CN111403708B - Lithium ion battery silicon monoxide composite negative electrode material and preparation method thereof, and lithium ion battery - Google Patents
Lithium ion battery silicon monoxide composite negative electrode material and preparation method thereof, and lithium ion battery Download PDFInfo
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Abstract
The invention discloses a preparation method of a silicon monoxide composite negative electrode material of a lithium ion battery, which comprises the following steps: carrying out high-temperature roasting disproportionation on a silicon monoxide raw material to prepare a disproportionated silicon monoxide raw material; the first stage is as follows: roasting the obtained disproportionated silicon monoxide raw material, heating to 500-1000 ℃ under protective gas, roasting, keeping the temperature for 0.5-2 h, introducing organic gas for 1-20 h, and closing the organic gas after the reaction is completed; and a second stage: continuously heating to 1000-1800 ℃, introducing hydrogen and organic gas for 1-20 h, and cooling after the reaction is completed to obtain the silicon monoxide composite negative electrode material; and crushing, screening and demagnetizing the obtained silicon monoxide composite negative electrode material to obtain the silicon monoxide composite negative electrode material of the lithium ion battery. The lithium ion battery silicon oxide composite negative electrode material prepared by the preparation method has good cycle performance and conductivity, and the service life of the battery is prolonged.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon monoxide composite negative electrode material of a lithium ion battery, a preparation method of the silicon monoxide composite negative electrode material and the lithium ion battery.
Background
Compared with the traditional battery, the lithium ion secondary battery mainly shows the aspects of large specific capacity, long cycle life, high safety, little environmental pollution and the like. At present, the cathode material of lithium ion secondary batteries, which has been commercialized, is mainly a carbon material, and has been successfully applied to various electronic products, automobiles, and other devices. However, the main problem of the carbon material is that the maximum theoretical specific capacity is only 372mAh/g, and the current requirement is difficult to meet.
The silicon-based material is used as a lithium ion battery cathode material with great potential at present, and has the main advantages of large specific capacity, wherein the theoretical specific capacity of a silicon single material reaches 4200 mAh/g, and the theoretical specific capacity of a silicon protoxide material also reaches 2100mAh/g, which is far larger than that of a carbon cathode material, but the defects of the silicon material are obvious, and mainly show that in the circulating process, the expansion rate can reach more than 300%, and meanwhile, the silicon-based material has poor conductivity, so that the circulating process is caused, the active material is easy to pulverize and fall off, the service life of the battery is seriously influenced, the circulating expansion problem and the conductivity of the silicon-based material are improved, and the silicon-based material is a research and a difficulty of the current silicon-based material.
Therefore, the silicon oxide composite negative electrode material of the lithium ion battery with excellent cycle performance and conductivity is provided.
Disclosure of Invention
The invention mainly aims to provide a silicon monoxide composite negative electrode material of a lithium ion battery and a preparation method thereof, and the silicon monoxide composite negative electrode material has the advantages of improving the conductivity and the cycle performance of the negative electrode material.
In order to achieve the purpose, the invention provides a preparation method of a silicon monoxide composite negative electrode material of a lithium ion battery, which comprises the following steps:
(1) carrying out high-temperature roasting disproportionation on the raw material of the inferior silicon oxide, wherein the temperature range is 1000-1500 ℃, and preserving the heat for 5-20 h to prepare a disproportionated inferior silicon oxide raw material; wherein, the high-temperature roasting adopts a rotary furnace, a box furnace or a roller kiln, and the heating rate is 1-10 ℃/min; preferably, the roasting equipment is a rotary furnace, and the rotation speed is 0.1-2 rpm.
(2) And a first stage: roasting the obtained disproportionated silicon monoxide raw material, heating to 500-1000 ℃ under protective gas, roasting, keeping the temperature for 0.5-5 h at the heating rate of 1-10 ℃/min, introducing organic gas for 1-20 h, and closing the organic gas after the reaction is completed; and a second stage: continuously heating to 1000-1800 ℃, wherein the heating rate is 1-10 ℃/min, introducing hydrogen and organic gas for 1-20 h, and cooling after the reaction is completed to obtain the silicon monoxide composite negative electrode material; wherein, the cooling is natural cooling under protective gas.
(3) And crushing, screening and demagnetizing the obtained silicon monoxide composite negative electrode material to obtain the silicon monoxide composite negative electrode material of the lithium ion battery.
Preferably, the median particle diameter D50 of the raw material of silica is 1 to 50 μm, and before step (1), the method further comprises: and controlling the granularity and the shape by adopting a ball mill, a crusher or a pulverizer, and then sieving and demagnetizing to prepare the qualified silicon monoxide raw material.
Preferably, the disproportionation temperature is controlled within the range of 800-1200 ℃; the obtained disproportionated silicon oxide raw material is mainly silicon dioxide material as an outer layer and is a silicon simple substance as an inner layer.
Preferably, the injection flow ratio of the organic gas to the protective gas in the first stage is 1: 1-1: 5, the flow of the protective gas in the first stage is 1-125L/min, and the flow of the organic gas in the first stage is 1-25L/min; the driving flow ratio of the organic gas to the hydrogen in the second stage is 1: 0.5-1: 5, the flow of the protective gas in the second stage is 1-50L/min, the flow of the organic gas is 1-10L/min, and the flow of the hydrogen is 0.5-50L/min.
Preferably, the adding amount of the disproportionated silicon monoxide in the step (2) is 1-5 kg, and the mass ratio of the high-temperature disproportionated silicon monoxide to the organic gas flow rate in the first stage is 1: 1-1: 5.
Preferably, the organic gas is one or more of acetylene, methane, natural gas, ethanol, propanol, benzene, ethane, ethylene, butane, butylene, hexane, toluene, xylene and ethylbenzene.
Preferably, the protective gas is an inert gas of nitrogen, argon, helium, neon and xenon.
The lithium ion battery silicon monoxide composite negative electrode material prepared by the preparation method is coated by a double-layer carbon structure, the inner layer is an amorphous carbon coating layer which grows on the surface of the silicon monoxide by adopting a vapor deposition CVD method, and the outer layer is a graphene coating layer which grows regularly in situ.
Preferably, the particle size median diameter D50 of the silicon monoxide composite negative electrode material of the lithium ion battery is 1-80 μm, the first reversible capacity is not less than 1650mAh/g, the first coulombic efficiency is more than 77%, the capacity retention rate is more than 90%, the expansion rate is less than 45% after 50 weeks of circulation, and the conductivity is more than 4.5S/m.
The lithium ion battery cathode material adopts the silicon monoxide composite cathode material of the lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
1. in the preparation method of the cathode material, the silicon monoxide is transformed into a core-shell structure with an outer layer rich in silicon dioxide and an inner core silicon simple substance after high-temperature disproportionation, so that the generation of non-chemical active silicon carbon compounds can be inhibited, and the performances such as material capacity and the like are obviously improved;
2. the structure of the outer-layer carbon material can be effectively controlled by a two-step vapor deposition method, the amorphous carbon layer generated by the first-step vapor deposition method can tightly coat the surface of the silicon oxide, and meanwhile, nucleation sites are provided for the subsequent in-situ generation of graphene; by adopting the double-layer carbon structure, the available expansion space of the prepared cathode material is obviously increased, the pulverization and the falling of the material caused by overlarge expansion in the circulation process can be obviously improved, and the coating uniformity of the silicon oxide cathode material is obviously improved by the double-layer carbon structure.
3. The structure of outer graphene is improved by controlling the flow rate and reaction temperature of the organic gas, a graphene carbon layer which is regularly arranged and extends outwards is obtained, the contact among negative electrode material particles is obviously improved, the contact area is obviously increased, and the overall conductivity of the material is obviously improved.
Drawings
FIG. 1 is a graph of conductivity data for example 1, example 2, and comparative example 1 at various compaction densities.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
2kg of SiO powder with the particle size median diameter D50 of 10 mu m is taken and added into a rotary furnace, nitrogen is introduced to exhaust oxygen, the flow rate is set to be 10L/min, after the oxygen exhaust is finished, the temperature is raised and the roasting is carried out, the roasting temperature is 1000 ℃, the temperature raising speed is 10 ℃/min, and the rotary speed is 1 rpm. After the reaction is finished, cooling the roasting temperature to 750 ℃, naturally cooling in a nitrogen atmosphere, keeping the temperature for 1h, introducing acetylene gas when the temperature is stable, setting the flow rate to be 3L/min, keeping the temperature unchanged, introducing air for 3h, closing the acetylene gas after the reaction is finished, raising the temperature to 1200 ℃, raising the temperature at the speed of 10 ℃/min, keeping the temperature for 1h, then introducing methane gas and hydrogen gas, setting the flow rate of methane gas to be 3L/min, setting the flow rate of hydrogen gas to be 1L/min, keeping the temperature unchanged, introducing air for 5h, closing the hydrogen gas and the methane gas after the reaction is finished, naturally cooling in the nitrogen atmosphere, taking out the material after the cooling is finished, and crushing, screening and demagnetizing the material to obtain the lithium ion battery silicon oxide composite negative electrode material with the median particle size D50 of 1-80 mu m.
Example 2
3kg of SiO powder with the particle size median diameter D50 of 6 mu m is taken and added into a rotary furnace, nitrogen is introduced to exhaust oxygen, the flow rate is set to be 10L/min, after the oxygen exhaust is finished, the temperature is increased and the roasting is carried out, the roasting temperature is 1000 ℃, the temperature increasing rate is 10 ℃/min, and the rotary speed is 1 rpm. After the reaction is finished, cooling the roasting temperature to 800 ℃, naturally cooling in a nitrogen atmosphere, keeping the temperature for 1h, introducing ethanol steam when the temperature is stable, setting the flow rate to be 2L/min, keeping the temperature unchanged, introducing air for 3h, after the reaction is finished, closing acetylene gas, raising the temperature to 1200 ℃, raising the temperature at the speed of 10 ℃/min, keeping the temperature for 1h, then introducing methane gas and hydrogen gas, setting the methane gas flow rate to be 3L/min, setting the hydrogen gas flow rate to be 1L/min, keeping the temperature unchanged, introducing air for 5h, after the reaction is finished, closing the hydrogen gas and the methane gas, naturally cooling in the nitrogen atmosphere, after the temperature is completely cooled, taking out the material, and crushing, screening and demagnetizing to obtain the lithium ion battery silicon oxide composite negative electrode material with the median particle size D50 of 1-80 mu m.
Example 3
Adding 4kg of SiO powder with the particle size median diameter D50 of 8 μm into a rotary furnace, introducing nitrogen gas for oxygen discharge, setting the flow rate at 10L/min, heating and roasting after the oxygen discharge is finished, wherein the roasting temperature is 1000 ℃, the heating rate is 10 ℃/min, and the rotary speed is 1 rpm. After the reaction is finished, introducing methane gas, setting the flow rate to be 4L/min, keeping the temperature and ventilating for 3h, after the reaction is finished, closing the methane gas, raising the temperature to 1200 ℃, raising the temperature rate to 10 ℃/min, keeping the temperature for 1h, then injecting the methane gas and the hydrogen gas, setting the flow rate of the methane gas to be 4L/min, setting the flow rate of the hydrogen gas to be 1L/min, keeping the temperature and ventilating for 5h, after the reaction is finished, closing the hydrogen gas and the methane gas, naturally cooling in the nitrogen atmosphere, after the cooling is finished, taking out the material, and crushing, screening and demagnetizing the material to obtain the lithium ion battery silicon monoxide composite negative electrode material with the median particle size D50 of 1-80 mu m.
Example 4
3kg of SiO powder material with the particle size median diameter D50 of 2 mu m is taken and added into a rotary furnace, nitrogen is introduced to exhaust oxygen, the flow rate is set to be 10L/min, after the oxygen exhaust is finished, the temperature is raised and the roasting is carried out, the roasting temperature is 1000 ℃, the temperature raising speed is 10 ℃/min, and the rotary speed is 1 rpm. After the reaction is finished, cooling the roasting temperature to 900 ℃, keeping the temperature for 1h, naturally cooling in a nitrogen atmosphere, introducing toluene gas when the temperature is stable, setting the flow rate to be 3L/min, keeping the temperature unchanged, introducing the gas for 3h, after the reaction is finished, closing the toluene, raising the temperature to 1200 ℃, raising the temperature rate to 10 ℃/min, keeping the temperature for 1h, then introducing acetylene gas and hydrogen gas, setting the flow rate of the acetylene gas to be 4L/min, setting the flow rate of the hydrogen gas to be 1L/min, keeping the temperature, introducing the gas for 5h, after the reaction is finished, closing the hydrogen gas and the methane gas, naturally cooling in the nitrogen atmosphere, after the temperature is completely reduced, taking out the material, and crushing, screening and demagnetizing to obtain the lithium ion battery silicon oxide composite negative electrode material with the median particle size D50 of 1-80 mu m.
Example 5
2kg of SiO powder material with the particle size median diameter D50 of 2 mu m is taken and added into a rotary furnace, nitrogen is introduced to exhaust oxygen, the flow rate is set to be 10L/min, after the oxygen exhaust is finished, the temperature is raised and the roasting is carried out, the roasting temperature is 1000 ℃, the temperature raising speed is 10 ℃/min, and the rotary speed is 1 rpm. After the reaction is finished, cooling the roasting temperature to 900 ℃, keeping the temperature for 1h, naturally cooling in a nitrogen atmosphere, introducing natural gas when the temperature is stable, setting the flow rate to be 5L/min, keeping the temperature unchanged, injecting gas for 3h, after the reaction is finished, closing toluene, raising the temperature to 1200 ℃, raising the temperature rate to 10 ℃/min, keeping the temperature for 1h, then injecting acetylene gas and hydrogen gas, setting the flow rate of acetylene gas to be 4L/min, setting the flow rate of hydrogen gas to be 1L/min, keeping the temperature unchanged, injecting gas for 5h, after the reaction is finished, closing hydrogen gas and methane gas, naturally cooling in a nitrogen atmosphere, after the cooling is finished, taking out the material, and crushing, screening and demagnetizing to obtain the lithium ion battery silicon oxide composite negative electrode material with the median particle size D50 of 1-80 mu m.
Comparative example 1
2kg of SiO powder material with the particle size median diameter D50 of 3 mu m is taken and added into a rotary furnace, nitrogen is introduced to exhaust oxygen, the flow rate is set as 10L/min, after the oxygen exhaust is finished, the temperature is raised and the roasting is carried out, the roasting temperature is 1000 ℃, the temperature raising speed is 10 ℃/min, and the rotary speed is 1 rpm. And after the reaction is finished, cooling the roasting temperature to 750 ℃, naturally cooling the roasting temperature in a nitrogen atmosphere, keeping the temperature for 1h, introducing acetylene gas when the temperature is stable, setting the flow rate to be 3L/min, keeping the temperature unchanged, introducing the air for 3h, closing the acetylene gas after the reaction is finished, naturally cooling the roasting temperature in the nitrogen atmosphere, and after the temperature is completely cooled, taking out the material, and crushing, screening and demagnetizing the material to obtain the lithium ion battery silicon oxide composite negative electrode material with the median particle size D50 of 1-80 mu m.
Comparative example 2
Taking 2kg of SiO powder with the median particle size D50 of 10 microns to perform solid-phase mixing with a carbon-based precursor material, wherein the mixing mass ratio of the silicon oxide powder to the carbon-based precursor is 1:0.1, then performing high-temperature roasting in a box-type furnace under the protection of nitrogen atmosphere, wherein the roasting temperature is 700 ℃, the heat preservation time is 5h, the heating rate is 5 ℃/min, naturally cooling after the roasting is completed, taking out the material, and crushing, screening and demagnetizing to obtain the lithium ion battery silicon oxide composite negative electrode material with the median particle size D50 of 1-80 microns.
The anode materials of examples 1-5 and comparative examples 1-2 were tested, and the particle size range and distribution of the materials were tested using a malvern laser particle size tester MS 3000; the specific surface area of the material is tested by adopting Tristar3000 full-automatic specific surface area and porosity analysis of American Michel instruments; the morphology and the particle size of the sample are observed by a scanning electron microscope of Hitachi S4800.
Testing the conductivity of the material by adopting MCP-PD51 powder conductivity testing equipment of Mitsubishi chemical company of Japan; fig. 1 reflects the variation in conductivity of different materials and the conductivity of different materials at the same compaction density.
Electrochemical cycling performance was tested using the following method: mixing a negative electrode material, a conductive agent and a binder in a solvent according to a mass ratio of 92:2:6, controlling the solid content to be 55%, coating the mixture on a copper foil current collector, and drying to obtain a negative electrode plate; then using a conventional positive plate and 1mol/L LiPF6The battery is characterized by comprising an/EC + DMC (V/V is 1:1) electrolyte, a CeLgard2400 diaphragm and a 18650 cylindrical battery, wherein the housing is assembled by adopting a conventional production process, constant-current charging and discharging are carried out under the rate of 1C, and the charging and discharging voltage is limited to 2.75-4.2V.
The electrochemical test results and the expansion ratio test results of the negative electrode materials prepared in examples 1 to 5 and comparative examples 1 and 2 are shown in table 1:
TABLE 1
By combining the electrochemical test results and the expansion rate test in examples 1 to 5, as can be seen from table 1, the particle size median diameter D50 of the silicon oxide composite negative electrode material of the lithium ion battery obtained in examples 1 to 5 is 1 to 80 μm, the first reversible capacity is not lower than 1650mAh/g, the first coulombic efficiency is greater than 77%, the capacity retention rate is greater than 90% after 50 weeks of circulation, the expansion rate is less than 45%, and the conductivity is greater than 4.5S/m.
In contrast, comparative example 1 and comparative example 2 are insufficient in capacity, cycle performance, expansion rate, conductivity, and the like, respectively. Compared with comparative examples 1 and 2, the lithium ion secondary battery composite negative electrode material prepared by the preparation method disclosed by the invention has good cycle performance, low expansion rate and excellent guiding performance under the condition of ensuring high capacity to be unchanged, and the service life of the battery is prolonged.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. The composite negative electrode material is characterized in that the composite negative electrode material is coated by a double-layer carbon structure, the inner layer is an amorphous carbon coating layer which grows on the surface of the silicon oxide by adopting a vapor deposition CVD method, and the outer layer is a graphene coating layer which grows in situ and is regularly arranged;
the preparation method comprises the following steps:
(1) carrying out high-temperature roasting disproportionation on the raw material of the inferior silicon oxide, wherein the temperature range is 1000-1500 ℃, and preserving the heat for 5-20 h to prepare a disproportionated inferior silicon oxide raw material;
(2) and a first stage: roasting the obtained disproportionated silicon monoxide raw material, heating to 500-1000 ℃ under protective gas, roasting, keeping the temperature for 0.5-5 h at the heating rate of 1-10 ℃/min, introducing organic gas for 1-20 h, and closing the organic gas after the reaction is completed; and a second stage: continuously heating to 1000-1800 ℃, wherein the heating rate is 1-10 ℃/min, introducing hydrogen and organic gas for 1-20 h, and cooling after the reaction is completed to obtain the silicon monoxide composite negative electrode material;
(3) crushing, screening and demagnetizing the obtained silicon monoxide composite negative electrode material to obtain a silicon monoxide composite negative electrode material of the lithium ion battery;
the obtained disproportionated silicon oxide raw material is mainly silicon dioxide material as an outer layer and is a silicon simple substance as an inner layer;
the injection flow ratio of the organic gas to the protective gas in the first stage is 1: 1-1: 5, the flow of the protective gas in the first stage is 1-125L/min, and the flow of the organic gas in the first stage is 1-25L/min; the driving flow ratio of the organic gas to the hydrogen in the second stage is 1: 0.5-1: 5, the flow of the protective gas in the second stage is 1-50L/min, the flow of the organic gas is 1-10L/min, and the flow of the hydrogen is 0.5-50L/min;
the structure of the outer-layer carbon material can be effectively controlled by a two-step vapor deposition method, and the amorphous carbon layer generated by the first-step vapor deposition method not only can tightly coat the surface of the silicon oxide, but also can provide nucleation sites for the subsequent in-situ generation of graphene.
2. The silicon monoxide composite negative electrode material of the lithium ion battery as claimed in claim 1, wherein the median particle diameter D50 of the silicon monoxide raw material is 1-50 μm, and the method further comprises the following steps before the step (1): and controlling the granularity and the shape by adopting a ball mill, a crusher or a pulverizer, and then sieving and demagnetizing to prepare the qualified silicon monoxide raw material.
3. The silicon oxide composite negative electrode material for the lithium ion battery as claimed in claim 1, wherein the amount of the disproportionated silicon oxide raw material added in step (2) is 1-5 kg.
4. The silicon oxide composite anode material for the lithium ion battery as claimed in claim 1, wherein the organic gas in the first stage and the second stage is one or more of acetylene, methane, natural gas, ethanol, propanol, benzene, ethane, ethylene, butane, butylene, hexane, toluene, xylene and ethylbenzene.
5. The lithium ion battery silicon monoxide composite negative electrode material as claimed in claim 1, wherein the protective gas is nitrogen, argon, helium, neon or xenon.
6. The lithium ion battery silicon monoxide composite negative electrode material of claim 1, wherein the particle size median diameter D50 of the lithium ion battery silicon monoxide composite negative electrode material is 1-80 μm, the first reversible capacity is not less than 1650mAh/g, the first coulombic efficiency is more than 77%, the capacity retention rate is more than 90% after 50 weeks of circulation, the expansion rate is less than 45%, and the conductivity is more than 4.5S/m.
7. A lithium ion battery, characterized in that the negative electrode material of the lithium ion battery adopts the silicon monoxide composite negative electrode material of the lithium ion battery according to claim 6.
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