CN112467092A - Silicon cathode for lithium ion battery and preparation method thereof - Google Patents
Silicon cathode for lithium ion battery and preparation method thereof Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 45
- 239000010703 silicon Substances 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 10
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229930192474 thiophene Natural products 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 9
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- -1 silicon oxide compound Chemical class 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000004804 winding Methods 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- IWICDTXLJDCAMR-UHFFFAOYSA-N trihydroxy(propan-2-yloxy)silane Chemical compound CC(C)O[Si](O)(O)O IWICDTXLJDCAMR-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 11
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract description 4
- 238000009830 intercalation Methods 0.000 abstract description 4
- 230000002687 intercalation Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000009831 deintercalation Methods 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010661 Li22Si5 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRXOKRLIIVYICJ-UHFFFAOYSA-N butoxy(trihydroxy)silane Chemical compound CCCCO[Si](O)(O)O BRXOKRLIIVYICJ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
- 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
-
- 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
-
- H—ELECTRICITY
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a silicon cathode for a lithium ion battery and a preparation method thereof, which relate to the technical field of preparation of lithium ion battery cathodes and comprise the following steps: adding organic silicon, ferrocene and thiophene into a carbon nano tube precursor solution, and stirring to prepare a mixed solution; continuously injecting the mixed solution into a furnace tube of a vertical tube furnace in a reducing atmosphere, and sintering at high temperature to obtain a silicon-carbon film; and collecting the silicon-carbon film to prepare the silicon cathode. According to the invention, organosilicon, ferrocene, thiophene and a carbon nano tube precursor solution are mixed and sintered, and when the carbon nano tube grows, the generated amorphous silicon oxide compound grows along the length direction of the carbon tube to form a composite material, so that the expansion of the silicon volume along the diameter direction in the lithium intercalation and deintercalation process is effectively relieved; when the lithium ion battery is applied to a lithium battery, the charging and discharging specific capacity and the electric conductivity of the lithium ion battery are improved, and the lithium ion battery has more stable cycle performance.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery cathodes, in particular to a silicon cathode for a lithium ion battery and a preparation method thereof.
Background
The lithium ion battery is an ideal power source for mobile phones, notebook computers, automobiles and the like because of its outstanding advantages of high working voltage, high specific energy, large capacity, small self-discharge, good cyclicity, long service life, light weight, small volume and the like. In order to meet the requirements of wearable devices, medical instruments, precision instruments and meters, and the like, higher requirements are put on key components in electronic products, such as circuit boards, batteries and the like. For example, with the development of intelligent wearable equipment and precision instruments, at the arc position of equipment, the current lithium cell can not satisfy the demand of buckling repeatedly. Meanwhile, in order to replace the used lithium battery more continuously and less, research on a high-capacity and long-life flexible lithium ion battery becomes an important research direction for the development of the lithium ion battery.
The traditional graphite is used as a lithium battery cathode, the research and development of the traditional graphite are close to the theoretical specific capacity 372mAh/g, and the future requirement is difficult to meet. Formation of LiC after lithium intercalation compared to conventional graphite6Intercalation compounds, silicon as the negative electrode material, usually alloyed with lithium to form Li22Si5The theoretical specific capacity of the intermetallic compound reaches 3572 mAh/g. However, silicon as a negative electrode material of a lithium ion battery has the following disadvantages: in the process of lithium ion release and insertion of the silicon material, the volume of the material can expand and contract by more than 300 percent, so that an electrode active substance can be separated from a current collector, electric contact is lost, and the cycle performance of the battery is greatly reduced; and silicon is a semiconductor material with low self-conductivity。
The silicon has defects, which seriously restrict the industrialization of silicon cathode materials. In order to meet the requirements of the modern society on high-capacity and high-density flexible lithium ion batteries, a plurality of technologies are needed to overcome the defects of the silicon negative electrode material.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a silicon cathode for a lithium ion battery and a preparation method thereof.
The invention provides a preparation method of a silicon cathode for a lithium ion battery, which comprises the following steps:
s1, adding organic silicon, ferrocene and thiophene into the carbon nano tube precursor solution, and stirring to prepare a mixed solution;
s2, continuously injecting the mixed solution into a furnace tube of the vertical tube furnace in a reducing atmosphere, and sintering at high temperature to obtain a silicon-carbon film; wherein, the furnace tube of the vertical tube furnace is a quartz tube;
and S3, collecting the silicon-carbon film to prepare the silicon cathode.
Preferably, the organosilicon is one of butyl orthosilicate, propyl orthosilicate, ethyl orthosilicate or isopropyl orthosilicate.
Preferably, the carbon nanotube precursor is at least one of ethanol, benzene-series aromatic hydrocarbon, n-hexane, linear low-carbon hydrocarbon or polymer thereof.
Preferably, in S1, magnetic stirring is adopted, and the stirring time is 0.5-4 h.
Preferably, in S2, the reducing atmosphere is H2(ii) a Preferably, H2The flow rate is 200-1000 mL/min.
Preferably, in S2, the mixed solution is continuously injected into a furnace tube of a vertical tube furnace at a certain speed, wherein the injection speed is 1-20 mL/h.
Preferably, in S2, the temperature of the high-temperature sintering is 1100-1300 ℃.
Preferably, in S3, collecting the silicon-carbon film by spindle stretch winding at the end of the vertical tube furnace to form a silicon negative electrode; preferably, the spindle size can be selected according to actual requirements.
The invention also provides a silicon cathode for the lithium ion battery, which is prepared by the method.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:
1. according to the invention, organosilicon, ferrocene, thiophene and a carbon nano tube precursor solution are mixed and sintered, and when a carbon nano tube grows, a generated amorphous silicon oxide compound grows along the length direction of the carbon tube to form a composite material, so that the expansion of the silicon volume along the diameter direction in the lithium intercalation and deintercalation process is effectively relieved, and the material has an efficient electron transport network, and also has excellent reversible capacity and cycle life;
2. the invention utilizes a vertical tube furnace with a quartz tube inside for sintering, theoretically, precursor solution can be continuously injected into the quartz tube, a material film is formed in a high-temperature sintering area, and the material film is gradually collected and prepared downwards; the spindle is used for stretching and winding the material film at the outlet of the quartz tube, and the required silicon cathode can be prepared by adjusting the rotating speed and the size of the spindle;
3. when the cathode prepared by the invention is applied to a lithium battery, the charge-discharge specific capacity and the conductivity are improved, and the cathode has more stable cycle performance and has wide application prospect in the fields of wearable equipment, medical instruments and precise instruments.
4. The raw materials used in the invention are common chemical raw materials, and the invention has the advantages of low price, no toxicity and harmlessness, simple process and suitability for large-scale industrial production.
Drawings
FIG. 1 is a schematic diagram of a silicon anode according to the present invention;
FIG. 2 is an SEM image of a silicon negative electrode prepared in example 1 of the present invention;
fig. 3 is a first charge-discharge diagram of a battery assembled according to example 1 of the present invention and a comparative example;
fig. 4 is a graph showing cycle performance of batteries assembled according to example 1 of the present invention and a comparative example.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of a silicon negative electrode comprises the following steps: adding 18g of tetraethyl orthosilicate, 3.42g of ferrocene and 1.8g of thiophene into 200ml of ethanol, and uniformly dispersing by magnetic stirring for 0.5h to obtain a mixed solution; and (3) injecting the mixed solution into a vertical high-temperature reaction kettle containing a quartz tube at 10ml/h, heating to 1100 ℃ at the speed of 10 ℃/min in a hydrogen atmosphere of 600ml/min, and collecting at an outlet by using a spindle to prepare the silicon cathode electrode. The whole preparation process is shown in figure 1.
Example 2
A preparation method of a silicon negative electrode comprises the following steps: adding 9g of tetraethyl orthosilicate, 3.42g of ferrocene and 1.8g of thiophene into 200ml of ethanol, and uniformly dispersing by magnetic stirring for 2 hours to obtain a mixed solution; and (3) injecting the mixed solution into a vertical high-temperature reaction kettle containing a quartz tube at 20ml/h, heating to 1100 ℃ at the speed of 10 ℃/min in 1000ml/min hydrogen atmosphere, and collecting at an outlet by using a spindle to prepare the silicon cathode electrode.
Example 3
A preparation method of a silicon negative electrode comprises the following steps: adding 18g of n-butyl orthosilicate, 3.42g of ferrocene and 1.8g of thiophene into 200ml of toluene, and uniformly dispersing by magnetic stirring for 0.5h to obtain a mixed solution; and (3) injecting the mixed solution into a vertical high-temperature reaction kettle containing a quartz tube at 10ml/h, heating to 1100 ℃ at the speed of 10 ℃/min in a hydrogen atmosphere of 600ml/min, and collecting at an outlet by using a spindle to prepare the silicon cathode electrode.
Example 4
A preparation method of a silicon negative electrode comprises the following steps: adding 24g of tetraethyl orthosilicate, 3.42g of ferrocene and 1.8g of thiophene into 200ml of ethanol, and uniformly dispersing by magnetic stirring for 1.5 hours to obtain a mixed solution; and (3) injecting the mixed solution into a vertical high-temperature reaction kettle containing a quartz tube at 12ml/h, heating to 1100 ℃ at the speed of 10 ℃/min in a hydrogen atmosphere of 700ml/min, and collecting at an outlet by using a spindle to prepare the silicon cathode electrode.
Example 5
A preparation method of a silicon negative electrode comprises the following steps: adding 30g of isopropyl n-silicate, 3.42g of ferrocene and 1.8g of thiophene into 200ml of n-hexane, and uniformly dispersing by magnetic stirring for 3 hours to obtain a mixed solution; and (3) injecting the mixed solution into a vertical high-temperature reaction kettle containing a quartz tube at 18ml/h, heating to 1300 ℃ at the speed of 10 ℃/min in the hydrogen atmosphere of 800ml/min, and collecting at an outlet by using a spindle to prepare the silicon cathode electrode.
The surface appearance and the performance of the silicon cathode material prepared by the invention are characterized and tested.
1. The flexible negative electrode sheet obtained in example 1 was taken for scanning by an electron microscope, and the result is shown in fig. 2. As can be seen from fig. 2, the amorphous silicon oxide grows along the length direction of the carbon tube, which can effectively improve the conductivity of the amorphous silicon oxide material and relieve the volume expansion.
2. The negative electrode diaphragm obtained by tabletting the silicon negative electrode prepared in the example 1 is dried in a constant temperature drying oven at 110 ℃ for 24 hours, then dried in vacuum at 80 ℃ for 12 hours, punched into a pole piece with the diameter of 12mm by a punch and transferred into a vacuum glove box for standby. The assembly of the button lithium ion battery uses a metal lithium sheet as a negative electrode, and uses (LiPF)6the/EC + EMC + DMC) is used as electrolyte, the pole piece with the diameter of 12mm is used as a positive pole piece, and all the operations are carried out in a glove box; note the lithium ion button cell of example 1.
Commercial silicon oxide compound material, conductive agent super-p, carbon nano tube and adhesive CMC + SBR in a mass ratio of 8: 1: 1, uniformly mixing and coating the mixture on copper foil to prepare an electrode slice; and then drying the negative electrode diaphragm obtained by tabletting in a constant-temperature drying oven at 110 ℃ for 24h, then carrying out vacuum drying at 80 ℃ for 12h, punching into a pole piece with the diameter of 12mm by using a punch, and transferring into a vacuum glove box for later use. Button type lithium ionThe battery is assembled by using a lithium metal sheet as a negative electrode, and by (LiPF)6the/EC + EMC + DMC) is used as electrolyte, the pole piece with the diameter of 12mm is used as a positive pole piece, and all the operations are carried out in a glove box; and is recorded as a comparative button type lithium ion battery.
Electrochemical performance of the button lithium ion batteries of example 1 and comparative example was measured, and the results are shown in fig. 3 and 4. Fig. 3 is a picture of the first charge and discharge of a button cell assembled with a flexible negative electrode sheet prepared according to the present invention and a commercial silicone oxide. Fig. 4 is a cycle picture of a button cell assembled with a flexible negative electrode sheet made according to the present invention and a commercial silicone compound. Fig. 3 shows that the flexible negative electrode plate can improve the capacity of the material and improve the first efficiency of the button cell; fig. 4 shows that the cycle life of the flexible negative electrode plate can be prolonged.
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. A preparation method of a silicon negative electrode for a lithium ion battery is characterized by comprising the following steps:
s1, adding organic silicon, ferrocene and thiophene into the carbon nano tube precursor solution, and stirring to prepare a mixed solution;
s2, continuously injecting the mixed solution into a furnace tube of the vertical tube furnace in a reducing atmosphere, and sintering at high temperature to obtain a silicon-carbon film; wherein, the furnace tube of the vertical tube furnace is a quartz tube;
and S3, collecting the silicon-carbon film to prepare the silicon cathode.
2. The method of claim 1, wherein the organosilicon is one of butyl orthosilicate, propyl orthosilicate, ethyl orthosilicate, or isopropyl orthosilicate.
3. The method of claim 1 or 2, wherein the carbon nanotube precursor solution is at least one of ethanol, benzene-based aromatic hydrocarbons, n-hexane, linear low carbon hydrocarbons, or polymers thereof.
4. The method for preparing the silicon negative electrode for the lithium ion battery according to any one of claims 1 to 3, wherein in S1, magnetic stirring is adopted, and the stirring time is 0.5-4 h.
5. The method for producing a silicon negative electrode for a lithium ion battery according to any one of claims 1 to 4, wherein in S2, the reducing atmosphere is H2(ii) a Preferably, H2The flow rate is 200-1000 mL/min.
6. The method for preparing the silicon negative electrode for the lithium ion battery according to any one of claims 1 to 5, wherein in S2, the mixed solution is continuously injected into a furnace tube of a vertical tube furnace at a certain speed, and the injection speed is 1-20 mL/h.
7. The method for preparing a silicon negative electrode for a lithium ion battery according to any one of claims 1 to 6, wherein the temperature of the high-temperature sintering in S2 is 1100 to 1300 ℃.
8. The method for preparing the silicon negative electrode for the lithium ion battery according to any one of claims 1 to 7, wherein in S3, the silicon carbon film is collected by spindle stretch winding at the tail end of the vertical tube furnace to form the silicon negative electrode; preferably, the spindle size can be selected according to actual requirements.
9. A silicon negative electrode for a lithium ion battery prepared based on the method of any one of claims 1 to 8.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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