CN112652744A - Preparation method of high-capacity high-cycle lithium battery negative electrode material and lithium battery - Google Patents
Preparation method of high-capacity high-cycle lithium battery negative electrode material and lithium battery Download PDFInfo
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Abstract
The invention relates to the technical field of lithium battery cathode materials, in particular to a preparation method of a high-capacity high-cycle lithium battery cathode material and a lithium battery, which comprises the following steps: A. carrying out ball milling and mixing on metal aluminum or silicon-aluminum alloy with the particle size of micron and SiOx with the particle size of micron according to the mass ratio of 1: 0.5-5; B. and heating the mixed powder to 600-900 ℃ in the atmosphere of protective gas, and performing surface carbon coating reaction for 20-300min by using a vapor deposition method to obtain the lithium battery cathode material powder.
Description
Technical Field
The invention relates to the technical field of lithium battery cathode materials, in particular to a preparation method of a high-capacity high-cycle lithium battery cathode material and a lithium battery.
Background
In recent years, the demand for energy density of batteries in various fields is rapidly increased, and particularly, new energy automobiles are required to continuously increase the endurance mileage, so that the development of lithium ion batteries with higher energy density is urgently needed at present. High energy density lithium ion batteries have evolved mainly from three directions: a positive electrode material, a negative electrode material, and an electrolyte. The development of the anode and cathode materials with high energy density has become the development focus of various large enterprises and research institutions.
The commercial lithium ion battery at present mainly uses graphite as a negative electrode material, the theoretical specific capacity of the graphite is 372mAh/g, the high-end graphite material in the market reaches 360-365mAh/g, and the energy density improvement space of the graphite is very limited. Therefore, the silicon-based negative electrode material is considered to be the next generation high-energy-density lithium battery negative electrode material with great potential due to the advantages of high theoretical specific capacity (4200 mAh/g at high temperature and 3580 mAh/g at room temperature), low de-intercalation potential (< 0.5V), environmental friendliness, abundant reserves, low cost and the like. However, the silicon-based negative electrode material has the problems of large volume change and continuous generation of an unstable SEI film in the lithium intercalation process, so that the cycle performance of the silicon negative electrode material is extremely poor. In order to solve the above problems, silicon nanocrystallization, silicon-carbon composite, and silica have been the main research directions.
The silicon oxide or the silicon material is coated by carbon, the telescopic carbon coating layer can effectively inhibit the volume expansion of the silicon material in the charging and discharging processes, and the carbon coating process improves the electrochemical performance of the material to different degrees compared with the silicon oxide and the silicon raw material. However, the problem of low coulombic efficiency in the first time is caused by poor conductivity of the silicon monoxide, and the problem of low coulombic efficiency cannot be solved although the problems of large volume change and poor circulation in the charge and discharge processes of the silicon cathode can be partially improved by carbon coating, and the problem of non-uniform coating caused by easy agglomeration of nano silicon is solved. Even if the silicon monoxide and the silicon are doped, the problems of low coulombic efficiency and poor capacity retention of the silicon material for the first time cannot be solved.
In addition to carbon coating, there have been studies on alumina coating, which can suppress decomposition of an electrolyte on the surface of a silicon-based negative electrode material to form a more stable solid electrolyte membrane. The atomic layer deposition technology is used for coating alumina, so that the uniform coating at an atomic level can be achieved, but the atomic layer deposition technology needs flammable and explosive organic aluminum compounds and a complex vacuum control system, the cost is high, the efficiency is low, and the coating of powder materials is difficult.
In order to solve the technical problem, chinese patent application 201610399056.8 discloses a method for preparing an aluminum oxide coated silicon negative electrode material, which comprises subjecting silicon nanopowder to a heat treatment at 1000 ℃ under an oxygen-containing atmosphere to obtain pre-oxidized silicon nanopowder, mixing the silicon nanopowder with aluminum powder and tin powder, performing a heat treatment at 900 ℃ to obtain an intermediate, and treating the intermediate with an acid or an oxidant to obtain the aluminum oxide coated silicon negative electrode material, wherein the total mass percentage of the aluminum powder and the tin powder is required to be greater than 0% and less than 80%, that is, the method necessarily comprises tin, and the particle size of the silicon nanopowder is 1nm-500 nm.
The method avoids the danger of organic aluminum compounds and a complex vacuum control system, but the scheme still has a larger problem because the preparation cost of the nano-silicon is higher, the lowest price of the common market price is about 6000-7000 yuan/kg, the smaller the particle size is, the higher the purity is, the price is higher, even the purity of each kilogram is about tens of thousands, and in the technical field of lithium batteries, the higher the purity requirement of the nano-silicon is, the safer the purity requirement is. Therefore, even though the cycle performance of nano silicon is improved, the nano silicon is more expensive at the research and test stage and cannot be put into quantitative production practically at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a high-capacity high-cycle lithium battery cathode material, which has the advantages of low production cost, high capacity and good cycle effect.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of a high-capacity high-cycle lithium battery negative electrode material comprises the following steps:
A. carrying out ball milling and mixing on metal aluminum or silicon-aluminum alloy with the particle size of micron and SiOx with the particle size of micron according to the mass ratio of 1: 0.5-5;
B. and heating the mixed powder to 600-900 ℃ in the atmosphere of protective gas, and performing surface carbon coating reaction for 20-300min by using a vapor deposition method to obtain the lithium battery cathode material powder.
SiOx has an amorphous structure, and there is a multiplicity of valence states of Si in SiOx (Si0, Si)2+、 Si4+Etc.), SiOx is composed of nano-Si clusters and nano-SiO according to the "interface cluster mixed type" model2The cluster and the SiOx interface region surrounding the cluster. The SiOx interface structure and common ultrathin Si/SiO2The interface layer is equivalent, but because of Si and SiO in SiOx2The cluster size is less than 2 nm, the volume of the interface area is larger, and the amorphous Si phase and amorphous SiO2Transition regions exist between the phases and account for about 20% to 25% of the total content, except for amorphous Si and amorphous SiO which are theoretically present2Outside the cluster, an amorphous SiO structure was characterized using the Angstrom beam electron diffraction technique (ABED), and the results demonstrate: there is indeed a SiO (Si: O ratio ≈ 1:1) interphase boundary layer in the Si/SiO2 phase interface region. SiOx is not composed of a single phase but of a plurality of uniformly distributed nano-sized Si clusters, SiO2The cluster and SiOx transition phase between two phases of Si/SiO2 interface, therefore, the lithium storage mechanism is very complicated. Intrinsic conductivity of SiOxThe rate is low, which is not beneficial to the exertion of the electrochemical performance of the material, compared with the lithium ion intercalation reaction cathode material (such as graphite), the generation of the SEI layer is more serious for high-capacity alloying cathode materials (including silicon-based, tin-based, metal oxide and the like). Furthermore, during the initial insertion of lithium, the oxygen atom in SiOx reacts irreversibly with Li + in the electrolyte to form Li in an inert phase2O and Li4SiO4And the first irreversible capacity of the SiOx negative electrode material is increased again, and finally, the problem of low first efficiency of the SiOx negative electrode material is caused. The carbon nano tube, the carbon nano fiber, the graphene and the like are adopted, and the electrochemical performance of the SiOx negative electrode is remarkably improved due to the fact that the carbon nano tube, the carbon nano fiber, the graphene and the like have an ultra-large specific surface area and a multi-dimensional conductive network. In addition, SiOx may be composited with a metal. On one hand, the metal material has good conductivity, and the dynamic performance of the silicon alloy material can be enhanced; on the other hand, the metal can be used as a supporting framework to improve the silicon volume effect, so that the electrochemical performance of the SiOx negative electrode can be effectively improved. However, the problems of expensive raw materials, unstable chemical properties and the like of the nano-grade novel material cannot be industrially produced in large quantities.
The invention firstly adopts micron-level metal aluminum or silicon aluminum alloy to mix with SiOx, uses a high-energy planetary ball milling mode to connect the metal aluminum or silicon aluminum alloy with the SiOx surface, and causes the silicon aluminum and the SiOx to be embedded into the surface of the SiOx by the coexistence of the connection mode at high temperature, and further to diffuse to the inside and to lead amorphous nano SiO in the sub-oxide layer to be2Extracting medium oxygen to make the oxide sublayer formed by Si/SiO2To Si/Al2O3Layer, high temperature can make aluminium liquefaction go on with higher speed above-mentioned process simultaneously, and aluminium can break through suboxide layer and SiO2The clusters contact and react to generate nano silicon clusters and are coated by the generated alumina to form a silicon-aluminum structure with an alumina coating structure. And finally, performing surface carbon coating by using a vapor deposition method (CVD method), and filling carbon atoms in gaps of the loose alumina layer to obtain the lithium battery cathode material, wherein the material conductivity can be increased, the rigidity of the alumina layer can be increased, and the improvement of the material cycle performance is facilitated.
The carbon source used for the CVD coating of the present invention is methane, propylene, propane, acetylene, but is not limited thereto.
Preferably, in the step B, when the heating temperature is lower than 800 ℃, the mixed powder obtained in the step A is independently heated and reacted for 30-180 min; when the heating temperature is equal to or more than 800 ℃, the vapor deposition reaction is directly carried out for surface carbon coating, and the reaction time is preferably 20-120 min.
Preferably, the SiOx has a particle size of 1.0 to 6.0um, preferably 1.7 to 5.0 um.
Preferably, x in the SiOx ranges from 1.0 to 1.5.
Preferably, the particle size of the metal aluminum or the silicon aluminum alloy is 1.0-6.0 um.
Preferably, the silicon content of the silicon-aluminum alloy is 5-50%, preferably 10-30%.
Preferably, the protective gas is any one of an inert gas, a reducing gas, hydrogen, carbon dioxide and nitrogen, and the inert gas is argon gas in common use. Such gases do not affect the reaction of the aluminum or aluminum alloy with SiOx nor CVD coating.
Preferably, the mixing ratio of the metal aluminum or silicon aluminum alloy and the SiOx in the step A is 1:1-4, the consumption mass ratio of the metal aluminum or silicon aluminum alloy and the SiOx in the reaction with Al is 1:1.9-2.5 theoretically, and the consumption ratio of the metal aluminum or silicon aluminum alloy and the SiOx in the silicon-aluminum alloy is 1.3-2.5, wherein the silicon content in the silicon-aluminum alloy is 10-30%. However, it is impossible to completely react Al with SiOx in the mixture, and the range is limited to 1:1-4, preferably x is 1-1.5, wherein the aluminum or aluminum-silicon alloy can be excessively added, metal aluminum can be accumulated in the material when the excessive amount is excessive, and the aluminum can be agglomerated during charging and discharging of the battery to cause short circuit and bring safety hazards. Theoretically, there could be an infinite excess of SiOx, but too much excess would not show the properties of the new material after reaction.
Preferably, the ball-milling mixing in the step A is carried out according to the ball-material ratio of 1:1-15, and the ball size is 1-15 mm.
Another object of the present invention is to provide a lithium battery, which includes a lithium ion negative electrode material prepared by the above method for preparing a high-capacity high-cycle lithium battery negative electrode material, and the lithium ion negative electrode material is applied to the preparation of a lithium ion battery, and a conductive material such as carbon black and graphite and other materials prepared by other lithium ion batteries can be added to obtain a lithium ion battery, which has the advantages of high coulombic efficiency and excellent capacity and cycle performance. The lithium battery prepared from the lithium ion negative electrode material prepared by the invention can adopt a conventional preparation method of the lithium battery, and is not particularly limited.
In summary, compared with the prior art, the beneficial effects of the invention are as follows:
(1) the aluminum metal has a low melting point, is in a liquid state when reacting with SiOx, and can be sufficiently contacted with SiOx.
(2) Al is obtained by reacting aluminum or aluminum alloy with SiOx to obtain nano-silicon2O3And (6) packaging.
(3) The silicon-aluminum oxide generated by the reaction is tightly combined, which is more beneficial to CVD carbon coating.
(4) The raw materials are simple and easy to obtain, the cost is lower, and the method is favorable for industrialization.
(5) The prepared material has the advantages of both Si and SiO, and not only ensures the first coulombic efficiency, but also ensures the capacity retention rate on the premise of not reducing the capacity of the material.
Drawings
FIG. 1 is an XRD pattern of the mixed powder and high temperature product of example 1;
FIG. 2 is an SEM image of a silicon aluminum alloy of example 6;
FIG. 3 is an SEM photograph of a silicon mixed powder of example 6;
fig. 4 is an SEM image of a negative electrode material for a lithium battery prepared in example 6.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings. In the following examples, nitrogen was used as a protective gas, and C was used for CVD coating3H6But is not limited to C3H6Further, acetylene, propane, methanol and the like are also employable. The silicon aluminum alloy used in this example was a commercially available silicon aluminum alloy powder.
Example 1
Silicon-aluminum alloy with silicon content of 20 percent and SiO with D50 of 1.7um1.51, according to the mass ratio: 2 mixing in a planetary ball mill to obtain AlSi/SiO mixed powder,then reacting for 30min at 630 ℃ to prepare a primary product; in N2In the atmosphere with C3H6And carrying out CVD coating on the primary product at 740 ℃ for 60min to obtain the lithium battery negative electrode material.
Example 2
Silicon-aluminum alloy with silicon content of 20 percent and SiO with D50 of 1.7um1.51, according to the mass ratio: 2 mixing in a planetary ball mill to obtain AlSi/SiO mixed powder, and then reacting for 60min at 630 ℃ to obtain a primary product; in N2In the atmosphere with C3H6And carrying out CVD coating on the primary product at 800 ℃ for 60min to obtain the lithium battery cathode material.
Example 3
Silicon-aluminum alloy with silicon content of 20 percent and SiO with D50 of 1.7um1.51, according to the mass ratio: 2 mixing in a planetary ball mill to obtain AlSi/SiO mixed powder, and then reacting for 90min at 630 ℃ to obtain a primary product; in N2In the atmosphere with C3H6And carrying out CVD coating on the primary product at 800 ℃ for 60min to obtain the lithium battery cathode material.
Example 4
Silicon-aluminum alloy with silicon content of 20 percent and SiO with D50 of 1.7um1.51, according to the mass ratio: 2 mixing in a planetary ball mill to obtain AlSi/SiO mixed powder, and then reacting for 30min at 740 ℃ to obtain a primary product; in N2In the atmosphere with C3H6And carrying out CVD coating on the primary product at 740 ℃ for 60min to obtain the lithium battery negative electrode material.
Example 5
Silicon-aluminum alloy with silicon content of 20 percent and SiO with D50 of 1.7um1.51, according to the mass ratio: 2 mixing in a planetary ball mill to obtain AlSi/SiO mixed powder, and then reacting for 30min at 740 ℃ to obtain a primary product; in N2In the atmosphere with C3H6And carrying out CVD coating on the primary product at 800 ℃ for 60min to obtain the lithium battery cathode material.
Example 6
Silicon-aluminum alloy with silicon content of 20 percent and SiO with D50 of 1.7um1.51, according to the mass ratio: 3 in a planetary ball millMixing to obtain AlSi/SiO mixed powder, and then reacting for 30min at 630 ℃ to obtain a primary product; in N2In the atmosphere with C3H6And carrying out CVD coating on the primary product at 740 ℃ for 60min to obtain the lithium battery negative electrode material.
Example 7
Silicon-aluminum alloy with silicon content of 20 percent and SiO with D50 of 1.7um1.51, according to the mass ratio: 4 mixing in a planetary ball mill to obtain AlSi/SiO mixed powder, and then reacting for 30min at 630 ℃ to obtain a primary product; in N2In the atmosphere with C3H6And carrying out CVD coating on the primary product at 740 ℃ for 60min to obtain the lithium battery negative electrode material.
Example 8
Silicon-aluminum alloy with silicon content of 5 percent and SiO with D50 of 1.7um1.51, according to the mass ratio: 2 mixing in a planetary ball mill to obtain AlSi/SiO mixed powder, and then reacting for 30min at 630 ℃ to obtain a primary product; in N2In the atmosphere with C3H6And carrying out CVD coating on the primary product at 740 ℃ for 60min to obtain the lithium battery negative electrode material.
Example 9
Silicon-aluminum alloy with silicon content of 50 percent and SiO with D50 of 1.7um1.51, according to the mass ratio: 2 mixing in a planetary ball mill to obtain AlSi/SiO mixed powder, and then reacting for 30min at 630 ℃ to obtain a primary product; in N2In the atmosphere with C3H6And carrying out CVD coating on the primary product at 740 ℃ for 60min to obtain the lithium battery negative electrode material.
Example 10
Aluminum powder and SiO1.51, according to the mass ratio: 2 mixing in a planetary ball mill to obtain Al/SiO mixed powder, and then reacting for 60min at 630 ℃ to obtain a primary product; in N2In the atmosphere with C3H6And carrying out CVD coating on the primary product at 740 ℃ for 60min to obtain the lithium battery negative electrode material.
Example 11
Silicon-aluminum alloy with silicon content of 20 percent and SiO with D50 of 3.0um1.01, according to the mass ratio: 2 mixing in a planetary ball millSynthesizing to obtain AlSi/SiO mixed powder, and then reacting for 30min at 630 ℃ to obtain a primary product; in N2In the atmosphere with C3H6And carrying out CVD coating on the primary product at 740 ℃ for 60min to obtain the lithium battery negative electrode material.
Example 12
Silicon-aluminum alloy with silicon content of 20 percent and SiO with D50 of 5.0um1.21, according to the mass ratio: 2 mixing in a planetary ball mill to obtain AlSi/SiO mixed powder, and then reacting for 30min at 630 ℃ to obtain a primary product; in N2In the atmosphere with C3H6And carrying out CVD coating on the primary product at 740 ℃ for 60min to obtain the lithium battery negative electrode material.
Example 13
Silicon-aluminum alloy with silicon content of 20 percent and SiO with D50 of 1.7um1.51, according to the mass ratio: 3 mixing in a planetary ball mill to obtain AlSi/SiO mixed powder, and adding N2In the atmosphere with C3H6And carrying out CVD coating on the AlSi/SiO mixed powder at 800 ℃ for 60min to obtain the lithium battery cathode material.
Comparative example 1
In N2In the atmosphere with C3H61.7um for D50 at 800 deg.C1.5CVD coating was performed for 60min to obtain comparative sample 2.
And (3) performance testing:
corresponding lithium-ion button half-cells were prepared according to the above-described examples and comparative examples. And carrying out electrochemical performance test on the prepared lithium ion button half cell.
Mixing sodium carboxymethylcellulose (CMC) powder with ultrapure deionized water at a ratio of 1:97 at normal temperature, stirring for 6h, and preparing a transparent viscous colloid solution with the mass fraction of 3% for later use. The lithium battery cathode material prepared by the method of the invention comprises the following steps: carbon nanotube: sodium carboxymethylcellulose = 8: 0.8: 1.2, adding CMC solution into a vertical stainless steel tank, adding the carbon tube slurry, stirring at a low speed for half an hour, adding a negative electrode material, and stirring at a high speed to obtain silicon negative electrode slurry for later use. According to the conventional production process of the lithium ion button cell, silicon negative electrode slurry is coated on a current collector by a wet film preparation method, and a negative electrode plate can be obtained by punching a dry film through punching equipment through drying and dehydrating and deoxidizing processes. And assembling the button half cell with a metal lithium sheet, a diaphragm, electrolyte, a positive and negative electrode shell, a spring sheet and a gasket in a glove box, and standing for 12 hours to obtain the lithium ion button half cell with fully soaked interior.
The embodiment can find that the capacity of the button type half cell prepared by the lithium battery cathode material prepared by the invention can reach more than 1000mAh/g in actual detection data gram, even up to 1539mAh/g, the first coulombic efficiency and the capacity retention rate of 5 circles of the lithium battery cathode material can keep better performance, the capacity retention rate of 100 circles of the half cell prepared by the method is higher than 50%, and compared with the theoretical value of the half cell prepared by the same method by using a nano-grade material, the lithium battery cathode material prepared by the invention by using the micron-grade silicon-aluminum alloy and the silicon-oxygen compound is close to the performance of the cell prepared by the nano-grade material.
Fig. 1 shows XRD patterns of the mixed powder and the high-temperature product exemplified in example 1, where the silicon-aluminum alloy reacts with the silica at 740 ℃ in a nitrogen atmosphere, and the high-temperature product shows a diffraction peak related to alumina but no peak corresponding to the simple substance of aluminum as compared with the mixed powder, indicating that the silicon-aluminum alloy is embedded in the silica to react, and at the same time, the diffraction peak intensity of the simple substance of silicon is significantly enhanced, indicating that nano-silicon is generated.
As can be seen from FIG. 2, the Si-Al alloy is spherical particles, and as can be seen from FIG. 3, the Si-Al alloy and the SiO are uniformly dispersed after being mixed by planetary ball milling, so that favorable conditions are created for the next high-temperature reaction or CVD coating. Compared with fig. 2 and 3, fig. 4 shows that the surface of the material prepared by the invention has more particles, and the SEM picture further illustrates that after high-temperature reaction and CVD coating, the silicon-aluminum alloy is tightly embedded into the silicon monoxide, and the silicon monoxide penetrates through the surface and then fully reacts with the silicon monoxide to generate aluminum oxide coated on the generated nano-silicon clusters, and simultaneously, carbon coating further improves the conductivity of the material and the rigidity of the material. The preparation method provided by the invention is further proved that the lithium battery cathode material prepared by using micron-grade silicon-aluminum oxide has excellent battery performance.
In combination with the raw material cost, the micron-level silicon-oxygen compound used in the invention is 200-300 yuan/kg, the nanometer-level silicon-oxygen compound is at least 6000-7000 yuan/kg, and the nanometer-level aluminum powder is flammable and explosive, is very dangerous, and has practical application value from the industrial production perspective. The lithium battery cathode material obtained by the preparation method can be mixed with carbon black, graphite and the like in the later period to prepare the lithium battery cathode material with practical use value.
The above description is intended to be illustrative of the present invention and not to limit the scope of the invention, which is defined by the claims appended hereto.
Claims (10)
1. A preparation method of a high-capacity high-cycle lithium battery cathode material is characterized by comprising the following steps: the method comprises the following steps:
A. carrying out ball milling and mixing on metal aluminum or silicon-aluminum alloy with the particle size of micron and SiOx with the particle size of micron according to the mass ratio of 1: 0.5-5;
B. and heating the mixed powder to 600-900 ℃ in the atmosphere with protective gas, and performing surface carbon coating reaction for 20-300min by using a vapor deposition method to obtain the lithium battery cathode material powder.
2. The method for preparing a negative electrode material for a lithium battery as claimed in claim 1, wherein: in the step B, when the heating temperature is lower than 800 ℃, the mixed powder obtained in the step A is independently heated and reacted for 30-180 min; when the heating temperature is equal to or more than 800 ℃, the vapor deposition reaction is directly carried out for surface carbon coating.
3. The method for preparing a negative electrode material for a lithium battery as claimed in claim 1, wherein: the particle size of the SiOx is 1.0-6.0 um.
4. The method for preparing a negative electrode material for a lithium battery as claimed in claim 1, wherein: the value range of x in the SiOx is 1.0-1.5.
5. The method for preparing a negative electrode material for a lithium battery as claimed in claim 1, wherein: the grain diameter of the metal aluminum or the silicon aluminum alloy is 1.0-6.0 um.
6. The method for preparing a negative electrode material for a lithium battery as claimed in claim 1, wherein: the silicon content of the silicon-aluminum alloy is 5-50%.
7. The method for preparing a negative electrode material for a lithium battery as claimed in claim 1, wherein: the protective gas is any one of inert gas, hydrogen, carbon dioxide and nitrogen.
8. The method for preparing a negative electrode material for a lithium battery as claimed in claim 1, wherein: the mixing ratio of the metal aluminum or the silicon-aluminum alloy and the SiOx in the step A is 1: 1-4.
9. The method for preparing a negative electrode material for a lithium battery as claimed in claim 1, wherein: the particle size of the SiOx is 1.7-5.0 um.
10. A lithium battery is characterized in that: the negative electrode material for the lithium battery prepared by the method for preparing the negative electrode material for the high-capacity high-cycle lithium battery as defined in any one of claims 1 to 9 is applied to the preparation of negative electrode slurry for the lithium battery, and finally the lithium battery is prepared.
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