CN111952569B - Silicon oxide-based negative electrode material for lithium ion battery and preparation method thereof - Google Patents
Silicon oxide-based negative electrode material for lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a silicon oxide-based negative active material for a lithium ion battery and a preparation method thereof, belonging to the technical field of lithium batteries. The material is a C-SiOx-M (0< x <2) composite material, wherein M is one or more of Al, Ga, Ge, In, Sn, Sb, Bi, Fe, Mn, Co, Sn, Ti, Cu and Ni, and C: SiOx: the mass ratio of M is (2-5): (2-5): 1; the invention has the beneficial effects that: the cathode made of the silicon oxide/metal/carbon composite material shows high first efficiency, excellent cycling stability and rate capability, and the conductivity of the composite material is effectively improved.
Description
Technical Field
The present invention relates to a silicon oxide-based negative active material for a lithium ion battery and a method for preparing the same, and more particularly, to a silicon oxide/metal (M, M = Al, Ga, Ge, In, Sn, Sb, Bi, Fe, Mn, Co, Sn, Ti, Cu, Ni, etc.)/carbon composite negative active material, a method for preparing the same, a negative electrode comprising the negative active material, and a secondary battery.
Background
In the current life, most of the lithium ion battery negative electrode materials used by people are carbon-based negative electrode materials, including graphite and graphite derivatives. However, the theoretical specific capacity of the cathode material is only 372mAh/g, which cannot meet the requirements of high-performance and large-capacity lithium ion batteries required by social development. And the preparation process of the carbon negative electrode material is relatively complex, so that the lithium ion battery negative electrode material which has high performance and large capacity and can be commercially produced in large scale is needed. Among various negative electrode materials, silicon-based negative electrode materials are always the focus of research, which is mainly due to the fact that the theoretical specific capacity of silicon reaches 4200mAh/g, and the storage capacity of silicon in the earth is large. However, silicon-based materials have a drawback that large volume deformation (about 300%) caused by intercalation and deintercalation of lithium ions during charging and discharging processes is unavoidable, and the conductivity of the silicon-based materials is low, so that the commercial application of the silicon-based negative electrode materials is restricted by the drawbacks. Compared with a pure silicon negative electrode, the silicon oxide (2615 mAh/g) generates a smaller volume expansion effect (160%) and a longer cycle life in the charging and discharging process, but the silicon oxide negative electrode material has the current difficulty, namely the low initial coulombic efficiency (ICE: 20-30%), and the development of the silicon oxide negative electrode material is seriously influenced by the difficulty.
CN111082006A discloses a silica composite negative electrode material and a preparation method thereof, the composite material firstly carries out carbon coating on the silica powder, then carries out surface in-situ growth of nano carbon fibers, and then carries out secondary granulation to obtain the silica composite negative electrode material. But the synthesis process has the defects of high toxicity, high cost and the like, and the obtained carbon has high hardness and cannot have good adaptability to the volume change of the silicon monoxide. The cycle stability of this composite is therefore poor and no mention is made of the first coulombic efficiency.
CN110526251A discloses a preparation method of a lithium battery silicon dioxide negative electrode material, wherein a proper amount of sodium bicarbonate is measured and added into a mixed solution of water and ethanol, and the mixture is stirred uniformly. And then sequentially adding weighed hexadecyl trimethyl ammonium bromide (CTAB) and Tetraethoxysilane (TEOS) into the mixed solution, stirring for reaction, and performing suction filtration cleaning, acid washing, suction filtration, calcination and heat preservation to obtain the catalyst. However, a large amount of organic solvent is used in the synthesis process, the toxicity is high, and the steps of the preparation process are complicated, so that the cost is greatly increased. Therefore, the composite material has high requirements on production cost.
To date, no composite system with silicon oxide, metal and carbon as a whole has been found to be useful as a negative electrode material for lithium ion batteries.
Disclosure of Invention
Aiming at the problems of large volume change, easy structure damage, poor conductivity and the like in the circulation process of silicon-based and metal negative electrode materials in the prior art, the inventor finds a silicon oxide/metal/carbon composite negative electrode material through experiments. In the composite anode material, metal particles are uniformly embedded on carbon skeletons, and meanwhile, silicon oxide particles are dispersed among the metal composite carbon skeletons, so that a unique porous structure is formed. The defect of poor conductivity of the silicon oxide and the silicon carbide is effectively overcome by compounding the carbon, the first effect of the silicon oxide is improved, and meanwhile, a space is reserved for the volume change of the silicon and the metal by the porous structure, so that the stability of the structure of the silicon carbide is ensured. The invention firstly proposes that the silicon oxide and the metal which are independently researched before are put into a composite system for research, so that the advantages of the silicon oxide and the metal are fully exerted, and the defects of the silicon oxide and the metal are overcome.
The technical scheme adopted for solving the technical problem of the invention is a freeze-drying and high-temperature solid-phase self-assembly synthesis method which is simple and can be used for large-scale commercial production, and the silicon oxide/metal/carbon composite material (C-SiO) with a three-phase porous structure is preparedx-M（0<x<2) To improve the conductivity of the composite, to improve its cycle performance and capacity.
A silicon-based negative electrode material for lithium ion battery is C-SiOx-M（0<x<2) The composite material is characterized In that M is one or more of Al, Ga, Ge, In, Sn, Sb, Bi, Fe, Mn, Co, Sn, Ti, Cu and Ni, wherein C: SiO 2x: the mass ratio of M is (2-5): (2-5): 1.
the material is prepared by the following method:
(1) dissolving a carbon source compound in deionized water according to the mass ratio of 0.3-2.0mg/10ml, and after fully dissolving, mixing silicon oxide powder and the carbon source compound according to the mass ratio of silicon to carbon of 1: 0.5 to 1: 2 to obtain a mixed solution A;
(2) carrying out ultrasonic treatment on the mixed solution A obtained in the step (1) for 15-30min to uniformly disperse silicon oxide powder in the mixed solution, immediately freezing the mixed solution at-40 ℃ to-60 ℃ for 6-8h after the ultrasonic treatment is finished, immediately carrying out vacuum drying treatment for 50-70h after the freezing is finished, and obtaining a precursor B after the vacuum drying is finished;
(3) placing the precursor B in a tubular furnace filled with one or more mixed gases of nitrogen, argon or hydrogen, controlling the heating rate at 5 ℃/min, heating from room temperature to 500 ℃, keeping at 500 ℃ for 3 hours (carbonization), and then naturally cooling to room temperature;
(4) and (3) mixing the precursor B obtained in the step (3) with metal according to a mass ratio of 5: 1-10: 1, mixing and grinding for 1-5h, heating to 1000 ℃ at the speed of 5-15 ℃/min under the condition of one or more of nitrogen, argon or hydrogen, preserving heat for 1-8h, and then naturally cooling to obtain a silicon-based negative electrode material or a mixture C containing the silicon-based negative electrode material;
preferably, the metal is one or more of Al, Ga, Ge, In, Sn, Sb, Bi, Fe, Mn, Co, Sn, Ti, Cu, Ni and the like;
preferably, the carbon source compound is one or more of citric acid, oleic acid, malic acid, glucose, sucrose, sodium oleate, sodium citrate, sodium malate and polyvinylpyrrolidone;
preferably, the silicon oxide refers to silicon oxide with the particle size of 5nm-50 um;
preferably, the drying treatment in the step (2) is preferably performed for 70 hours;
preferably, the gas introduced in the step (3) and the step (4) is a mixed gas of argon and hydrogen, wherein the hydrogen accounts for 5% of the total volume of the gas.
Has the advantages that:
the freeze drying method and the high-temperature solid phase synthesis method have the advantages of simplicity, large-scale production and the like, so that the method can be favorable for effectively popularizing and recognizing the novel silicon-based negative electrode material in the application in future commercial application. Meanwhile, the metal and the carbon source compound can spontaneously carry out self-assembly reaction in a high-temperature solid-phase reaction, so as to obtain the metal modified carbon compound. Therefore, the defects of metal in the process of serving as the lithium battery cathode material are effectively overcome, and the defects of poor conductivity, serious volume expansion and the like of the silicon oxide-based cathode material are complemented.
The negative electrode made of the silicon oxide/metal/carbon composite material shows high first effect, excellent cycling stability and rate capability, and the conductivity of the composite material is effectively improved.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of example 1 prepared in accordance with the present invention;
FIG. 2 is an X-ray diffraction (XRD) of example 1 prepared according to the present invention and comparative example 1;
FIG. 3 is a charge and discharge curve of example 1 prepared in accordance with the present invention;
FIG. 4 is a charge and discharge curve of example 2 prepared in accordance with the present invention;
FIG. 5 is an electrochemical cycling test curve for example 1 prepared in accordance with the present invention;
FIG. 6 is a graph of rate capability test for example 1 prepared in accordance with the present invention;
FIG. 7 is an electrochemical impedance spectrum of example 1 prepared in accordance with the present invention;
fig. 8 is an electrochemical impedance spectrum of comparative example 1.
Detailed Description
The technical solution of the present invention is described in detail by the following examples, which are carried out on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention to be protected is not limited to the following examples.
Example 1
0.3g of glucose and 0.3g of polyvinylpyrrolidone are dissolved in 10ml of deionized water, 1.2g of silica is added after the glucose and the polyvinylpyrrolidone are fully stirred and dissolved, the mixture is stirred and then is subjected to ultrasonic treatment for 20 minutes, the mixture is subjected to freezing treatment for 6 hours after the ultrasonic treatment is finished, the freezing temperature is-50 ℃, and the vacuum drying treatment is carried out for 60 hours after the freezing is finished. After the vacuum drying treatment is finished, the sample is carbonized, the sample is placed in a tube furnace filled with argon-hydrogen mixed gas (5% hydrogen), the heating rate is controlled at 5 ℃/min, the sample is kept at 500 ℃ for 3 hours and then is naturally cooled to the room temperature. Fully mixing and grinding the carbonized sample and germanium powder according to the mass ratio of 5:1, carrying out high-temperature heat treatment on the sample after mixing and grinding, placing the sample in a tubular furnace filled with argon-hydrogen mixed gas (5% hydrogen), controlling the temperature rise rate at 8 ℃/min, and keeping the temperature for 1 hour at 1000 ℃. And after the mixture is cooled to room temperature, taking out the obtained solid powder to obtain the target product C-SiO-Ge.
Example 2
0.3g of glucose and 0.3g of polyvinylpyrrolidone are dissolved in 10ml of deionized water, 1.2g of silicon oxide is added after the complete stirring and dissolution, the ultrasonic treatment is carried out for 20 minutes after the stirring, the freezing treatment is carried out for 6 hours after the ultrasonic treatment is finished, the freezing temperature is-40 ℃, and the vacuum drying treatment is carried out for 60 hours after the freezing is finished. After the vacuum drying treatment is finished, the sample is carbonized, the sample is placed in a tube furnace filled with argon-hydrogen mixed gas (5% hydrogen), the heating rate is controlled at 5 ℃/min, the sample is kept at 500 ℃ for 3 hours and then is naturally cooled to the room temperature. Fully mixing and grinding the carbonized sample and tin powder according to the mass ratio of 5:1, carrying out high-temperature heat treatment on the sample after mixing and grinding, placing the sample in a tubular furnace filled with argon-hydrogen mixed gas (5% hydrogen), controlling the temperature rise rate at 5 ℃/min, and keeping the temperature for 1 hour at 400 ℃. After the mixture is cooled to room temperature, the obtained solid powder is taken out to obtain a target product C-SiO2-Sn。
Example 3
0.3g of glucose and 0.3g of polyvinylpyrrolidone are dissolved in 10ml of deionized water, 0.6g of silica is added after the glucose and the polyvinylpyrrolidone are fully stirred and dissolved, the mixture is stirred and then is subjected to ultrasonic treatment for 20 minutes, the mixture is subjected to freezing treatment for 6 hours after the ultrasonic treatment is finished, the freezing temperature is-60 ℃, and the vacuum drying treatment is carried out for 60 hours after the freezing is finished. After the vacuum drying treatment is finished, the sample is carbonized, the sample is placed in a tube furnace filled with argon-hydrogen mixed gas (5% hydrogen), the heating rate is controlled at 5 ℃/min, the sample is kept at 500 ℃ for 3 hours and then is naturally cooled to the room temperature. Fully mixing and grinding the carbonized sample and germanium powder according to the mass ratio of 5:1, carrying out high-temperature heat treatment on the sample after mixing and grinding, placing the sample in a tubular furnace filled with argon-hydrogen mixed gas (5% hydrogen), controlling the temperature rise rate at 8 ℃/min, and keeping the temperature for 1 hour at 1000 ℃. And after the mixture is cooled to room temperature, taking out the obtained solid powder to obtain the target product C-SiO-Ge.
Comparative example 1
To compare with the three-phase product of example 1, we carried out a comparative experiment. 0.3g of glucose and 0.3g of polyvinylpyrrolidone are dissolved in 10ml of deionized water, 1.2g of silica is added after the glucose and the polyvinylpyrrolidone are fully stirred and dissolved, the mixture is stirred and then is subjected to ultrasonic treatment for 20 minutes, the mixture is subjected to freezing treatment for 6 hours after the ultrasonic treatment is finished, and the mixture is subjected to vacuum drying treatment for 60 hours after the freezing treatment is finished. After the vacuum drying treatment is finished, the sample is carbonized, the sample is placed in a tube furnace filled with argon-hydrogen mixed gas (5% hydrogen), the heating rate is controlled at 5 ℃/min, the sample is kept at 500 ℃ for 3 hours and then is naturally cooled to the room temperature. And after the mixture is cooled to room temperature, taking out the obtained solid powder to obtain a target product C-SiO.
Experimental example 1 characterization of anode material
The scanning electron micrograph shows that example 1 has a porous structure. As a result, referring to fig. 1, the silicon oxide is uniformly embedded on the carbon layers, and the metal germanium is dispersed between the carbon layers compounded by the silicon oxide, thereby forming a unique porous structure.
The materials prepared in example 1 and comparative example 1 were examined by X-ray powder diffraction. The results are shown in FIG. 2. As can be seen by X-ray diffraction pattern (XRD), we succeeded in obtaining the target product by this synthesis process.
Experimental example 1 electrochemical characterization
Uniformly dispersing the negative electrode materials prepared in examples 1-3 and comparative example 1, acetylene black as a conductive agent and sodium alginate as a binder in deionized water to form slurry, uniformly coating the slurry on copper foil, drying the copper foil in a drying oven at 50-140 ℃, cutting the electrode plate coated with the active substances into small wafers, and adopting a conventional button battery as a test battery, wherein lithium foil is used as a counter electrode, and LiPF is used as a binder6The organic solution is electrolyte and is assembled in a glove box.
The cells consisting of the material of example 1 and the material of example 2 were subjected to electrochemical tests, the results of which are shown in fig. 3 and 4.
It can be seen from the charge and discharge curves of the cycle test that the first coulombic efficiency of example 1 can reach 72%, and the first coulombic efficiency of example 2 can reach 68%, so that the high first coulombic efficiency can indicate that the performance of the material is good.
The electrochemical test was performed on the battery composed of the material of example 1 and the material of comparative example 1, and the results thereof are shown in fig. 4 and 5.
It can be seen from the cycle performance test that example 1 having a three-phase composite composition has good capacity retention. This is probably due to its unique porous structure, which can provide sufficient volume change space for the active material, and the carbon layer can effectively expand and contract to adapt to the volume change of the loaded metal during the charge and discharge process. As can be seen from the rate tests at different current densities, example 1 has very good high rate charge and discharge characteristics.
As can be seen from the impedance tests of fig. 7 and 8, example 1 has a very small impedance, whereas comparative example 1 exhibits a larger impedance. This is mainly because the metal greatly shortens the transmission path of lithium ions inside these active materials, thereby improving the conductivity thereof.
In addition, the method adopts a freeze drying method and a high-temperature solid-phase reaction, the reaction method is simple and controllable, large-scale production can be realized, and the synthesis process is favorable for cost control and commercial popularization and application.
Claims (9)
1. A silicon oxide-based negative electrode material for lithium ion batteries is characterized in that the material is C-SiOx-Ge (0<x<2) A composite material, wherein C: SiO 2x: the mass ratio of Ge is (2-5): (2-5): 1; in the composite cathode material, Ge particles are uniformly embedded on carbon skeletons, and meanwhile, silicon oxide particles are also dispersed among the Ge-compounded carbon skeletons, so that a unique porous structure is formed.
2. The silicon oxide-based anode material for the lithium ion battery according to claim 1, wherein the particle size of the silicon oxide is 5nm to 50 um.
3. A preparation method of a silicon oxide-based negative electrode material for a lithium ion battery is characterized by comprising the following steps:
(1) dissolving a carbon source compound in deionized water according to the mass ratio of 0.3-2.0mg/10ml, and after fully dissolving, mixing silicon oxide powder and the carbon source compound according to the mass ratio of silicon to carbon of 1: 0.5 to 1: 2 to obtain a mixed solution A; (2) performing ultrasonic treatment on the mixed solution A obtained in the step (1) for 10-30min to uniformly disperse silicon oxide powder in the mixed solution, immediately performing freezing treatment after the ultrasonic treatment is completed, freezing for 6-8h at-40 ℃ to-60 ℃, immediately performing vacuum drying for 50-70h after the freezing is completed, and obtaining a precursor B after the vacuum drying is completed;
(3) placing the precursor B in a tubular furnace filled with one or more mixed gases of nitrogen, argon or hydrogen, controlling the heating rate at 5 ℃/min, heating from room temperature to 500 ℃, keeping at 500 ℃ for 3 hours, and then naturally cooling to room temperature;
(4) and (3) mixing the precursor B obtained in the step (3) with metal according to a mass ratio of 5: 1-10: 1, mixing and grinding for 1-5h, heating to 1000 ℃ at the speed of 5-15 ℃/min under the condition of one or more mixed gases of nitrogen, argon or hydrogen, preserving heat for 1-8h, and then naturally cooling to obtain the silicon-based negative electrode material or the mixture C containing the silicon-based negative electrode material.
4. The method for preparing the silicon oxide-based anode material for the lithium ion battery as claimed in claim 3, wherein the carbon source compound is one or more of citric acid, oleic acid, malic acid, glucose, sucrose, sodium oleate, sodium citrate, sodium malate, chitosan, and polyvinylpyrrolidone.
5. The method for preparing a silicon oxide-based anode material for a lithium ion battery according to claim 3, wherein,
the metal is one or more of Al, Ga, Ge, In, Sn, Sb, Bi, Fe, Mn, Co, Sn, Ti, Cu or Ni.
6. The method for preparing a silicon oxide-based anode material for a lithium ion battery according to claim 3, wherein the mixed gas in the step (3) is a mixed gas of argon and hydrogen, and the hydrogen content is 5%.
7. The method for preparing a silicon oxide-based anode material for a lithium ion battery according to claim 3, wherein the drying treatment in the step (2) is for 70 hours.
8. The method of claim 3, wherein the metal is Ge.
9. The method according to claim 3, wherein the mixed gas in the steps (3) and (4) is argon and hydrogen, and the hydrogen accounts for 5% of the total volume of the gas.
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