CN113555535A - Silicon-carbon cathode for lithium ion battery and lithium ion battery - Google Patents
Silicon-carbon cathode for lithium ion battery and lithium ion battery Download PDFInfo
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- CN113555535A CN113555535A CN202110614359.8A CN202110614359A CN113555535A CN 113555535 A CN113555535 A CN 113555535A CN 202110614359 A CN202110614359 A CN 202110614359A CN 113555535 A CN113555535 A CN 113555535A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 47
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 55
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 52
- 239000002409 silicon-based active material Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004642 Polyimide Substances 0.000 claims abstract description 6
- 229920001721 polyimide Polymers 0.000 claims abstract description 6
- 229920006254 polymer film Polymers 0.000 claims abstract description 6
- 150000004985 diamines Chemical class 0.000 claims abstract description 5
- 238000005576 amination reaction Methods 0.000 claims abstract description 4
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 claims description 14
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 9
- 239000011863 silicon-based powder Substances 0.000 claims description 9
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 5
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 2
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 claims description 2
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 229910018540 Si C Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 229910052710 silicon Inorganic materials 0.000 abstract description 11
- 239000010703 silicon Substances 0.000 abstract description 11
- 239000002388 carbon-based active material Substances 0.000 abstract description 2
- 239000007773 negative electrode material Substances 0.000 abstract 1
- 238000012643 polycondensation polymerization Methods 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 40
- 238000001035 drying Methods 0.000 description 35
- 238000003756 stirring Methods 0.000 description 32
- 239000000243 solution Substances 0.000 description 31
- 238000001816 cooling Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 12
- 238000000498 ball milling Methods 0.000 description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 238000007865 diluting Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- -1 carbon or silicon Chemical class 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 231100000647 material safety data sheet Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
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- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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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
- H01M4/13—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
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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
- H01M4/38—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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- H01M4/00—Electrodes
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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Abstract
The invention provides a silicon-carbon negative electrode for a lithium ion battery and the lithium ion battery, wherein the silicon-carbon negative electrode comprises a negative current collector and a polymer film attached to the negative current collector, the polymer film comprises a silicon-based active material, graphene and polyimide, and the silicon-carbon negative electrode for the lithium ion battery is prepared by adopting the following method: performing condensation polymerization on dianhydride and diamine to form polyamic acid, and then condensing with amination modified graphene to obtain a graphene polyamic acid copolymer; and mixing the copolymer of the graphene polyamic acid and a silicon-based active material to form slurry, coating the slurry on a negative current collector, and heating for imidization to obtain the silicon-carbon negative electrode for the lithium ion battery. The silicon-carbon negative electrode material can effectively inhibit the volume expansion of silicon, and has the high specific capacity characteristic of a silicon active material and the high cycle stability of a carbon active material.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon-carbon cathode 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, self-discharge rate and the like. And the basic structure of a secondary battery is such that an electrolyte (an electrolytic solution or a solid electrolyte) is sandwiched between a positive electrode and a negative electrode. Both the positive electrode and the negative electrode have a structure including a current collector and an active material provided on the current collector. Among these, the active material is selected from materials capable of occluding and releasing lithium.
At present, a material capable of being used as an occlusion and release of carrier ions, such as carbon or silicon, is generally selected by a skilled person. However, the theoretical specific capacity of carbon is only 372mAh g-1Compared with carbon, the theoretical specific capacity of silicon is up to 4200 mAh g-110 times as much as carbon. And the low lithium-removing/inserting potential (0-0.45V) of silicon is closest to the voltage platform of graphite, and the discharge platform is long and stable, so the silicon is considered to be the most promising active substitute material at present.
However, the electronic conductivity and the ionic conductivity of silicon are low, so that the dynamic performance of the electrochemical reaction is poor; and the cycle stability of the general pure silicon is also poor. Meanwhile, the phase change and the volume expansion of the silicon in the lithiation process can generate larger stress, so that the electrode is broken and pulverized, the resistance is increased, the cycle performance is suddenly reduced, and the like.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a silicon-carbon negative electrode for a lithium ion battery and the lithium ion battery, wherein the silicon-carbon negative electrode can effectively inhibit the volume expansion of silicon, and has the high specific capacity characteristic of a silicon active material and the high cycle stability of a carbon active material.
The invention provides a silicon-carbon negative electrode for a lithium ion battery, which comprises a negative electrode current collector and a polymer film attached to the negative electrode current collector, wherein the polymer film comprises a silicon-based active material, graphene and polyimide, and is characterized in that the silicon-carbon negative electrode for the lithium ion battery is prepared by adopting the following steps:
s1, carrying out polycondensation on dianhydride and diamine to form polyamic acid, and then condensing with amination modified graphene to obtain a graphene polyamic acid copolymer;
and S2, mixing the copolymer of the graphene polyamic acid and a silicon-based active material to form slurry, coating the slurry on a negative current collector, and heating for imidization to obtain the silicon-carbon negative electrode for the lithium ion battery.
Preferably, the dianhydride is at least one of pyromellitic dianhydride, 3', 4, 4' -biphenyltetracarboxylic dianhydride, 4, 4' -oxydiphthalic dianhydride, 3', 4, 4' -benzophenonetetracarboxylic dianhydride, or 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride;
the diamine is at least one of p-phenylenediamine, 4' -diaminobiphenyl, 4' -diaminodiphenyl ether, 4' -diaminodiphenyl sulfide, 4' -diaminobenzophenone, 4' -diaminodiphenyl sulfone or 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane.
Preferably, the aminated modified graphene is obtained by condensing graphene oxide with organic amine and then reducing the graphene oxide and the organic amine;
preferably, the organic amine is at least one of ethylenediamine, butanediamine or hexanediamine.
Preferably, the amount of the aminated and modified graphene is 15-30 wt% of the mass of the polyamic acid.
Preferably, the silicon-based active material is silicon powder with the particle size of 20-200 nm.
Preferably, the mass ratio of the copolymer of graphene polyamic acid to silicon-based active material is 1-3: 1.
Preferably, the heating temperature is 100-300 ℃, and the time is 1-3 h.
The invention also provides a lithium ion battery which comprises the silicon-carbon cathode for the lithium ion battery.
According to the silicon-carbon cathode for the lithium ion battery, polyamide acid and amination modified graphene are subjected to copolymerization condensation, so that graphene is grafted on a polyamide acid molecular chain, and a copolymer of graphene polyamide acid is obtained; and then mixing the copolymer of the graphene polyamic acid with a silicon-based active material, heating and roasting to imidize the polyamic acid, and forming the silicon-carbon negative electrode with polyimide and graphene coated silicon.
In the present invention, on the one hand, in consideration of poor dispersibility of graphene, uniform dispersibility of graphene is objectively improved after graft copolymerization of graphene and polyamic acid, and when mixed with a silicon-based active material, graphene and the silicon-based active material are uniformly combined and form an effective coating, and when the silicon-based active material occludes and releases ions as carriers, the migration of electrons can be accelerated when the ions as carriers pass through graphene, thereby improving the conductivity of the ions of the carriers. On the other hand, when the copolymer of graphene polyamic acid is mixed with the silicon-based active material, the polyimide may also form a coating on the silicon-based active material, and the polyimide serves as a binder at this time, thereby enhancing the adhesion between the silicon-based active material and the current collector and reducing the deterioration of battery characteristics caused by the expansion and contraction of the active material made of silicon.
Therefore, compared with a silicon-carbon cathode formed by simply ball-milling and mixing a silicon-based active material and a carbon source material of graphene in the prior art, the surface of the silicon-based active material is specifically treated, so that the electrochemical cycling stability of the silicon-carbon cathode can be effectively improved, and higher specific capacity of a battery can be obtained.
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 cathode for a lithium ion battery is prepared by the following method:
(1) under the protection of nitrogen, adding 0.54g (5mmol) of p-phenylenediamine PPD and 1.00g (5mmol) of 4, 4 '-diaminodiphenyl ether ODA into 20mL of anhydrous N-methylpyrrolidone NMP, uniformly stirring, adding 3.10g (10mmol) of 4, 4' -oxydiphthalic dianhydride ODPA, and stirring at room temperature for 5 hours to react to obtain a polyamic acid solution;
adding 1.00g of graphene oxide (prepared by a classical Hunmers method) into 10mL of N-methylpyrrolidone NMP, performing ultrasonic dispersion uniformly, adding 0.10g of hexamethylenediamine, stirring at 80 ℃ for reaction for 2 hours, introducing hydrogen, stirring at 100 ℃ for reduction reaction for 6 hours, filtering, and washing to obtain aminated modified graphene;
adding the aminated modified graphene into the polyamic acid solution, stirring and reacting for 3 hours at 50 ℃, and cooling to room temperature to obtain a copolymer solution of graphene polyamic acid;
(2) adding N-methyl pyrrolidone (NMP) into the copolymer solution of the graphene polyamic acid, and diluting until the solid content is 15 wt%; adding 50 wt% of silicon powder (with the average particle size of 60nm) serving as a silicon-based active material according to the mass of the copolymer of the graphene polyamic acid corresponding to the solid content, performing ball milling and uniformly mixing to obtain slurry, and coating the slurry on a copper foil current collector, wherein the thickness is controlled to be 15 micrometers; drying the silicon carbide anode in a drying oven at 70 ℃ for 1 hour for curing, cooling to room temperature, taking out, placing in a tubular furnace, heating to 120 ℃, drying for 0.5 hour, heating to 250 ℃, drying for 0.5 hour, heating to 300 ℃, drying for 1 hour, cooling to room temperature, and taking out to obtain the silicon carbide anode for the lithium ion battery.
Example 2
A silicon-carbon cathode for a lithium ion battery is prepared by the following method:
(1) under the protection of nitrogen, adding 0.92g (5mmol) of 4, 4 '-diaminobiphenyl MSDS and 1.00g (5mmol) of 4, 4' -diaminodiphenyl ether ODA into 20mL of anhydrous N-methylpyrrolidone NMP, uniformly stirring, adding 3.22g (10mmol) of 3, 3', 4, 4' -benzophenone tetracarboxylic dianhydride BTDA, and stirring at room temperature for 5 hours to react to obtain a polyamic acid solution;
adding 1.00g of graphene oxide (prepared by a classical Hunmers method) into 10mL of N-methylpyrrolidone NMP, performing ultrasonic dispersion uniformly, adding 0.10g of hexamethylenediamine, stirring at 80 ℃ for reaction for 2 hours, introducing hydrogen, stirring at 100 ℃ for reduction reaction for 6 hours, filtering, and washing to obtain aminated modified graphene;
adding the aminated modified graphene into the polyamic acid solution, stirring and reacting for 3 hours at 50 ℃, and cooling to room temperature to obtain a copolymer solution of graphene polyamic acid;
(2) adding N-methyl pyrrolidone (NMP) into the copolymer solution of the graphene polyamic acid, and diluting until the solid content is 15 wt%; adding 50 wt% of silicon powder (with the average particle size of 60nm) serving as a silicon-based active material according to the mass of the copolymer of the graphene polyamic acid corresponding to the solid content, performing ball milling and uniformly mixing to obtain slurry, and coating the slurry on a copper foil current collector, wherein the thickness is controlled to be 15 micrometers; drying the silicon carbide anode in a drying oven at 70 ℃ for 1 hour for curing, cooling to room temperature, taking out, placing in a tubular furnace, heating to 120 ℃, drying for 0.5 hour, heating to 250 ℃, drying for 0.5 hour, heating to 300 ℃, drying for 1 hour, cooling to room temperature, and taking out to obtain the silicon carbide anode for the lithium ion battery.
Example 3
A silicon-carbon cathode for a lithium ion battery is prepared by the following method:
(1) under the protection of nitrogen, adding 2.00g (10mmol) of 4, 4 '-diaminodiphenyl ether ODA into 20mL of anhydrous N-methylpyrrolidone NMP, uniformly stirring, adding 1.55g (5mmol) of 4, 4' -oxydiphthalic dianhydride ODPA and 1.12g (5mmol) of 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride PMDA, and stirring at room temperature for 5 hours to react to obtain a polyamic acid solution;
adding 1.00g of graphene oxide (prepared by a classical Hunmers method) into 10mL of N-methylpyrrolidone NMP, performing ultrasonic dispersion uniformly, adding 0.05g of ethylenediamine and 0.05g of butanediamine, stirring at 80 ℃ for reaction for 2 hours, introducing hydrogen, stirring at 100 ℃ for reduction reaction for 6 hours, filtering, and washing to obtain aminated modified graphene;
adding the aminated modified graphene into the polyamic acid solution, stirring and reacting for 3 hours at 50 ℃, and cooling to room temperature to obtain a copolymer solution of graphene polyamic acid;
(2) adding N-methyl pyrrolidone (NMP) into the copolymer solution of the graphene polyamic acid, and diluting until the solid content is 15 wt%; adding 50 wt% of silicon powder (with the average particle size of 60nm) serving as a silicon-based active material according to the mass of the copolymer of the graphene polyamic acid corresponding to the solid content, performing ball milling and uniformly mixing to obtain slurry, and coating the slurry on a copper foil current collector, wherein the thickness is controlled to be 15 micrometers; drying the silicon carbide anode in a drying oven at 70 ℃ for 1 hour for curing, cooling to room temperature, taking out, placing in a tubular furnace, heating to 120 ℃, drying for 0.5 hour, heating to 250 ℃, drying for 0.5 hour, heating to 300 ℃, drying for 1 hour, cooling to room temperature, and taking out to obtain the silicon carbide anode for the lithium ion battery.
Example 4
A silicon-carbon cathode for a lithium ion battery is prepared by the following method:
(1) under the protection of nitrogen, adding 0.54g (5mmol) of p-phenylenediamine PPD and 1.00g (5mmol) of 4, 4 '-diaminodiphenyl ether ODA into 20mL of anhydrous N-methylpyrrolidone NMP, uniformly stirring, adding 3.10g (10mmol) of 4, 4' -oxydiphthalic dianhydride ODPA, and stirring at room temperature for 5 hours to react to obtain a polyamic acid solution;
adding 1.40g of graphene oxide (prepared by a classical Hunmers method) into 10mL of N-methylpyrrolidone NMP, performing ultrasonic dispersion uniformly, adding 0.14g of hexamethylenediamine, stirring at 80 ℃ for reaction for 2 hours, introducing hydrogen, stirring at 100 ℃ for reduction reaction for 6 hours, filtering, and washing to obtain aminated modified graphene;
adding the aminated modified graphene into the polyamic acid solution, stirring and reacting for 3 hours at 50 ℃, and cooling to room temperature to obtain a copolymer solution of graphene polyamic acid;
(2) adding N-methyl pyrrolidone (NMP) into the copolymer solution of the graphene polyamic acid, and diluting until the solid content is 15 wt%; adding 33 wt% of silicon powder (with the average particle size of 60nm) serving as a silicon-based active material according to the mass of the copolymer of the graphene polyamic acid corresponding to the solid content, performing ball milling and mixing uniformly to obtain slurry, and coating the slurry on a copper foil current collector, wherein the thickness is controlled to be 15 micrometers; drying the silicon carbide anode in a drying oven at 70 ℃ for 1 hour for curing, cooling to room temperature, taking out, placing in a tubular furnace, heating to 120 ℃, drying for 0.5 hour, heating to 250 ℃, drying for 0.5 hour, heating to 300 ℃, drying for 1 hour, cooling to room temperature, and taking out to obtain the silicon carbide anode for the lithium ion battery.
Example 5
A silicon-carbon cathode for a lithium ion battery is prepared by the following method:
(1) under the protection of nitrogen, adding 0.54g (5mmol) of p-phenylenediamine PPD and 1.00g (5mmol) of 4, 4 '-diaminodiphenyl ether ODA into 20mL of anhydrous N-methylpyrrolidone NMP, uniformly stirring, adding 3.10g (10mmol) of 4, 4' -oxydiphthalic dianhydride ODPA, and stirring at room temperature for 5 hours to react to obtain a polyamic acid solution;
adding 0.70g of graphene oxide (prepared by a classical Hunmers method) into 10mL of N-methylpyrrolidone NMP, performing ultrasonic dispersion uniformly, adding 0.07g of hexamethylenediamine, stirring at 80 ℃ for reaction for 2 hours, introducing hydrogen, stirring at 100 ℃ for reduction reaction for 6 hours, filtering, and washing to obtain aminated modified graphene;
adding the aminated modified graphene into the polyamic acid solution, stirring and reacting for 3 hours at 50 ℃, and cooling to room temperature to obtain a copolymer solution of graphene polyamic acid;
(2) adding N-methyl pyrrolidone (NMP) into the copolymer solution of the graphene polyamic acid, and diluting until the solid content is 15 wt%; adding 100 wt% of silicon powder (with an average particle size of 60nm) serving as a silicon-based active material according to the mass of the copolymer of the graphene polyamic acid corresponding to the solid content, performing ball milling and mixing uniformly to obtain slurry, and coating the slurry on a copper foil current collector, wherein the thickness is controlled to be 15 micrometers; drying for 1h in a drying oven at 70 ℃ for curing, cooling to room temperature, taking out, placing in a tubular furnace, heating to 120 ℃, drying for 0.5h, heating to 250 ℃, drying for 0.5h, heating to 300 ℃, drying for 1h, cooling to room temperature, and taking out to obtain the silicon-carbon cathode for the lithium ion battery.
Comparative example 1
A silicon-carbon cathode for a lithium ion battery is prepared by the following method:
(1) under the protection of nitrogen, adding 0.54g (5mmol) of p-phenylenediamine PPD and 1.00g (5mmol) of 4, 4 '-diaminodiphenyl ether ODA into 20mL of anhydrous N-methylpyrrolidone NMP, uniformly stirring, adding 3.10g (10mmol) of 4, 4' -oxydiphthalic dianhydride ODPA, and stirring at room temperature for 5 hours to react to obtain a polyamic acid solution;
adding 1.00g of graphene oxide (prepared by a classical Hunmers method) into 10mL of N-methylpyrrolidone NMP, ultrasonically dispersing uniformly, introducing hydrogen, stirring at 100 ℃, carrying out reduction reaction for 6 hours, filtering, and washing to obtain graphene;
adding the graphene into the polyamic acid solution, stirring and reacting for 3 hours at 50 ℃, and cooling to room temperature to obtain a graphene polyamic acid mixture solution;
(2) adding N-methyl pyrrolidone (NMP) into the mixture solution of the graphene polyamic acid, and diluting until the solid content is 15 wt%; adding 50 wt% of silicon powder (with the average particle size of 60nm) serving as a silicon-based active material according to the mass of the copolymer of the graphene polyamic acid corresponding to the solid content, performing ball milling and uniformly mixing to obtain slurry, and coating the slurry on a copper foil current collector, wherein the thickness is controlled to be 15 micrometers; drying the silicon carbide anode in a drying oven at 70 ℃ for 1 hour for curing, cooling to room temperature, taking out, placing in a tubular furnace, heating to 120 ℃, drying for 0.5 hour, heating to 250 ℃, drying for 0.5 hour, heating to 300 ℃, drying for 1 hour, cooling to room temperature, and taking out to obtain the silicon carbide anode for the lithium ion battery.
Comparative example 2
A silicon-carbon cathode for a lithium ion battery is prepared by the following method:
(1) under the protection of nitrogen, adding 0.54g (5mmol) of p-phenylenediamine PPD and 1.00g (5mmol) of 4, 4 '-diaminodiphenyl ether ODA into 20mL of anhydrous N-methylpyrrolidone NMP, uniformly stirring, adding 3.10g (10mmol) of 4, 4' -oxydiphthalic dianhydride ODPA, and stirring at room temperature for 5 hours to react to obtain a polyamic acid solution;
adding 1.00g of graphene oxide (prepared by a classical Hunmers method) into the polyamic acid solution, stirring at 50 ℃ for reacting for 3 hours, and cooling to room temperature to obtain a graphene polyamic acid mixture solution;
(2) adding N-methyl pyrrolidone (NMP) into the mixture solution of the graphene polyamic acid, and diluting until the solid content is 15 wt%; adding 50 wt% of silicon powder (with the average particle size of 60nm) serving as a silicon-based active material according to the mass of the copolymer of the graphene polyamic acid corresponding to the solid content, performing ball milling and uniformly mixing to obtain slurry, and coating the slurry on a copper foil current collector, wherein the thickness is controlled to be 15 micrometers; drying the silicon carbide anode in a drying oven at 70 ℃ for 1 hour for curing, cooling to room temperature, taking out, placing in a tubular furnace, heating to 120 ℃, drying for 0.5 hour, heating to 250 ℃, drying for 0.5 hour, heating to 300 ℃, drying for 1 hour, cooling to room temperature, and taking out to obtain the silicon carbide anode for the lithium ion battery.
The silicon-carbon negative electrodes for lithium ion batteries prepared in examples and comparative examples were assembled into a battery and subjected to charge and discharge performance tests, and the results were as follows:
the silicon-carbon cathode for the lithium ion battery prepared in the example and the comparative example is used as the working electrode of the button cell, the metal lithium sheet is used as the counter electrode, Celgard2400 is used as the diaphragm, and 1mol/L LiPF6The solution (EC: EMC: DMC mixed solvent in volume ratio of 1:1: 1) is used as electrolyte, and is assembled into a CR2032 type button cell in a glove box, and the button cell is subjected to constant current charge and discharge test on a LAND cell test system.
The first charge and discharge was carried out at 0.05C (current density: 100mA/g), and the second and subsequent charges and discharges were carried out at 0.5C (current density: 1000mA/g), and the charge and discharge voltage ranged from 0.01 to 3.0V.
Table 1:
as can be seen from the above description of examples and comparative examples, the first discharge capacity, the first coulombic ratio, and the 200-cycle performance of the silicon-carbon negative electrode prepared in the examples are significantly higher than those of the silicon-carbon negative electrode prepared in the comparative example.
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 equivalent substitutions or changes according to the technical solution and the inventive concept of the present invention should be covered by the scope of the present invention.
Claims (8)
1. The silicon-carbon negative electrode for the lithium ion battery comprises a negative electrode current collector and a polymer film attached to the negative electrode current collector, wherein the polymer film comprises a silicon-based active material, graphene and polyimide, and is characterized in that the silicon-carbon negative electrode for the lithium ion battery is prepared by the following steps:
s1, carrying out polycondensation on dianhydride and diamine to form polyamic acid, and then condensing with amination modified graphene to obtain a graphene polyamic acid copolymer;
and S2, mixing the copolymer of the graphene polyamic acid and a silicon-based active material to form slurry, coating the slurry on a negative current collector, and heating for imidization to obtain the silicon-carbon negative electrode for the lithium ion battery.
2. The silicon-carbon negative electrode for a lithium ion battery according to claim 1, wherein the dianhydride is at least one of pyromellitic dianhydride, 3', 4, 4' -biphenyltetracarboxylic dianhydride, 4, 4' -oxydiphthalic dianhydride, 3', 4, 4' -benzophenonetetracarboxylic dianhydride, or 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride;
the diamine is at least one of p-phenylenediamine, 4' -diaminobiphenyl, 4' -diaminodiphenyl ether, 4' -diaminodiphenyl sulfide, 4' -diaminobenzophenone, 4' -diaminodiphenyl sulfone or 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane.
3. The silicon-carbon negative electrode for the lithium ion battery according to claim 1 or 2, wherein the aminated modified graphene is obtained by condensing graphene oxide with organic amine and then reducing the resultant;
preferably, the organic amine is at least one of ethylenediamine, butanediamine or hexanediamine.
4. The silicon-carbon negative electrode for a lithium ion battery according to any one of claims 1 to 3, wherein the amount of the aminated modified graphene is 15 to 30 wt% based on the mass of the polyamic acid.
5. The silicon-carbon negative electrode for a lithium ion battery according to any one of claims 1 to 4, wherein the silicon-based active material is silicon powder having a particle size of 20 to 200 nm.
6. The silicon-carbon negative electrode for the lithium ion battery according to any one of claims 1 to 5, wherein the mass ratio of the copolymer of the graphene polyamic acid to the silicon-based active material is 1-3: 1.
7. The Si-C anode for lithium ion batteries according to any of claims 1 to 6, wherein the heating temperature is 100 ℃ and 300 ℃ for 1 to 3 hours.
8. A lithium ion battery comprising the silicon carbon negative electrode for a lithium ion battery according to any one of claims 1 to 7.
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| CN103258991A (en) * | 2012-02-17 | 2013-08-21 | 株式会社半导体能源研究所 | Method for forming negative electrode and method for manufacturing lithium secondary battery |
| CN108091861A (en) * | 2017-12-14 | 2018-05-29 | 东华大学 | A kind of preparation method of the organic electrode materials based on polyimide structures |
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| CN103258991A (en) * | 2012-02-17 | 2013-08-21 | 株式会社半导体能源研究所 | Method for forming negative electrode and method for manufacturing lithium secondary battery |
| CN108091861A (en) * | 2017-12-14 | 2018-05-29 | 东华大学 | A kind of preparation method of the organic electrode materials based on polyimide structures |
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| CN115710352A (en) * | 2022-10-31 | 2023-02-24 | 浙江中科玖源新材料有限公司 | Binder for lithium ion battery silicon cathode and lithium ion battery silicon cathode |
| CN115710352B (en) * | 2022-10-31 | 2024-04-16 | 浙江中科玖源新材料有限公司 | Binder for silicon negative electrode of lithium ion battery and silicon negative electrode of lithium ion battery |
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