy are shown in FIG. 5, and FIG. 5 shows the modified SiO obtained in example 1 x Photoelectron spectrum of the material. Showing a decrease in the intermediate valence state silicon oxide on the surface and an increase in the ratio of high valence silicon to 0 valence silicon.
The modified SiO obtained in example 1 was subjected to a solid-state nuclear magnetic resonance apparatus x Material is subjected to 29 Si magic angle NMR analysis, results are shown in FIG. 6, FIG. 6 shows modified SiO obtained in example 1 x NMR spectrum of the material. Showing the presence of lithium silicate.
Example 2
50mg of metallic sodium, 3g of SiO x The materials were mixed in a Schlenk tube, the upper outlet of the tube was closed with a balloon, the air inlet was filled with ammonia gas, and the mixture was kept in a dry ice-acetone bath for 1 hour with stirring. Placing the Schlenk tube in 25 deg.C ethanol bath, opening air outlet, rotating and stirring to volatilize liquid ammonia, transferring into a glove box filled with argon after volatilization is completed, and taking out sample (i.e. sodium amide coated SiO) x ). Uniformly mixing the mixture with anhydrous sodium chloride according to the mass ratio of 1:15, heating to 650 ℃ in a tube furnace protected by argon, and preserving heat for 10 hours to obtain a product. Then washing, centrifuging and drying to obtain modified silicon oxide SiO x A material.
Example 3
40mg of metallic potassium, 3g of SiO x The materials were mixed in a Schlenk tube, the upper outlet of the tube was closed with a balloon, the air inlet was filled with ammonia gas, and the mixture was kept in a dry ice-acetone bath for 0.5 hour with rotary stirring. Placing the Schlenk tube in 25 deg.C ethanol bath, opening air outlet, stirring while rotating to volatilize liquid ammonia, transferring into a glove box filled with argon after volatilization is completed, and taking out sample (i.e. SiO coated with potassium amino x ). Uniformly mixing the mixture with anhydrous potassium chloride according to the mass ratio of 1:18, heating to 620 ℃ in a tube furnace protected by argon, and preserving heat for 5 hours to obtain a product. Then washing, centrifuging and drying to obtain modified silicon oxide SiO x A material.
Example 4
25mg of metallic lithium, 2g of SiO x Mixing the materials in a Schlenk tube, sealing the upper outlet of the tube with a balloon, introducing methylamine gas into the air inlet, and spinningThe mixture was stirred and incubated in a dry ice-ethanol bath for 1 hour. Placing the Schlenk tube in 25 deg.C ethanol bath, opening air outlet, rotating and stirring to volatilize methylamine, transferring into a glove box filled with argon gas after volatilization is completed, and taking out sample (i.e. SiO coated with lithium amide x ). Uniformly mixing the mixture with anhydrous lithium chloride according to the mass ratio of 1:10, heating to 700 ℃ in a tubular furnace under the protection of argon, and preserving heat for 8 hours to obtain a product. Then washing, centrifuging and drying to obtain modified silicon oxide SiO x A material.
Example 5
The modified silica SiO obtained in example 1 x The materials were assembled into CR2016 button cells: the material electrode is prepared by adopting active substances (namely modified silicon oxide SiO) with the mass ratio of 80 percent x ) 10% of sodium carboxymethyl cellulose, 10% of conductive carbon black and deionized water are mixed to prepare the electrode plate, a current collector adopts copper foil, and the electrode plate is prepared by heat preservation for 6 hours at 100 ℃. Lithium foil is used as a counter electrode, celgard2500 is used as a diaphragm, a mixed solution of ethylene carbonate and dimethyl carbonate (volume ratio of 1:1) of lithium hexafluorophosphate is used as an electrolyte, and 10% fluoroethylene carbonate and 2% vinylene carbonate are used as additives. The assembly process was completed in an argon glove box.
Setting a control sample: siO as a raw material x The CR2016 button cell was assembled as described above.
The electrochemical performance of the CR2016 button cell obtained was tested at a test temperature of 25deg.C to give the modified SiO of example 1 x Material and raw material SiO x As shown in fig. 7-9. FIG. 7 shows the modified SiO obtained in example 1 x FIG. 8 is a graph showing the lithium storage performance of the material, siO, as a raw material x Lithium storage performance graph of the control. It can be seen that the modified SiO obtained in example 1 is obtained at a current density of 0.2A/g x The reversible charging capacity of the material reaches 1351.6mAh/g, the first efficiency reaches 86.43 percent, compared with the SiO raw material x In the comparison sample, the initial effect is improved by almost 28%, and the energy density of the battery is greatly improved.
FIG. 9 shows the modified SiO obtained in example 1 x Cycling performance graph of material: at a current density of 0.2A/g, after 100 cycles,the reversible capacity can reach 740mAh/g, the capacity retention rate reaches 54.75 percent, and no attenuation phenomenon occurs later.
For the modified SiO obtained in example 1 x The material is subjected to air stability test, in particular to thermal stability test in an air environment, and the result shows that: the material quality is hardly changed in the heating process within 0-200 ℃, and the air stability is excellent.
The above test was performed on other examples, and the results are shown in table 1:
TABLE 1 modified SiO's obtained in examples 1 to 4 x Material and control properties
The above examples prove that the method of the invention which utilizes liquid phase coated amino salt to assist molten salt induction can effectively realize high first efficiency modification of silicon oxide SiO x The material is prepared, has good air stability, can show a lithium storage capacity far higher than graphite and a first efficiency far higher than a conventional silicon oxide material when being applied to a lithium ion battery cathode, and can be used as a potential next-generation high-performance lithium ion battery cathode material.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The preparation method of the modified silicon oxide material is characterized by comprising the following steps of:
a) Mixing alkali metal and silicon oxide in nitrogen-based liquid, and then heating to obtain an amino salt coated silicon oxide composite material;
b) Mixing the amino salt coated silica composite material with molten salt, and performing heat treatment to obtain a modified silica material;
the nitrogen-based liquid is liquid ammonia and/or liquid amine;
the molten salt is an alkali halide.
2. The preparation method according to claim 1, wherein the amine compound in the liquid amine is methylamine and/or ethylamine.
3. The method according to claim 1, wherein in the step a), the temperature of the heating treatment is 20-80 ℃ and the heat preservation time is 10 min-2 h.
4. The method according to claim 1, wherein in the step a), the molar ratio of the alkali metal to the silica is 1: (5-20);
the molar ratio of the silicon oxide to the nitrogen-based compound in the nitrogen-based liquid is (5-20) to 1.
5. The preparation method according to any one of claims 1 to 4, wherein the step a) specifically includes:
after mixing alkali metal and silicon oxide, charging nitrogen-based gas into the system, and converting the nitrogen-based gas into nitrogen-based liquid by cooling; then carrying out heat treatment to volatilize the nitrogen-based liquid to obtain an amino salt coated silica composite material;
the nitrogen-based gas is ammonia gas and/or amine gas.
6. The method according to claim 1, wherein in the step b), the heat treatment is performed at a temperature of 500 to 900 ℃ for 3 to 24 hours;
the heat treatment is performed under a protective atmosphere.
7. The method according to claim 1, wherein the molten salt is one or more selected from the group consisting of lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide and potassium bromide.
8. The preparation method of claim 1, wherein in the step b), the mass ratio of the amino salt coated silica composite material to the molten salt is 1: (5-20).
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