CN112133909A - Antimony sulfide-based negative electrode material for lithium ion battery and preparation method thereof - Google Patents

Antimony sulfide-based negative electrode material for lithium ion battery and preparation method thereof Download PDF

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CN112133909A
CN112133909A CN202011020805.4A CN202011020805A CN112133909A CN 112133909 A CN112133909 A CN 112133909A CN 202011020805 A CN202011020805 A CN 202011020805A CN 112133909 A CN112133909 A CN 112133909A
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negative electrode
lithium ion
antimony sulfide
electrode material
based negative
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CN112133909B (en
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程勇
王少华
申亚斌
王立民
尹东明
梁飞
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Zhejiang Linrun New Energy Technology Co ltd
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides an antimony sulfide-based negative electrode material for a lithium ion battery and a preparation method thereof, and relates to the field of negative electrode materials for lithium ion batteries. The method comprises the steps of mechanically mixing antimony trioxide, expanded graphite and sulfur powder at a high speed for a long time by adopting a mechanical ball milling method to form a composite material, and annealing and vulcanizing in argon to obtain the antimony sulfide-based composite material with the sulfur-doped graphite packaging antimony sulfide structure. The composite material is compounded with the sulfur-doped graphite material and the graphene stripped from the expanded graphite, so that the electronic conductivity of the antimony sulfide can be increased, and meanwhile, an encapsulation structure formed by the existence of sulfur powder during ball milling is favorable for relieving the agglomeration of the antimony sulfide caused by volume expansion; the combined action of the two greatly improves the initial coulombic efficiency, the reversibility of conversion reaction, the circulation stability and the rate capability. The mechanical ball milling method is simple and easy to operate and convenient for large-scale production.

Description

Antimony sulfide-based negative electrode material for lithium ion battery and preparation method thereof
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to an antimony sulfide-based cathode material for a lithium ion battery and a preparation method thereof.
Background
Lithium ion batteries have been widely used in many fields such as portable electronic devices, electric vehicles, and energy storage due to their advantages such as high energy density and long cycle life, and have become a necessity in daily life. However, the theoretical specific capacity of the commercial graphite negative electrode widely applied at present is only 372mAh g-1And the development of high-capacity and high-power lithium ion batteries is severely restricted, so that the development of high-specific-capacity cathode materials is imminent. At present, high-specific-capacity cathode materials such as silicon-based, tin-based, antimony-based and transition metal oxides are widely researched, but the high-specific-capacity cathode materials have the defects of high raw material price, huge volume expansion in the lithium desorption process of the materials, low first coulombic efficiency and the like, and the development of the high-specific-capacity cathode materials is severely limited.
The antimony sulfide cathode material has rich raw materials, low price and 947mAh g-1The material has many advantages such as high theoretical specific capacity and the like, and is hopeful to become a next-generation high-cost performance anode material for replacing graphite. However, it also has the problems of low first coulombic efficiency, poor cycle stability and low capacity output caused by poor conductivity, large volume expansion and poor reversibility of conversion reaction, and the research on antimony-based materials is relatively few, and patent CN107331842A discloses Sb prepared by high energy ball milling method2S3-C composite material having good cycling stability when used in the negative electrode of a lithium ion battery, but which hasHas relatively poor rate capability, and can only output specific capacity of 400mAh/g under the current density of 2A/g. Patent CN110364706A discloses a method for preparing Sb/Sb alloy by high-energy ball milling2O3A lamellar secondary particle composite material having particles distributed on a graphitic carbon material, which has a high output capacity when used in a negative electrode of a lithium ion battery, but has relatively poor initial coulombic efficiency and cycle stability. Therefore, the design of the antimony sulfide-based negative electrode material with high electronic conductivity, high first coulombic efficiency and high cycling stability is very important, and meanwhile, the simple, feasible and low-cost preparation method is also beneficial to large-scale production of the antimony sulfide negative electrode material, and the combination of the two advantages has important significance for wide application of the antimony sulfide negative electrode material.
Disclosure of Invention
The invention aims to solve the problems of low first coulombic efficiency, poor cycle stability and low capacity output of the conventional antimony sulfide-based negative electrode material, and provides an antimony sulfide-based negative electrode material for a lithium ion battery and a preparation method thereof.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a preparation method of antimony sulfide-based negative electrode material for lithium ion batteries comprises the following steps:
the method comprises the following steps: placing antimony trioxide, expanded graphite and sulfur powder in a ball milling tank to obtain a premixed material;
step two: mixing the premixed material obtained in the step one with ball milling beads to obtain a ternary mixed material of antimony trioxide/expanded graphite/sulfur powder;
step three: and (4) annealing the ternary mixed material obtained in the step two in an inert protective atmosphere to obtain the antimony sulfide-based negative electrode material for the lithium ion battery.
Preferably, the mass ratio of the antimony trioxide, the expanded graphite and the sulfur powder in the first step is (0.2-0.6): (0.05-0.15): (0.4-0.6).
Preferably, the antimony trioxide has an average size of 700 nm.
Preferably, the expanded graphite is obtained by treating commercial expandable graphite in a tube furnace filled with inert atmosphere at a high temperature of 1000 ℃ for 1min, the heating rate is 10 ℃ per minute, and the diameter of the expandable graphite is 75 microns.
Preferably, the ball milling beads in the second step are made of zirconium dioxide.
Preferably, in the second step, the ball-to-material ratio of the ball milling beads to the premix material is (20:1) - (100: 1).
Preferably, the mixing time of the second step is 5-40 h, and the speed is 200-480 r/min.
Preferably, the inert protective atmosphere in the third step is argon or nitrogen.
Preferably, the annealing temperature in the third step is 350-550 ℃, and the annealing time is 1-3 hours.
The invention also provides the antimony sulfide-based negative electrode material for the lithium ion battery, which is obtained by the preparation method.
The invention has the advantages of
The invention provides an antimony sulfide-based negative electrode material for a lithium ion battery and a preparation method thereof, the method adopts a simple mechanical ball milling method to mechanically mix antimony trioxide, expanded graphite and sulfur powder at a high speed for a long time to form a composite material, and the antimony sulfide-based composite material with an antimony sulfide structure encapsulated by sulfur-doped graphite is obtained after annealing and vulcanization in an inert atmosphere; the combined action of the two greatly improves the initial coulombic efficiency, the reversibility of conversion reaction, the circulation stability and the rate capability. The mechanical ball milling method is simple and easy to operate and convenient for large-scale production.
The experimental results show that: sb prepared by the method2S3The @ EG' -S composite material has the first-turn coulombic efficiency of 86.78% and the first discharge specific capacity of 93% under the current density of 0.2C in the voltage range of 0.01-3.0V8.3mAh g-1. At 1000mA g-1Output specific capacity 666.2mAh g after 100 times of circulation under current density-1The capacity retention rate can reach 91.2%. At 5000mA g-1The current density of the capacitor is cycled for 100 times and then the specific capacity of the capacitor is 548mAh g-1The capacity retention rate can reach 89.1%. The specific capacity of 444mAh g can be output under the high current density of 15C-1. Matched with a commercial NCM333 ternary positive electrode material to be matched with a full battery, and the full battery outputs 136.3mAh g of specific capacity after being cycled for 100 times under the current density of 0.5C-1The capacity retention rate can reach 89.7%, and the specific capacity of 107mAh g can be output under the high current density of 4C-1. Therefore, the antimony sulfide-based composite negative electrode material prepared by the method has good electrochemical lithium storage property, can be widely applied to negative electrode materials of lithium ion batteries, and is suitable for popularization and application.
Drawings
FIG. 1 shows Sb obtained in example 12S3An XRD spectrogram of the @ EG' -S composite anode material.
FIG. 2 shows Sb obtained in example 12S3SEM, TEM and EDS pictures of the @ EG' -S composite negative electrode material. Wherein a is Sb obtained in example 12S3SEM pictures of the @ EG' -S composite negative electrode material; b is Sb obtained in example 12S3TEM picture of @ EG' -S composite negative electrode material; c is Sb obtained in example 12S3HRTEM picture of graphene stripped from @ EG' -S composite negative electrode material; d is Sb obtained in example 12S3EDS spectrum picture of @ EG' -S composite negative electrode material.
FIG. 3 shows Sb obtained in example 12S3The initial charge-discharge curve graph of the @ EG' -S composite negative electrode material for the lithium half-cell is in a voltage range of 0.01-3.0V and under a current density of 200 mA/g.
FIG. 4 shows Sb obtained in example 12S3A circulation stability test chart of the @ EG' -S composite negative electrode material for the lithium half-cell under the voltage range of 0.01-3.0V and the current densities of 1000mA/g and 5000 mA/g;
FIG. 5 shows Sb obtained in example 12S3The voltage of the @ EG' -S composite anode material to the lithium half-cell is 0.01-3.0VAnd (4) a multiplying power performance test chart in the interval.
FIG. 6 shows Sb obtained in example 12S3And a full battery electrochemical performance diagram matching the @ EG' -S composite negative electrode material with a commercial NCM333 ternary positive electrode material. Wherein a is a cyclic stability test chart at a current density of 0.5C; and b is a multiplying power performance test chart.
FIG. 7 shows Sb obtained in example 22S3The initial charge-discharge curve graph of the @ EG' -S composite negative electrode material is used for a lithium half-battery under the voltage range of 0.01-3.0V and the current density of 200mA/g when the ball milling time is 8h and 15 h.
FIG. 8 shows Sb obtained in example 32S3The material proportion of the @ EG' -S composite negative electrode material is 6: 1:5 (antimony trioxide: expanded graphite: sulfur powder) on the lithium half-cell under the voltage range of 0.01-3.0V and the current density of 200 mA/g.
Detailed Description
A preparation method of antimony sulfide-based negative electrode material for lithium ion batteries comprises the following steps:
the method comprises the following steps: placing antimony trioxide, expanded graphite and sulfur powder in a ball milling tank to obtain a premixed material; the mass ratio of the antimony trioxide to the expanded graphite to the sulfur powder is preferably (0.2-0.6): (0.05-0.15): (0.4-0.6), more preferably 0.3:0.1:0.5, wherein the antimony trioxide and the sulfur powder are all commercially available, and the expanded graphite is obtained by treating commercial expandable graphite in a tubular furnace filled with inert atmosphere at the high temperature of 1000 ℃ for 1min, and the heating rate is 10 ℃ per minute. The size of the antimony trioxide is micron-sized or less, the average size is preferably 700nm, the diameter of the expandable graphite is preferably 75 microns, the sulfur powder is preferably sublimed sulfur, and the ball milling tank is preferably a low-energy planetary ball milling tank;
step two: mixing the premixed material obtained in the first step with ball milling beads, wherein the mixing time is preferably 5-40 h, more preferably 30h, the speed is 200-480r/min, more preferably 400r/min, and the antimony trioxide/expanded graphite/sulfur powder ternary mixed material is obtained; the ball milling bead material is made of zirconium dioxide, and the ball material ratio of the ball milling beads to the premixed material is preferably (20-100):1, and more preferably 50: 1;
step three: and (3) annealing the ternary mixed material obtained in the second step in an inert protective atmosphere, wherein the annealing temperature is preferably 350-550 ℃, more preferably 500 ℃, the annealing time is preferably 1-3 hours, more preferably 2 hours, so as to obtain the antimony sulfide-based negative electrode material for the lithium ion battery, and the inert protective atmosphere is preferably argon or nitrogen.
The invention also provides the antimony sulfide-based negative electrode material for the lithium ion battery, which is obtained by the preparation method.
The following detailed description of the invention, which is to be construed as part of the specification and by way of example
Other aspects, features and advantages of the present invention will become apparent from the detailed description, which illustrates the principles of the invention. But this example does not limit the invention.
Example 1
1) Weighing 0.3g of antimony trioxide (size of 700nm), 0.1g of expanded graphite (obtained by treating commercial expandable graphite in a tubular furnace filled with inert atmosphere at high temperature of 1000 ℃ for 1min, the heating rate is 10 ℃ per minute, the diameter of the expandable graphite is 75 microns) and 0.5g of sublimed sulfur powder material in a low-energy planetary ball milling tank according to the mass ratio of 3:1:5 to obtain a premixed material;
2) weighing ball-milling beads made of zirconium dioxide according to a ball material mass ratio of 50:1, and mixing the ball-milling beads with the premixed material obtained in the step 1), wherein the ball-milling time is 30 hours, and the speed is 400r/min, so as to obtain the antimony trioxide/expanded graphite/sulfur powder ternary mixed material.
3) Annealing the ternary mixed material obtained in the step 2) in argon protective gas at the temperature of 500 ℃ for 2 hours to obtain an antimony sulfide-based negative electrode material Sb for the lithium ion battery2S3@EG’-S。
Sb obtained in example 12S3The XRD pattern of the @ EG' -S composite negative electrode material is shown in figure 1, all characteristic peaks of the material accord with 74-1046PDF cards, and no impurity peak exists.
Sb obtained in example 12S3SEM test of @ EG' -S composite anode materialThe result is shown in FIG. 2a, which can be seen as a micron-sized block. FIG. 2b shows the TEM results, and it can be seen that the graphite encapsulates some fine particles (antimony sulfide particles). Fig. 2c is HRTEM results, and it can be seen that the lattice spacing of graphene produced by exfoliation is 0.34 nm. FIG. 2d is the EDS spectrum, and it can be seen that the Sb, S and C elements are uniformly distributed.
Example 2
The preparation method and conditions are the same as example 1, except that the ball milling time is 8h and 15h compared with example 1.
FIG. 7 shows Sb obtained in example 22S3The initial charge-discharge curve graph of the @ EG' -S composite negative electrode material is used for a lithium half-battery under the voltage range of 0.01-3.0V and the current density of 200mA/g when the ball milling time is 8h and 15 h. When the ball milling time is 8 hours, the first discharge specific capacity is 890.9mAh/g, the first charge specific capacity is 730.4mAh/g, and the first coulombic efficiency is 82%; when the ball milling time is 15 hours, the first discharge specific capacity is 930.1mAh/g, the first charge specific capacity is 772.9mAh/g, and the first coulombic efficiency is 83.1 percent.
Example 3
The preparation method and conditions are the same as those in example 1, and the difference from example 1 is that the mass ratio of the raw materials is 6: 1:5, 0.6g of antimony trioxide, 0.1g of expanded graphite, 0.5g of sublimed sulfur. FIG. 8 shows Sb obtained in example 32S3The material proportion of the @ EG' -S composite negative electrode material is 6: 1:5 (antimony trioxide: expanded graphite: sulfur powder) on the lithium half-cell under the voltage range of 0.01-3.0V and the current density of 200 mA/g. The first discharge specific capacity is 742.8mAh/g, the first charge specific capacity is 594.8mAh/g, and the first coulombic efficiency is 80%.
Application example 1
The antimony sulfide-based composite negative electrode material prepared in example 1 was subjected to electrochemical lithium storage performance test. The method comprises the following specific steps:
weighing the negative electrode active material, acetylene black and CMC according to the mass ratio of 8:1:1, putting the materials into an agate mortar, mixing the materials in a water solvent, grinding the materials for 30 minutes, coating the materials on a copper foil, drying the copper foil in a 60 ℃ oven for 3 hours, rolling and cutting the materials, and standing the materials in a vacuum oven overnight. The obtained pole piece active material loading capacityAbout 1.2mg cm-2. The counter electrode adopts a metal lithium sheet, the diaphragm is a polypropylene porous membrane, and the electrolyte adopts 1mol L-1LiPF of6The lithium salt is dissolved in a solvent system with the volume ratio of FEC/EC/DEC being 1/3/6, a 2025 type button cell is adopted for the cell, and lithium storage performance test is carried out in a voltage range of 0.01-3.0V.
Sb obtained in example 12S3The battery prepared from the @ EG' -S composite negative electrode material is 200mAg-1The first charge-discharge curve under the current density is shown in figure 3, the first coulombic efficiency can reach 86.7 percent, and the first discharge specific capacity is 938.3mAh g-1。
The charge-discharge cycle performance test of the battery prepared from the material obtained in example 1 under different current densities is shown in fig. 4, and it can be seen that: at 1000mAg-1Under the current density, the discharge specific capacity of the lithium ion battery is 666.2mAh g after 100 cycles-1And the capacity retention rate can reach 91.2%. At 5000mAg-1Under the current density, the discharge specific capacity of the material is higher than 548mAh g after 100 cycles-1And the capacity retention rate can reach 89.1%.
FIG. 5 shows the rate capability of the material of example 1, which can still output higher specific capacity 444mAh g at high current density of 15C-1. This fully demonstrates the Sb obtained by the process of the invention2S3The @ EG' -S composite material has excellent electrochemical performance, so that the method has more commercial popularization superiority.
Application example 2
The material obtained in example 1 is matched with a commercial NCM333 cathode material to carry out an electrochemical lithium storage performance test on a full cell, and the specific steps are as follows:
the electrode sheet of the material of example 1 prepared in application example 1 above was used and pre-lithiated beforehand to improve the coulombic efficiency. The preparation process of the electrode plate made of the commercial NCM333 cathode material is as follows: mixing the positive active material, C45, KS-6 and PVDF in a mass ratio of 91:2:2:5 in an N-methylpyrrolidone (NMP) solvent, setting the solid content of the slurry to be 55%, uniformly mixing the slurry by using a homogenizer, coating the mixture on an aluminum foil, drying the mixture in an oven at 100 ℃ for 1 hour, rolling and cutting the mixture into pieces, and drying the pieces in vacuumThe box was left overnight. The loading capacity of the obtained pole piece active material is about 5.2mg cm-2. Design N/P as 1.1, carry on the full cell matching. The diaphragm is a polypropylene porous membrane, and 1mol L of electrolyte is adopted-1LiPF of6Dissolving lithium salt in solvent system with volume ratio of FEC/EC/DEC being 1/3/6, using 2025 button cell as cell, Sb2S3The commercial NCM333 positive electrode full cell is subjected to a lithium storage performance test in a voltage range of 0.5-4.3V by the @ EG' -S negative electrode.
The charge-discharge cycle performance and rate performance test of the material obtained in example 1 and the commercial NCM333 cathode material matched with the full cell is shown in FIG. 6, and the specific capacity output after 100 cycles under the current density of 0.5C is 136.3mAh g-1The capacity retention rate can reach 89.7%, and the specific capacity of 107mAh g can be output under the high current density of 4C-1. This fully illustrates the Sb obtained in example 12S3The @ EG' -S composite negative electrode material also shows good electrochemical performance in a full cell, and is not limited to a lithium half cell, so that the invention has practical significance in wide application.
The present invention includes, but is not limited to, the above embodiments, and any equivalent substitutions or partial modifications made under the principle of the spirit of the present invention are considered to be within the scope of the present invention.

Claims (10)

1. A preparation method of antimony sulfide-based negative electrode material for lithium ion batteries is characterized by comprising the following steps:
the method comprises the following steps: placing antimony trioxide, expanded graphite and sulfur powder in a ball milling tank to obtain a premixed material;
step two: mixing the premixed material obtained in the step one with ball milling beads to obtain a ternary mixed material of antimony trioxide/expanded graphite/sulfur powder;
step three: and (4) annealing the ternary mixed material obtained in the step two in an inert protective atmosphere to obtain the antimony sulfide-based negative electrode material for the lithium ion battery.
2. The preparation method of the antimony sulfide-based negative electrode material for the lithium ion battery according to claim 1, wherein the mass ratio of the antimony trioxide, the expanded graphite and the sulfur powder in the first step is (0.2-0.6): (0.05-0.15): (0.4-0.6).
3. The method for preparing an antimony sulfide-based negative electrode material for a lithium ion battery according to claim 1, wherein the average size of the antimony trioxide is 700 nm.
4. The method of claim 1, wherein the expanded graphite is obtained by treating commercial expandable graphite in a tube furnace filled with inert gas at 1000 ℃ for 1min, the heating rate is 10 ℃ per minute, and the diameter of the expandable graphite is 75 microns.
5. The method according to claim 1, wherein in the second step, the ball milling beads are made of zirconium dioxide.
6. The method for preparing an antimony sulfide-based negative electrode material for a lithium ion battery according to claim 1, wherein the ball-to-material ratio of the ball milling beads to the pre-mixed material in the second step is (20:1) - (100: 1).
7. The preparation method of the antimony sulfide-based negative electrode material for the lithium ion battery, according to claim 1, is characterized in that the mixing time of the second step is 5-40 h, and the speed is 200-480 r/min.
8. The method for preparing an antimony sulfide-based negative electrode material for a lithium ion battery according to claim 1, wherein the inert protective atmosphere in the third step is argon or nitrogen.
9. The preparation method of the antimony sulfide-based negative electrode material for the lithium ion battery according to claim 1, wherein the annealing temperature in the third step is 350-550 ℃, and the annealing time is 1-3 hours.
10. Antimony sulfide-based negative electrode material for lithium ion batteries obtained by the production method according to any one of claims 1 to 9.
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CN112875751A (en) * 2020-12-29 2021-06-01 内蒙古工业大学 Preparation method of sulfur-doped bismuth trioxide, negative electrode material and supercapacitor
CN113036099A (en) * 2021-02-22 2021-06-25 武汉纺织大学 Biomass-based graphitized carbon/Fe7S8Method for preparing composite material
CN114725361A (en) * 2022-05-11 2022-07-08 滨州裕能化工有限公司 Iron-containing oxide coated sulfur-doped expanded graphite/silicon electrode material and preparation method thereof
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