CN111740084B - Sulfur-doped pre-lithiated silicon-carbon composite material and preparation method thereof - Google Patents
Sulfur-doped pre-lithiated silicon-carbon composite material and preparation method thereof Download PDFInfo
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 150000002898 organic sulfur compounds Chemical class 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 3
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 3
- 235000018417 cysteine Nutrition 0.000 claims description 3
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 3
- 229930182817 methionine Natural products 0.000 claims description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 28
- 239000000463 material Substances 0.000 abstract description 22
- 238000003763 carbonization Methods 0.000 abstract description 7
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052912 lithium silicate Inorganic materials 0.000 abstract description 6
- 125000001741 organic sulfur group Chemical group 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000011056 performance test Methods 0.000 description 7
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- LTRVAZKHJRYLRJ-UHFFFAOYSA-N lithium;butan-1-olate Chemical compound [Li+].CCCC[O-] LTRVAZKHJRYLRJ-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- -1 stirring uniformly Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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Abstract
The invention relates to a sulfur-doped pre-lithiated silicon-carbon composite material and a preparation method thereof. The preparation method comprises the following steps: adding an organic sulfur compound into the graphene oxide solution, and uniformly stirring to obtain a solution a; adding organic lithium and an organic solvent into the solution a, sealing and uniformly stirring to obtain a solution b; adding silicon monoxide into the solution b, uniformly stirring, heating and pressurizing to react, filtering, and drying to obtain a composite material intermediate; and (3) putting the composite material intermediate into an inert atmosphere for carbonization, and obtaining the sulfur-doped pre-lithiated silicon-carbon composite material after the carbonization. By doping organic sulfur and organic lithium in the silicon monoxide, the invention forms lithium silicate to improve the first efficiency of the material, and simultaneously forms a-Li-S-structure and a-CO-NH-structure to improve the structural stability and specific capacity of the material and improve the cycle performance of the material.
Description
Technical Field
The invention belongs to the field of lithium ion battery preparation, and particularly relates to a sulfur-doped pre-lithiated silicon-carbon composite material and a preparation method thereof.
Background
With the improvement of the energy density requirement of the lithium ion battery, the negative electrode material is required to have high energy density and electrochemical performance thereof, and the silicon-carbon material is applied to the field of the high energy density battery due to the characteristics of high specific capacity and the like, but the silicon-carbon material has the defects of poor conductivity, large expansion, low initial efficiency, poor cycle and the like, so that the application of the silicon-carbon material is limited.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a sulfur-doped pre-lithiated silicon-carbon composite material and a preparation method thereof. Aiming at the defects of poor electronic conductivity, poor structural stability caused by expansion in the circulation process, poor circulation performance and the like of the existing silicon-carbon material, the invention dopes organic sulfur and organic lithium in the silicon monoxide, and simultaneously forms a structure of Li-S-to improve the structural stability and specific capacity of the material and improve the circulation performance of the material while forming lithium silicate to improve the first efficiency of the material.
The scheme of the invention is to provide a preparation method of a sulfur-doped pre-lithiated silicon-carbon composite material, which comprises the following steps:
(1) adding an organic sulfur compound into the graphene oxide solution, and uniformly stirring to obtain a solution a;
(2) adding organic lithium and an organic solvent into the solution a obtained in the step (1), and sealing and uniformly stirring to obtain a solution b;
(3) adding silicon monoxide into the solution b obtained in the step (2), uniformly stirring, heating and pressurizing to react, filtering, and drying to obtain a composite material intermediate;
(4) and (4) putting the composite material intermediate obtained in the step (3) into an inert atmosphere for carbonization, and obtaining the sulfur-doped pre-lithiation silicon-carbon composite material after the carbonization.
Preferably, in the step (1), the organic sulfur compound is one of methionine, cysteine or 2-mercaptoethanol.
Preferably, in the step (1), the concentration of the graphene oxide solution is 0.1-1 wt.%; the ratio of hydroxyl and carboxyl in the graphene oxide is 0.5-2%.
Preferably, in the step (2), the organolithium is one of methyllithium, lithium n-butoxide, n-butyllithium or tert-butyllithium.
Preferably, in step (2), the organic solvent is N-methylpyrrolidone.
Preferably, the weight ratio of the organic sulfur compound, the graphene oxide, the organic lithium and the organic solvent is 10: 0.1-1: 1-5: 100.
Preferably, the weight ratio of the silicon monoxide to the solution b is 100: 100-500.
Preferably, in the step (3), the heating temperature is 100-200 ℃, the pressurizing pressure is 1-5 Mpa, and the reaction time is 1-24 hours.
Preferably, in the step (4), the carbonization temperature is 800-1100 ℃, and the carbonization time is 1-12 h.
Based on the same technical concept, the invention further provides the sulfur-doped pre-lithiated silicon-carbon composite material prepared by the preparation method.
The design idea of the invention is as follows:
one of the methods for improving the conductivity of the silicon-carbon material is to dope the high-conductivity graphene and other conductivity materials, and simultaneously dope and modify the high-conductivity graphene and other conductivity materials to improve the specific capacity and reduce the expansion of the high-conductivity graphene and other conductivity materials.
The invention has the beneficial effects that:
according to the preparation method of the sulfur-doped pre-lithiated silicon-carbon composite material, the specific capacity of the material is improved and the expansion of the material is reduced by using sulfur, the electronic conductivity of the material is improved by using graphene, the irreversible capacity loss of the material is reduced by using lithium silicate formed by organic lithium and silicon monoxide, and the first efficiency of the composite material is improved. Meanwhile, sulfur in the organic compound and organic lithium form a-Li-S-structure, so that the structural stability of the material can be improved. Through hydrothermal reaction, silicon monoxide can be uniformly doped among compounds with a structure of-Li-S-, and a formed complex has the characteristics of high structural stability, high first-time efficiency, high specific capacity and the like. Meanwhile, the structure of the-CO-NH-structure formed by the acid groups such as hydroxyl, carboxyl and the like on the surface of the graphene oxide and the amino group on the surface of the organic sulfur compound through chemical reaction has the characteristic of stable structure, and the structural stability of the material is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a scanning electron micrograph of a sulfur-doped prelithiated silicon carbon composite prepared in accordance with example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
The embodiment provides a preparation method of a sulfur-doped pre-lithiated silicon-carbon composite material, which comprises the following steps:
(1) adding 10g of methionine into 100g of graphene oxide N-methyl pyrrolidone solution with the concentration of 0.5 wt.%, and uniformly stirring to obtain a solution a; wherein, the ratio of hydroxyl and carboxyl in the graphene oxide is 1 percent.
(2) Adding 3g of tert-butyl lithium and 100g N-methyl pyrrolidone solvent into the solution a obtained in the step (1), and sealing and uniformly stirring to obtain a solution b;
(3) adding 100g of silicon monoxide into 300g of the solution b, uniformly stirring, transferring into a high-pressure reaction kettle, reacting for 12 hours at 180 ℃ and 3Mpa, sequentially filtering, and drying at 80 ℃ for 12 hours to obtain a composite material intermediate;
(4) and (4) transferring the composite material intermediate obtained in the step (3) to a tubular furnace, heating to 900 ℃ at a heating rate of 5 ℃/min in an argon inert atmosphere for carbonization for 6h, and then naturally cooling to room temperature to obtain the sulfur-doped pre-lithiated silicon-carbon composite material.
Example 2
The embodiment provides a preparation method of a sulfur-doped pre-lithiated silicon-carbon composite material, which comprises the following steps:
(1) adding 10g of cysteine into 100g of graphene oxide N-methyl pyrrolidone solution with the concentration of 0.1 wt.%, and uniformly stirring to obtain a solution a; wherein, the ratio of hydroxyl and carboxyl in the graphene oxide is 0.5 percent.
(2) Adding 1g of lithium n-butoxide and 100g of carbon tetrachloride solvent into the solution a obtained in the step (1), and sealing and uniformly stirring to obtain a solution b;
(3) adding 100g of silicon monoxide into 100g of the solution b, uniformly stirring, transferring into a high-pressure reaction kettle, reacting for 24 hours at 100 ℃ and 1Mpa, sequentially filtering, and drying at 80 ℃ for 12 hours to obtain a composite material intermediate;
(4) and (4) transferring the composite material intermediate obtained in the step (3) to a tubular furnace, heating to 800 ℃ at a heating rate of 5 ℃/min in an argon inert atmosphere, carbonizing for 12h, and naturally cooling to room temperature to obtain the sulfur-doped pre-lithiated silicon-carbon composite material.
Example 3
The embodiment provides a preparation method of a sulfur-doped pre-lithiated silicon-carbon composite material, which comprises the following steps:
(1) adding 10g of 2-mercaptoethanol into 100g of graphene oxide N-methylpyrrolidone solution with the concentration of 1 wt.%, and uniformly stirring to obtain a solution a; wherein, the ratio of hydroxyl and carboxyl in the graphene oxide is 2 percent.
(2) Adding 5g of n-butyllithium and 100g of tetrahydrofuran solvent into the solution a obtained in the step (1), and sealing and uniformly stirring to obtain a solution b;
(3) adding 100g of silicon monoxide into 500g of the solution b, uniformly stirring, transferring the solution to a high-pressure reaction kettle, reacting for 1h at 200 ℃ and 5Mpa, sequentially filtering, and drying at 80 ℃ for 12h to obtain a composite material intermediate;
(4) and (4) transferring the composite material intermediate obtained in the step (3) to a tubular furnace, heating to 1100 ℃ at a heating rate of 5 ℃/min in an argon inert atmosphere, carbonizing for 1h, and naturally cooling to room temperature to obtain the sulfur-doped pre-lithiated silicon-carbon composite material.
Comparative example
The comparative example provides a preparation method of a silicon-carbon composite material, comprising the following steps:
adding 100g of silicon monoxide and 100g of graphene oxide N-methyl pyrrolidone solution with the concentration of 1 wt.% into 100g of tetrahydrofuran, uniformly stirring, transferring into a high-pressure reaction kettle, reacting for 12h at the temperature of 180 ℃ and the pressure of 3Mpa, filtering, vacuum drying at the low temperature of 80 ℃ for 12h, transferring into a tubular furnace, heating to 900 ℃ at the heating rate of 5 ℃/min under the inert atmosphere of argon, carbonizing for 6h, and naturally cooling to room temperature to obtain the silicon monoxide/carbon composite material.
Examples of the experiments
(1) Scanning Electron Microscope (SEM) testing
Fig. 1 is an SEM image of the sulfur-doped pre-lithiated silicon-carbon composite material prepared in example 1, and it can be seen from fig. 1 that the sulfur-doped pre-lithiated silicon-carbon composite material of example 1 has a particle size of 5 to 10 μm and a uniform and reasonable size distribution.
(2) Physicochemical property test and button cell performance test
The specific surface area, tap density and powder conductivity of the composite material prepared according to the test examples and comparative examples of the national standard GB/T-245131-2009 graphite cathode materials for lithium ion batteries are shown in Table 1.
The preparation method comprises the following steps of respectively taking the sulfur-doped pre-lithiated silicon-carbon composite material obtained in the examples 1-3 and the silicon monoxide/carbon composite material obtained in the comparative example as negative electrode materials to prepare the pole piece, and specifically comprises the following steps: weighing 9g of negative electrode material, 0.5g of conductive agent SP and 0.5g of LA132 binder, adding into 220ml of deionized water, stirring uniformly, coating on a copper foil to prepare a membrane,then, LiPF with a lithium sheet as a negative electrode, celegard2400 as a diaphragm and electrolyte solute of 1mol/L6The button cell is assembled in a glove box with the content of oxygen and water lower than 0.1ppm to form the button cell, the button cell is arranged on a blue tester, the button cell is charged and discharged at the rate of 0.1C, the voltage range is 0.05V-2.0V, and the button cell is stopped after circulation for 3 weeks. The results of the button cell performance tests are shown in table 1.
TABLE 1 comparison of physicochemical and performance test results for button cell
As can be seen from table 1, the sulfur-doped pre-lithiated silicon-carbon composite materials obtained in examples 1 to 3 are superior to comparative examples in terms of the first efficiency and the first discharge capacity thereof, because the pre-lithiation reduces the loss of the irreversible capacity thereof to improve the first efficiency thereof, and the sulfur doping improves the specific capacity thereof; the density of the material can be improved by adopting the hydrothermal reaction, so that the tap density of the material can also be improved; in the sulfur-doped pre-lithiated silicon-carbon composite material obtained in the embodiment, the organic lithium and silicon form lithium silicate, so that the electronic conductivity of the material is improved, and the powder conductivity of the material is improved.
(3) Manufacturing of soft package battery
And (3) doping 90% of artificial graphite into the sulfur-doped pre-lithiated silicon-carbon composite material obtained in the examples 1-3 and the silicon monoxide/carbon composite material obtained in the comparative example to serve as negative electrode materials, and preparing a negative electrode piece. With ternary materials (LiNi)1/3Co1/3Mn1/ 3O2) As the positive electrode, LiPF6(the solvent is EC + DEC, the volume ratio is 1:1, and the concentration is 1.3mol/l) is used as electrolyte, and celegard2400 is a diaphragm to prepare 5Ah soft package batteries C1, C2, C3 and D. And then testing the cycle performance and the rate capability of each soft package battery and the expansion rate of the pole piece of each soft package battery.
(3.1) Pole piece thickness test
Testing the expansion rate of the pole piece: the method comprises the steps of firstly testing the thickness D1 of a negative pole piece of the soft package battery after constant volume, then circulating for 100 times and fully charging the soft package battery, then testing the thickness D2 of the negative pole piece of the soft package battery after the soft package battery is dissected, and then calculating the expansion rate (D2-D1)/D1. The results are shown in Table 2.
TABLE 2 comparison of pole piece thickness for examples and comparative examples
| D1/μm | D2/μm | Expansion ratio (D2-D1)/D1 | |
| Example 1 | 105 | 137 | 30.5％ |
| Example 2 | 104 | 137 | 31.5％ |
| Example 3 | 106 | 140 | 32.5％ |
| Comparative example | 105 | 148 | 40.5％ |
It can be seen from table 2 that the expansion rate of the negative electrode plate prepared by using the sulfur-doped pre-lithiated silicon-carbon composite material obtained in the example is significantly smaller than that of the comparative example, because the lithium silicate contained in the material of the example can relieve the expansion in the charging and discharging processes, and the chemical bond structures of the-Li-S-and-CO-NH-in the sulfur-doped pre-lithiated silicon-carbon composite material have the advantage of firm combination, and the expansion rate can be reduced.
(3.2) cycle Performance test
And carrying out cycle test on the soft package lithium ion battery under the conditions that the charge and discharge voltage is 2.5-4.2V, the temperature is 25 +/-3.0 ℃ and the charge and discharge multiplying power is 0.5C/0.5C, and the test results are shown in Table 3.
TABLE 3 comparison of the cycles of the examples and comparative examples
| Examples | Initial capacity retention (%) | Capacity retention rate (%). about 500 times |
| Example 1 | 100 | 93.3 |
| Example 2 | 100 | 93.0 |
| Example 3 | 100 | 92.7 |
| Comparative example | 100 | 88.1 |
As can be seen from table 3, the cycle performance of the soft-packed lithium ion battery prepared by using the sulfur-doped pre-lithiated silicon-carbon composite material obtained in the example is superior to that of the comparative example at each stage of the cycle, because the sulfur-doped pre-lithiated silicon-carbon composite material obtained in the example can increase the amount of lithium ions in the charging and discharging process by means of sufficient lithium ions, and the pre-lithiated material structure formed at the same time has a small expansion force, so that the cycle performance of the pre-lithiated silicon-carbon composite material can be improved.
(3.3) Rate Performance test
Conditions of rate performance test: the charging and discharging voltage is 2.5-4.2V, the temperature is 25 +/-3.0 ℃, the charging multiplying factor is 1.0C, and the discharging multiplying factor is 1.0C, 2.0C, 3.0C and 5.0C. The results of the rate performance test are shown in table 4.
TABLE 4 comparison of Rate Properties of examples and comparative examples
It can be seen from table 4 that the rate capability of the soft-packed lithium ion battery using the sulfur-doped pre-lithiated silicon carbon composite material obtained in the example is significantly better than that of the comparative example, because the sulfur-doped pre-lithiated silicon carbon composite material obtained in the example contains lithium silicate, which provides sufficient lithium ions during the charging and discharging process, thereby improving the high rate capability thereof.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (2)
1. The preparation method of the sulfur-doped prelithiation silicon-carbon composite material is characterized by comprising the following steps of:
(1) adding an organic sulfur compound into the graphene oxide solution, and uniformly stirring to obtain a solution a; the organic sulfur compound is one of methionine, cysteine or 2-mercaptoethanol; the concentration of the graphene oxide solution is 0.1-1 wt.%; the ratio of hydroxyl and carboxyl in the graphene oxide is 0.5-2%;
(2) adding organic lithium and an organic solvent into the solution a obtained in the step (1), and sealing and uniformly stirring to obtain a solution b; the organic lithium is one of n-butyl alcohol lithium, n-butyl lithium or tert-butyl lithium; the organic solvent is one of N-methyl pyrrolidone, carbon tetrachloride or tetrahydrofuran;
(3) adding SiO into the solution b obtained in the step (2) and uniformly stirring, wherein the weight ratio of the SiO to the solution b is 100: 100-500; heating and pressurizing at 100-200 ℃ under 1-5 Mpa for reaction for 1-24 h, filtering and drying to obtain a composite material intermediate;
(4) putting the composite material intermediate obtained in the step (3) into an inert atmosphere, and carbonizing at 800-1100 ℃ for 1-12 h to obtain a sulfur-doped pre-lithiated silicon-carbon composite material;
wherein the weight ratio of the organic sulfur compound, the graphene oxide, the organic lithium and the organic solvent is 10: 0.1-1: 1-5: 100.
2. The sulfur-doped prelithiated silicon-carbon composite material produced by the method of claim 1.
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