CN112510175A - Silicon-carbon negative electrode material for lithium ion battery and lithium ion battery - Google Patents

Silicon-carbon negative electrode material for lithium ion battery and lithium ion battery Download PDF

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CN112510175A
CN112510175A CN202011282986.8A CN202011282986A CN112510175A CN 112510175 A CN112510175 A CN 112510175A CN 202011282986 A CN202011282986 A CN 202011282986A CN 112510175 A CN112510175 A CN 112510175A
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徐娟
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Fuyang Shenbang New Material Technology Co Ltd
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Abstract

The invention provides a silicon-carbon cathode material for a lithium ion battery, which comprises the following components: firstly, carrying out surface treatment on silicon powder by adopting an acid or alkali compound, and then carrying out high-temperature treatment to obtain surface hydroxylated silicon powder; then mixing the silicon powder with the hydroxylated surface with polyimide containing hydroxyl to obtain a polyimide silicon powder-coated composite material; and finally, carbonizing the composite material of the polyimide coated silicon powder to obtain the silicon-carbon cathode material for the lithium ion battery. The silicon-carbon negative electrode material provided by the invention can simultaneously have the high lithium storage characteristics of silicon materials and the high cycle stability of carbon materials, effectively inhibits the volume expansion of the silicon negative electrode, and has high specific capacity and long cycle life.

Description

Silicon-carbon negative electrode material for lithium ion battery and lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon-carbon negative electrode material for a lithium ion battery and the lithium ion battery.
Background
In the existing secondary battery system, the lithium ion battery is the most competitive secondary battery at present from the aspects of development space and technical indexes such as service life, specific energy, working voltage and self-discharge rate. With the continuous development of electronic technology, higher requirements are also put forward on lithium ion batteries, and higher energy density, better cycle life, better high and low temperature charge and discharge performance, better safety performance and the like are required, so that the positive electrode and negative electrode materials for the lithium ion batteries are required to be further developed and perfected.
In the aspect of negative electrode materials, the theoretical specific capacity of the traditional commercialized graphite is 372mAh g-1It is difficult to meet the requirement of high specific energy lithium ion batteries, so the development of high specific capacity negative electrode materials is not easy. The theoretical lithium storage specific capacity of the silicon negative electrode material is up to 4200 mAh g-110 times that of the commercial graphite cathode, the low lithium removal/insertion potential (0-0.45V) is closest to the voltage plateau of graphite, the discharge plateau is long and stable, and is considered as the most promising alternative material for the commercial graphite.
However, the electronic conductivity and ionic conductivity of silicon are low, resulting in poor kinetics of electrochemical reactions; the cycle stability of ordinary pure silicon is poor. And the phase change and volume expansion of silicon in the lithiation process can generate larger stress, so that the electrode is broken and pulverized, the resistance is increased, and the cycle performance is suddenly reduced.
At present, silicon negative electrode materials are mainly researched by ball-milling and mixing silicon powder and a carbon source material and then pyrolyzing the mixture to prepare a silicon-carbon composite material, so that the volume expansion phenomenon in the charging and discharging processes of a battery is relieved, and the cycle performance of the silicon-based material is improved. However, the silicon-based negative electrode material obtained by the method has poor stability and is not obvious for improving the volume expansion phenomenon of silicon during charging and discharging.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a silicon-carbon negative electrode material for a lithium ion battery and the lithium ion battery.
The invention provides a silicon-carbon cathode material for a lithium ion battery, which is prepared by the following steps:
s1, carrying out surface treatment on the silicon powder by adopting an acid or alkali compound, and then carrying out high-temperature treatment to obtain surface hydroxylated silicon powder;
s2, mixing the silicon powder with the hydroxylated surface with polyimide containing hydroxyl to obtain a polyimide silicon powder-coated composite material;
and S3, carbonizing the polyimide silicon powder-coated composite material to obtain the silicon-carbon negative electrode material for the lithium ion battery.
Preferably, the average particle size of the silicon powder is 50-500 nm; the acid compound is hydrofluoric acid; the alkali compound is sodium hydroxide or potassium hydroxide.
Preferably, the temperature of the high-temperature treatment is 400-600 ℃, and the time is 1-30 min.
Preferably, the hydroxyl group-containing polyimide is obtained by polycondensing a dianhydride monomer of a tetracarboxylic dianhydride with a diamine monomer containing a phenolic hydroxyl group diamine.
Preferably, the tetracarboxylic dianhydride is at least one of 3, 3', 4, 4' -biphenyltetracarboxylic dianhydride, 4, 4' -oxydiphthalic dianhydride, 3', 4, 4' -benzophenonetetracarboxylic dianhydride, 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentanetetracarboxylic dianhydride or 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride; the diamine containing phenolic hydroxyl is 3, 3' -dihydroxy benzidine;
preferably, the diamine monomer further includes at least one of 4, 4 '-diaminodiphenyl ether, 4' -diaminodiphenyl sulfide, 4 '-diaminobenzophenone, or 4, 4' -diaminodiphenylmethane.
Preferably, the mass ratio of the surface hydroxylated silicon powder to the hydroxyl-containing polyimide is 1: 1-20.
Preferably, the temperature of the carbonization treatment is 400-.
The invention provides a negative pole piece of a lithium ion battery, which comprises the silicon-carbon negative pole material for the lithium ion battery.
The invention also provides a lithium ion battery which comprises the negative pole piece.
According to the silicon-carbon cathode material, the surface of silicon powder is treated by acid or alkali to remove a natural oxide layer on the surface of the silicon powder, the treated silicon powder is subjected to high-temperature treatment to reconstruct a continuous, compact and uniform silicon oxide layer on the surface of the silicon powder, and finally rich silicon hydroxyl functional groups are formed on the surface of silicon particles to obtain a surface hydroxylated silicon powder material; and then mixing the silicon powder material with the hydroxylated surface with polyimide containing hydroxyl, wherein hydrogen bonds can be formed between the hydroxyl on the surface of the silicon powder material and the hydroxyl contained in the polyimide, so that the silicon powder material and the polyimide can be connected through similar covalent bonds (hydrogen bond effect), and finally the polyimide is taken as an organic carbon source to be tightly bound around the silicon, so that the silicon powder is wrapped by the sufficient organic carbon source, and then the surface of the obtained silicon-carbon negative electrode material is densely covered by a carbon layer through carbonization treatment, so that the silicon-carbon negative electrode material with good performance is obtained.
Therefore, compared with the existing silicon carbon cathode material formed by simply ball-milling and mixing silicon powder and a carbon source material, the surface of the silicon powder is treated, and the polyimide with a specific structure is selected to coat the silicon powder, so that a carbon layer on the surface of the silicon powder is more uniform and compact, the electrochemical cycle stability of the silicon carbon cathode material can be effectively improved, and higher cycle coulomb efficiency can be obtained.
Drawings
Fig. 1 shows the cycling stability of a lithium ion battery corresponding to the silicon-carbon negative electrode material in example 1 of the present invention at a current density (100 mAg-1).
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A silicon-carbon negative electrode material for a lithium ion battery is prepared by the following steps:
(1) adding 1g of nano silicon powder (with the average particle size of 100nm) into 10mL of hydrofluoric acid solution (10 wt%), stirring for reaction for 10min, centrifugally separating to obtain a solid, washing with water for 3 times, drying at 80 ℃ for 2h, and then carrying out heat preservation treatment on the dried silicon powder at 500 ℃ for 10min to obtain surface hydroxylated silicon powder;
(2) adding 2.16g of 3, 3 '-dihydroxybenzidine and 4.00g of 4, 4' -diaminodiphenyl ether into 60mL of anhydrous N, N-dimethylacetamide under the protection of nitrogen, uniformly stirring, adding 8.83g of 3, 3', 4, 4' -biphenyltetracarboxylic dianhydride, stirring at room temperature for 5 hours for reaction to obtain a polyamide acid solution, adding 1.8mL of pyridine into the polyamide acid solution as an imidizing agent, completely dispersing, adding 5mL of acetic anhydride as a dehydrating agent, heating to 80 ℃, stirring for reaction for 4 hours, and cooling to room temperature to obtain a polyimide solution; adding the silicon powder with the hydroxylated surface into the polyimide solution, stirring and mixing for 3 hours, and evaporating the solvent to dryness to obtain the polyimide-coated silicon powder composite material;
(3) and placing the polyimide-coated silicon powder composite material in an argon atmosphere, heating to 400 ℃ at room temperature at a heating rate of 5 ℃/min, preserving heat for 1h, continuously heating to 900 ℃, preserving heat for 3h, naturally cooling to room temperature, crushing and sieving to obtain the silicon-carbon cathode material for the lithium ion battery.
Example 2
A silicon-carbon negative electrode material for a lithium ion battery is prepared by the following steps:
(1) adding 1g of nano silicon powder (with the average particle size of 100nm) into 10mL of hydrofluoric acid solution (10 wt%), stirring for reaction for 10min, centrifugally separating to obtain a solid, washing with water for 3 times, drying at 80 ℃ for 2h, and then carrying out heat preservation treatment on the dried silicon powder at 500 ℃ for 20min to obtain surface hydroxylated silicon powder;
(2) adding 2.16g of 3, 3 '-dihydroxybenzidine and 4.00g of 4, 4' -diaminodiphenyl ether into 60mL of anhydrous N, N-dimethylacetamide under the protection of nitrogen, uniformly stirring, adding 6.73g of 1, 2, 4, 5-cyclohexane tetracarboxylic dianhydride, stirring at room temperature for 5 hours for reaction to obtain a polyamide acid solution, adding 1.8mL of pyridine into the polyamide acid solution as an imidizing agent, completely dispersing, adding 5mL of acetic anhydride as a dehydrating agent, heating to 80 ℃, stirring for reaction for 4 hours, and cooling to room temperature to obtain a polyimide solution; adding the silicon powder with the hydroxylated surface into the polyimide solution, stirring and mixing for 3 hours, and evaporating the solvent to dryness to obtain the polyimide-coated silicon powder composite material;
(3) and placing the polyimide-coated silicon powder composite material in an argon atmosphere, heating to 800 ℃ at room temperature at a heating rate of 3 ℃/min, preserving the temperature for 5 hours, naturally cooling to room temperature, crushing and sieving to obtain the silicon-carbon cathode material for the lithium ion battery.
Example 3
A silicon-carbon negative electrode material for a lithium ion battery is prepared by the following steps:
(1) adding 1g of nano silicon powder (with the average particle size of 100nm) into 10mL of sodium hydroxide aqueous solution (10 wt%), heating to 50 ℃, stirring for reaction for 30min, centrifugally separating to obtain a solid, washing with water for 3 times, drying at 80 ℃ for 2h, and then carrying out heat preservation treatment on the dried silicon powder at 600 ℃ for 5min to obtain surface hydroxylated silicon powder;
(2) adding 2.16g of 3, 3 '-dihydroxybenzidine and 4.33g of 4, 4' -diaminodiphenyl sulfide into 60mL of anhydrous N, N-dimethylacetamide under the protection of nitrogen, uniformly stirring, adding 8.83g of 3, 3', 4, 4' -biphenyltetracarboxylic dianhydride, stirring at room temperature for 5 hours for reaction to obtain a polyamide acid solution, adding 1.8mL of pyridine into the polyamide acid solution as an imidizing agent, completely dispersing, adding 5mL of acetic anhydride as a dehydrating agent, heating to 80 ℃, stirring for reaction for 4 hours, and cooling to room temperature to obtain a polyimide solution; adding the silicon powder with the hydroxylated surface into the polyimide solution, stirring and mixing for 3 hours, and evaporating the solvent to dryness to obtain the polyimide-coated silicon powder composite material;
(3) and placing the polyimide-coated silicon powder composite material in an argon atmosphere, heating to 500 ℃ at room temperature at a heating rate of 2 ℃/min, preserving heat for 1h, continuously heating to 800 ℃, preserving heat for 4h, naturally cooling to room temperature, crushing and sieving to obtain the silicon-carbon cathode material for the lithium ion battery.
Example 4
A silicon-carbon negative electrode material for a lithium ion battery is prepared by the following steps:
(1) adding 1g of nano silicon powder (with the average particle size of 100nm) into 10mL of sodium hydroxide aqueous solution (10 wt%), heating to 50 ℃, stirring for reaction for 30min, centrifugally separating to obtain a solid, washing with water for 3 times, drying at 80 ℃ for 2h, and then carrying out heat preservation treatment on the dried silicon powder at 600 ℃ for 5min to obtain surface hydroxylated silicon powder;
(2) adding 2.16g of 3, 3 '-dihydroxybenzidine and 3.97g of 4, 4' -diaminodiphenylmethane into 60mL of anhydrous N, N-dimethylacetamide under the protection of nitrogen, uniformly stirring, adding 6.73g of 1, 2, 4, 5-cyclohexane tetracarboxylic dianhydride, stirring at room temperature for 5 hours for reaction to obtain a polyamide acid solution, adding 1.8mL of pyridine serving as an imidization agent into the polyamide acid solution, completely dispersing, adding 5mL of acetic anhydride serving as a dehydrating agent, heating to 80 ℃, stirring for reaction for 4 hours, and cooling to room temperature to obtain a polyimide solution; adding the silicon powder with the hydroxylated surface into the polyimide solution, stirring and mixing for 3 hours, and evaporating the solvent to dryness to obtain the polyimide-coated silicon powder composite material;
(3) and placing the polyimide-coated silicon powder composite material in an argon atmosphere, heating to 1000 ℃ at room temperature at a heating rate of 6 ℃/min, keeping the temperature for 1h, naturally cooling to room temperature, crushing and sieving to obtain the silicon-carbon cathode material for the lithium ion battery.
Example 5
A silicon-carbon negative electrode material for a lithium ion battery is prepared by the following steps:
(1) adding 1g of nano silicon powder (with the average particle size of 100nm) into 10mL of hydrofluoric acid solution (10 wt%), stirring for reaction for 10min, centrifugally separating to obtain a solid, washing with water for 3 times, drying at 80 ℃ for 2h, and then carrying out heat preservation treatment on the dried silicon powder at 700 ℃ for 5min to obtain surface hydroxylated silicon powder;
(2) adding 1.08g of 3, 3 '-dihydroxybenzidine and 2.00g of 4, 4' -diaminodiphenyl ether into 40mL of anhydrous N, N-dimethylacetamide under the protection of nitrogen, uniformly stirring, adding 4.41g of 3, 3', 4, 4' -biphenyltetracarboxylic dianhydride, stirring at room temperature for reacting for 5 hours to obtain a polyamide acid solution, adding 1.0mL of pyridine into the polyamide acid solution as an imidizing agent, completely dispersing, adding 3mL of acetic anhydride as a dehydrating agent, heating to 80 ℃, stirring for reacting for 4 hours, and cooling to room temperature to obtain a polyimide solution; adding the silicon powder with the hydroxylated surface into the polyimide solution, stirring and mixing for 3 hours, and evaporating the solvent to dryness to obtain the polyimide-coated silicon powder composite material;
(3) and placing the polyimide-coated silicon powder composite material in an argon atmosphere, heating to 500 ℃ at room temperature at a heating rate of 3 ℃/min, preserving heat for 1h, continuously heating to 900 ℃, preserving heat for 4h, naturally cooling to room temperature, crushing and sieving to obtain the silicon-carbon cathode material for the lithium ion battery.
Comparative example 1
A silicon-carbon negative electrode material for a lithium ion battery is prepared by the following steps:
(1) 1g of nano silicon powder (with the average particle size of 100nm) is subjected to heat preservation treatment at 500 ℃ for 10min to obtain heat-treated silicon powder;
(2) adding 2.16g of 3, 3 '-dihydroxybenzidine and 4.00g of 4, 4' -diaminodiphenyl ether into 60mL of anhydrous N, N-dimethylacetamide under the protection of nitrogen, uniformly stirring, adding 8.83g of 3, 3', 4, 4' -biphenyltetracarboxylic dianhydride, stirring at room temperature for 5 hours for reaction to obtain a polyamide acid solution, adding 1.8mL of pyridine into the polyamide acid solution as an imidizing agent, completely dispersing, adding 5mL of acetic anhydride as a dehydrating agent, heating to 80 ℃, stirring for reaction for 4 hours, and cooling to room temperature to obtain a polyimide solution; adding the silicon powder subjected to heat treatment into the polyimide solution, stirring and mixing for 3 hours, and evaporating the solvent to dryness to obtain a composite material;
(3) and placing the composite material in an argon atmosphere, heating to 400 ℃ at room temperature at a heating rate of 5 ℃/min, preserving heat for 1h, continuing heating to 900 ℃, preserving heat for 3h, naturally cooling to room temperature, crushing and sieving to obtain the silicon-carbon cathode material for the lithium ion battery.
Comparative example 2
A silicon-carbon negative electrode material for a lithium ion battery is prepared by the following steps:
(1) adding 1g of nano silicon powder (with the average particle size of 100nm) into 10mL of hydrofluoric acid solution (10 wt%), stirring for reaction for 10min, centrifugally separating to obtain a solid, washing with water for 3 times, drying at 80 ℃ for 2h, and then carrying out heat preservation treatment on the dried silicon powder at 500 ℃ for 10min to obtain surface hydroxylated silicon powder;
(2) adding 1.84g of 4, 4 '-diaminobiphenyl and 4.00g of 4, 4' -diaminodiphenyl ether into 60mL of anhydrous N, N-dimethylacetamide under the protection of nitrogen, uniformly stirring, adding 8.83g of 3, 3', 4, 4' -biphenyltetracarboxylic dianhydride, stirring at room temperature for 5 hours for reaction to obtain a polyamide acid solution, adding 1.8mL of pyridine into the polyamide acid solution as an imidization agent, completely dispersing, adding 5mL of acetic anhydride as a dehydrating agent, heating to 80 ℃, stirring for reaction for 4 hours, and cooling to room temperature to obtain a polyimide solution; adding the silicon powder with the hydroxylated surface into the polyimide solution, stirring and mixing for 3 hours, and evaporating the solvent to dryness to obtain a composite material;
(3) and placing the composite material in an argon atmosphere, heating to 400 ℃ at room temperature at a heating rate of 5 ℃/min, preserving heat for 1h, continuing heating to 900 ℃, preserving heat for 3h, naturally cooling to room temperature, crushing and sieving to obtain the silicon-carbon cathode material for the lithium ion battery.
The silicon-carbon anode materials for lithium ion batteries obtained in examples 1 to 5 and comparative examples 1 to 2 were subjected to performance tests as shown in the following method, and the results are shown in table 1:
the silicon-carbon negative electrode material, acetylene black serving as a conductive agent, CMC (sodium carboxymethyl cellulose) and SBR are ball-milled and mixed uniformly according to the mass ratio of 80:10:5:5, deionized water is used as a solvent to prepare negative electrode slurry, the negative electrode slurry is uniformly coated on copper foil, and the copper foil is dried in a drying oven at the temperature of 80 ℃ in vacuum and rolled to prepare a negative electrode piece.
The anode plate is taken as a working electrode, a round metal lithium plate is taken as a counter electrode, Celgard2400 is taken as a diaphragm, and 1mol/L LiPF is prepared into the CR2032 type button cell6The solution (EC: DMC mixed solvent in a volume ratio of 1: 1) is used as the electrolyte. The button cell is subjected to constant current charge and discharge test by adopting an LAND cell test system, and is charged and discharged under the current density of 100mA/g, and the charge and discharge voltage rangeThe circumference is 0.01-1.5V, and the test results are shown in Table 1.
TABLE 1 result of charge-discharge cycle test of silicon carbon anode materials of examples 1-5 and comparative examples 1-2
Figure BDA0002781414950000091
Referring to the results of the above example 1 and comparative examples 1-2, it can be seen that the cyclic charge and discharge performance of the electrode can be significantly improved by the combined action of treating the surface of the silicon powder and coating the silicon powder with the polyimide with a specific structure.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (9)

1. The silicon-carbon negative electrode material for the lithium ion battery is characterized by being prepared by the following steps:
s1, carrying out surface treatment on the silicon powder by adopting an acid or alkali compound, and then carrying out high-temperature treatment to obtain surface hydroxylated silicon powder;
s2, mixing the silicon powder with the hydroxylated surface with polyimide containing hydroxyl to obtain a polyimide silicon powder-coated composite material;
and S3, carbonizing the polyimide silicon powder-coated composite material to obtain the silicon-carbon negative electrode material for the lithium ion battery.
2. The silicon-carbon anode material for the lithium ion battery according to claim 1, wherein the silicon powder has an average particle size of 50-500 nm; the acid compound is hydrofluoric acid; the alkali compound is sodium hydroxide or potassium hydroxide.
3. The silicon-carbon anode material for the lithium ion battery as claimed in claim 1 or 2, wherein the temperature of the high-temperature treatment is 400-600 ℃, and the time is 1-30 min.
4. The silicon-carbon negative electrode material for a lithium ion battery according to any one of claims 1 to 3, wherein the hydroxyl group-containing polyimide is obtained by polycondensation of a dianhydride monomer of a tetracarboxylic dianhydride with a diamine monomer containing a phenolic hydroxyl group diamine.
5. The silicon-carbon negative electrode material for a lithium ion battery according to any one of claims 1 to 4, wherein the tetracarboxylic dianhydride is at least one of 3, 3', 4, 4' -biphenyltetracarboxylic dianhydride, 4, 4' -oxydiphthalic dianhydride, 3', 4, 4' -benzophenonetetracarboxylic dianhydride, 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentanetetracarboxylic dianhydride, or 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride; the diamine containing phenolic hydroxyl is 3, 3' -dihydroxy benzidine;
preferably, the diamine monomer further includes at least one of 4, 4 '-diaminodiphenyl ether, 4' -diaminodiphenyl sulfide, 4 '-diaminobenzophenone, or 4, 4' -diaminodiphenylmethane.
6. The silicon-carbon anode material for the lithium ion battery according to any one of claims 1 to 5, wherein the mass ratio of the surface-hydroxylated silicon powder to the hydroxyl-containing polyimide is 1:1 to 20.
7. The Si-C anode material for lithium ion batteries according to any one of claims 1 to 6, wherein the temperature of the carbonization treatment is 400-1000 ℃, the time is 1-10h, and the temperature rise rate is 1-10 ℃/min.
8. A negative electrode plate of a lithium ion battery, which comprises the silicon-carbon negative electrode material for the lithium ion battery in any one of claims 1 to 7.
9. A lithium ion battery comprising the negative electrode tab of claim 8.
CN202011282986.8A 2020-11-17 2020-11-17 Silicon-carbon negative electrode material for lithium ion battery and lithium ion battery Withdrawn CN112510175A (en)

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Cited By (2)

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CN113066972A (en) * 2021-03-19 2021-07-02 厦门高容新能源科技有限公司 Lithium-supplementing silicon material, preparation method thereof, electrode containing lithium-supplementing silicon material and battery
CN113823780A (en) * 2021-08-20 2021-12-21 广东邦普循环科技有限公司 Silicon-carbon composite negative electrode material and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113066972A (en) * 2021-03-19 2021-07-02 厦门高容新能源科技有限公司 Lithium-supplementing silicon material, preparation method thereof, electrode containing lithium-supplementing silicon material and battery
CN113066972B (en) * 2021-03-19 2022-06-17 厦门高容新能源科技有限公司 Lithium-supplementing silicon material, preparation method thereof, electrode containing lithium-supplementing silicon material and battery
CN113823780A (en) * 2021-08-20 2021-12-21 广东邦普循环科技有限公司 Silicon-carbon composite negative electrode material and preparation method and application thereof

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