CN114695892B - Diamine cross-linked polyimide for negative electrode binder and preparation method thereof - Google Patents
Diamine cross-linked polyimide for negative electrode binder and preparation method thereof Download PDFInfo
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- CN114695892B CN114695892B CN202210202784.0A CN202210202784A CN114695892B CN 114695892 B CN114695892 B CN 114695892B CN 202210202784 A CN202210202784 A CN 202210202784A CN 114695892 B CN114695892 B CN 114695892B
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 108
- 229920001721 polyimide Polymers 0.000 title claims abstract description 108
- 150000004985 diamines Chemical class 0.000 title claims abstract description 85
- 239000011883 electrode binding agent Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 diamine compound Chemical class 0.000 claims description 31
- 239000002202 Polyethylene glycol Substances 0.000 claims description 22
- 229920001223 polyethylene glycol Polymers 0.000 claims description 22
- AJYDKROUZBIMLE-UHFFFAOYSA-N 4-[2-[2-[2-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=CC=C(OC=2C=CC(N)=CC=2)C=1C(C)(C)C1=CC=CC=C1OC1=CC=C(N)C=C1 AJYDKROUZBIMLE-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 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 description 16
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 claims description 15
- 239000002798 polar solvent Substances 0.000 claims description 15
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 14
- NABYEWFUAONMMH-UHFFFAOYSA-N 1,8-diaminooctane-3,6-dione Chemical group NCCC(=O)CCC(=O)CCN NABYEWFUAONMMH-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 claims description 11
- NHEZUKBLVBOLTI-UHFFFAOYSA-N 4h-2-benzofuran-1,3,5-trione Chemical compound C1C(=O)C=CC2=C1C(=O)OC2=O NHEZUKBLVBOLTI-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052710 silicon Inorganic materials 0.000 abstract description 24
- 239000010703 silicon Substances 0.000 abstract description 24
- 238000004132 cross linking Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 12
- 230000008961 swelling Effects 0.000 abstract description 11
- 239000007773 negative electrode material Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000010405 anode material Substances 0.000 description 10
- 239000002981 blocking agent Substances 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 9
- 150000002513 isocyanates Chemical group 0.000 description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical group NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- BWAPJIHJXDYDPW-UHFFFAOYSA-N 2,5-dimethyl-p-phenylenediamine Chemical compound CC1=CC(N)=C(C)C=C1N BWAPJIHJXDYDPW-UHFFFAOYSA-N 0.000 description 1
- MJAVQHPPPBDYAN-UHFFFAOYSA-N 2,6-dimethylbenzene-1,4-diamine Chemical compound CC1=CC(N)=CC(C)=C1N MJAVQHPPPBDYAN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002633 protecting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
Classifications
-
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of C09D179/08, in particular to diamine cross-linking type polyimide for a negative electrode binder and a preparation method thereof, wherein 60-100 parts of linear polyimide, 100-150 parts of water and 30-50 parts of diamine solution are adopted, and diamine is adopted to cross-link the linear polyimide from the preparation of the linear polyimide, so that the provided diamine cross-linking type polyimide has higher mechanical strength and lower swelling degree, has stronger bonding effect with a silicon-based negative electrode material, ensures the cycle performance under the condition of high-current density charge and discharge, meets the actual use requirement of the high-capacity silicon-based negative electrode material, and has high practical popularization and application values.
Description
Technical Field
The invention relates to the field of C09D179/08, in particular to diamine cross-linked polyimide for a negative electrode binder and a preparation method thereof.
Background
The binder is an important component in lithium ion batteries and functions to bind the active material and the conductive agent together and to adhere to the current collector, allowing electrons to flow out of or to the external current through the active material, the conductive agent, and the current collector.
The traditional PVDF binder is widely applied to lithium ion batteries due to the advantages of strong oxidation and reduction resistance, good thermal stability, easy dispersion and the like. Chinese patent CN107004844a discloses a prelithiated silicon anode containing PVDF binder, which, although prolonging the cycle life to some extent, has a weak van der waals force with silicon particles, which cannot buffer the huge volume expansion effect in the charge-discharge process, and is very liable to cause pulverization of electrode material or falling off from current collector, ultimately affecting the electrochemical performance of the electrode. Polyimide has good mechanical property, chemical stability, extremely low dielectric constant and excellent thermal stability, and is widely applied to various fields at present, but the existing polyimide adhesive is difficult to directly use in a high-capacity silicon-based negative electrode material, huge volume change can be generated in the charge and discharge process, and the pole piece is difficult to keep integrity, so that poor cycle performance under the high-current density charge and discharge conditions is caused; chinese patent CN111777984a discloses a sulfonated polyimide binder, an electrode sheet and a lithium ion battery, and although the performance of the lithium ion battery is enhanced to some extent, the sulfonated polyimide faces swelling in an electrolyte to deteriorate the electrochemical performance of the battery.
Therefore, the diamine cross-linked polyimide for the negative electrode binder and the preparation method thereof are provided, the linear polyimide is used as a main raw material, diamine is used for cross-linking the linear polyimide, so that the diamine cross-linked polyimide provided has higher mechanical strength and lower swelling degree, has stronger bonding effect with the silicon-based negative electrode material, ensures the cycle performance under the condition of high-current density charge and discharge, meets the actual use requirement of the high-capacity silicon-based negative electrode material, and has high practical popularization and application values.
Disclosure of Invention
The invention provides diamine cross-linked polyimide for a negative electrode binder, which comprises the following preparation raw materials in parts by weight: 60-100 parts of linear polyimide, 100-150 parts of water and 30-50 parts of diamine solution.
As a preferable technical scheme, the preparation raw materials of the linear polyimide at least comprise, by weight, 10-15 parts of diamine, 15-25 parts of dianhydride, 3-6 parts of end capping agent, 5-10 parts of flexible compound and 4-6 parts of polar solvent;
as a preferred technical scheme, the preparation method of the linear polyimide at least comprises the following steps:
(1) Dissolving diamine in a polar solvent to obtain a diamine solution;
(2) Adding dianhydride into diamine solution to react to obtain short-chain hard segments, and adding a blocking agent to block;
(3) And then adding a flexible compound to perform polymerization reaction to obtain the linear polyimide.
As a preferred technical scheme, the diamine is a combination of aliphatic diamine and aromatic diamine;
preferably, the aliphatic diamine is 1, 8-octanediamine or 3, 6-dioxo-1, 8-octanediamine;
preferably, the aromatic diamine structure at least contains one of imidazole group, fluoroalkyl group and hydroxyl group;
Preferably, the diamine is a combination of 3, 6-dioxo-1, 8-octanediamine and 2- (4-aminophenyl) -5-aminobenzimidazole; the molar ratio of 3, 6-dioxo-1, 8-octanediamine to 2- (4-aminophenyl) -5-aminobenzimidazole is (1-2): (0.8-1.5).
As a preferable technical scheme, the dianhydride is at least one selected from 4, 4-oxo-phthalic anhydride, 3, 4-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride and 1,4,5, 8-naphthalene tetracarboxylic anhydride;
Preferably, the dianhydride is 4, 4-oxo-phthalic anhydride;
as a preferable technical scheme, the polar solvent is at least one selected from dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, N-methylformamide, dimethylacetamide and dimethyl sulfoxide;
Preferably, the polar solvent is dimethylformamide;
As a preferred technical scheme, the blocking agent is isocyanate; preferably, the isocyanate is hexamethylene diisocyanate.
As a preferable technical scheme, the flexible compound is at least one of water-soluble diamine, water-soluble dianhydride and water-soluble diol;
Preferably, the flexible compound is a combination of propylene diamine and polyethylene glycol; the mass ratio of the propylene diamine to the polyethylene glycol is (4-6): (0.5-1.5); preferably, the polyethylene glycol has a weight average molecular weight of 400-600;
The invention starts from the preparation of polyimide by adopting the following mole ratio (1-2): (0.8-1.5) reacting 3, 6-dioxo-1, 8-octanediamine and 2- (4-aminophenyl) -5-aminobenzimidazole with 4, 4-oxo-phthalic anhydride, and then blocking by adopting hexamethylene diisocyanate to obtain a short-chain hard segment, thereby endowing the linear polyimide with good thermal stability and chemical stability and ensuring the mechanical property and adhesive property of the polyimide; the inventor speculates that the reason is probably that the application stability of the polyimide product is lower due to the strong intermolecular interaction force of the wholly aromatic polyimide, the introduction of the 3, 6-dioxo-1, 8-octanediamine properly reduces the strong intermolecular interaction force in the aromatic polyimide structure under the molar ratio, the linear polyimide is endowed with excellent thermal stability and chemical stability on the basis of ensuring the mechanical property of the polyimide, the subsequent processing is facilitated, and meanwhile, the imidazole group in the molecular chain structure of the linear polyimide can show good cohesiveness with the silicon-based anode material through coordination.
Although polyimide has good mechanical properties, chemical stability, extremely low dielectric constant and excellent thermal stability, and is widely applied to various fields at present, the existing polyimide adhesive is difficult to directly use in high-capacity silicon-based anode materials, huge volume change is generated in the charge and discharge process, and the pole piece is difficult to keep integrity, so that poor cycle performance under the charge and discharge condition with high current density is caused, and the inventor discovers that in the research process, by introducing a flexible compound into a reaction system of the linear polyimide, especially when the flexible compound is in a mass ratio of (4-6): (0.5-1.5) when the propylene diamine and the polyethylene glycol are combined, the propylene diamine and the polyethylene glycol exert synergistic effect to the greatest extent, so that the electrochemical performance of the battery is effectively improved when the battery is used as a silicon-based negative electrode binder, and the capacity cycle attenuation is reduced; the inventor speculates that the reason is probably that the small molecular flexible chain segments propylene diamine and polyethylene glycol are introduced into the linear polyimide molecular structure under the mass ratio, so that the flexibility of the linear polyimide is obviously improved, the pole piece is prevented from being damaged due to volume change when the linear polyimide is subsequently applied to a battery, the electrochemical performance of the battery when the linear polyimide is used as a silicon-based negative electrode adhesive is effectively improved, and the poor cycle performance under the high-current density charge and discharge conditions is ensured. The inventor unexpectedly found in the research process that when the weight average molecular weight of polyethylene glycol is controlled to be 400-600, the linear polyimide is endowed with good water solubility, and the subsequent processing performance of the linear polyimide is effectively improved. The inventor speculates that the reason is probably that when the weight average molecular weight of the polyethylene glycol is 400-600, the polyethylene glycol can be fully and effectively polymerized with the short-chain hard segment after the end capping of the isocyanate, and the hydroxyl-containing polyethylene glycol flexible segment is introduced into the linear polyimide structure, so that the linear polyimide is endowed with good water solubility, and the subsequent processing performance of the linear polyimide is effectively improved.
As a preferred technical scheme, the diamine solution at least comprises a diamine compound and a solvent; preferably, the mass ratio of the diamine compound to the solvent is (5-7): (3-5).
As a preferred embodiment, the diamine compound comprises at least 2, 2-bis (4-aminophenoxyphenyl) propane (BAPP), 2' -divinyl-4, 4' -diaminobiphenyl (VAB), 2' -dimethyl-4, 4' -diaminobiphenyl (m-TB), 2' -diethyl-4, 4' -diaminobiphenyl, 2', one of 6,6' -tetramethyl-4, 4' -diaminobiphenyl, 2' -diphenyl-4, 4' -diaminobiphenyl, 2, 4-diaminotoluene, m-xylene-2, 5-diamine, p-xylene-2, 5-diamine; preferably, the diamine compound comprises 2, 2-bis (4-aminophenoxyphenyl) propane.
As a preferred embodiment, the diamine compound further comprises 1, 3-bis (3-aminopropyl) tetramethyl disiloxane; as a preferable technical scheme, the molar ratio of the 2, 2-bis (4-aminophenoxy phenyl) propane to the 1, 3-bis (3-aminopropyl) tetramethyl disiloxane is (2-4): (1-2).
As a preferred technical scheme, the solvent is N-methyl pyrrolidone.
In the practical application process of the lithium ion battery, the final electrochemical performance is determined to a certain extent due to the huge volume expansion effect in the charge and discharge process, and the electrode material falls off from the current collector due to swelling of polyimide in electrolyte, so that the electrochemical performance of the battery is reduced, and the service life of the battery is reduced. The invention adopts diamine to crosslink the linear polyimide, so as to improve the bonding effect between the polyimide binder and the silicon-based anode material, ensure the electrochemical performance and prolong the service life of the battery, and the inventor discovers that the diamine crosslinked polyimide has higher mechanical strength and stronger bonding effect with the silicon-based anode material by adopting 2, 2-bis (4-aminophenoxy phenyl) propane to crosslink the linear polyimide in the research process; the inventor speculates that the reason is probably that 2, 2-bis (4-aminophenoxy phenyl) propane and the linear polyimide provided by the invention have good crosslinking action, the structure of the linear polyimide is opened in the process of crosslinking the 2, 2-bis (4-aminophenoxy phenyl) propane, the strong polar functional group in the linear polyimide structure can generate strong interaction with the active group on the surface of the silicon-based anode material, the formed crosslinking structure has high mechanical strength, and the crosslinking structure has buffering and protecting effects on huge volume expansion effect of the subsequent battery in the charge and discharge process, so that the pulverization and the falling of the electrode material are avoided, and the electrochemical performance of the electrode is improved;
Although the electrochemical performance of the electrode can be improved to a certain extent by adopting 2, 2-bis (4-aminophenoxyphenyl) propane for crosslinking, the problem that the electrochemical performance of the battery is poor due to swelling of a polyimide binder in an electrolyte cannot be effectively solved, and the inventor finds through creative research experiments that the molar ratio of the 2, 2-bis (4-aminophenoxyphenyl) propane to the 1, 3-bis (3-aminopropyl) tetramethyl disiloxane is controlled to be (2-4) by introducing 1, 3-bis (3-aminopropyl) tetramethyl disiloxane: and (1-2), on the basis of ensuring the mechanical properties of the provided diamine cross-linked polyimide, the diamine cross-linked polyimide has a stronger bonding effect with the silicon-based anode material, so that the provided diamine cross-linked polyimide has a lower swelling degree, the cycle performance of the battery under the high-current density charge and discharge conditions is ensured, and the actual use requirements of the high-capacity silicon-based anode material are met. The inventors speculate that the reason may be to control the molar ratio of 2, 2-bis (4-aminophenoxyphenyl) propane, 1, 3-bis (3-aminopropyl) tetramethyldisiloxane introduced to be (2-4): in the process (1-2), the existence of the siloxane structure promotes the crosslinking of the linear polyimide by the 2, 2-bis (4-aminophenoxy phenyl) propane, and the synergistic effect between the crosslinking agents is the best, so that the diamine crosslinked polyimide structure after crosslinking has lower swelling degree in electrolyte, and the problem that the electrochemical performance of a battery is poor due to the swelling of the existing polyimide binder in the electrolyte is solved.
The invention also provides a preparation method of diamine cross-linked polyimide for the negative electrode binder, which is to dissolve linear polyimide in water and add diamine solution for cross-linking.
Advantageous effects
1. The invention provides diamine cross-linked polyimide for a negative electrode binder and a preparation method thereof, wherein linear polyimide is used as a main raw material, diamine is used for cross-linking the linear polyimide, so that the diamine cross-linked polyimide has higher mechanical strength and lower swelling degree, has stronger bonding effect with a silicon-based negative electrode material, ensures the cycle performance under the condition of high-current density charge and discharge, meets the actual use requirement of the high-capacity silicon-based negative electrode material, and has high practical popularization and application values.
2. The invention starts from the preparation of polyimide by adopting the following mole ratio (1-2): (0.8-1.5) 3, 6-dioxo-1, 8-octanediamine and 2- (4-aminophenyl) -5-aminobenzimidazole are blocked by hexamethylene diisocyanate after being reacted with 4, 4-oxo-phthalic anhydride, so that a short chain hard segment can be obtained, good thermal stability and chemical stability are endowed to linear polyimide, and the mechanical property and adhesive property of polyimide are ensured.
3. In the invention, the flexible compound is introduced into a reaction system of the linear polyimide, especially when the flexible compound is prepared by the following components in mass ratio of (4-6): and (0.5-1.5) when the propylene diamine and the polyethylene glycol are combined, the propylene diamine and the polyethylene glycol exert synergistic effect to the greatest extent, so that the electrochemical performance of the battery is effectively improved when the battery is used as a silicon-based negative electrode binder, and the capacity cycle attenuation is reduced.
4. The linear polyimide is crosslinked by adopting 2, 2-bis (4-aminophenoxyphenyl) propane, so that the diamine crosslinked polyimide has high mechanical strength and has strong bonding effect with the silicon-based anode material.
5. By introducing 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, in particular controlling the molar ratio of said 2, 2-bis (4-aminophenoxyphenyl) propane, 1, 3-bis (3-aminopropyl) tetramethyldisiloxane to (2-4): and (1-2), on the basis of ensuring the mechanical properties of the provided diamine cross-linked polyimide, the diamine cross-linked polyimide has a stronger bonding effect with the silicon-based anode material, so that the provided diamine cross-linked polyimide has a lower swelling degree, the cycle performance of the battery under the high-current density charge and discharge conditions is ensured, and the actual use requirements of the high-capacity silicon-based anode material are met.
Detailed Description
Example 1
In one aspect, the embodiment 1 of the present invention provides a diamine cross-linked polyimide for a negative electrode binder, which is prepared from the following raw materials in parts by weight: 80 parts of linear polyimide, 120 parts of water and 40 parts of diamine solution.
The linear polyimide is prepared from the following raw materials in parts by weight, wherein the raw materials comprise 12 parts of diamine, 20 parts of dianhydride, 5 parts of end-capping agent, 8 parts of flexible compound and 5 parts of polar solvent;
The preparation method of the linear polyimide comprises the following steps:
(1) Dissolving diamine in a polar solvent to obtain a diamine solution;
(2) Adding dianhydride into diamine solution to react to obtain short-chain hard segments, and adding a blocking agent to block;
(3) And then adding a flexible compound to perform polymerization reaction to obtain the linear polyimide.
The diamine is a combination of aliphatic diamine and aromatic diamine;
The diamine is a combination of 3, 6-dioxo-1, 8-octanediamine and 2- (4-aminophenyl) -5-aminobenzimidazole; the molar ratio of the 3, 6-dioxo-1, 8-octanediamine to the 2- (4-aminophenyl) -5-aminobenzimidazole is 1.5:1.
The dianhydride is 4, 4-oxo-phthalic anhydride;
the polar solvent is dimethylformamide;
the blocking agent is isocyanate; the isocyanate is hexamethylene diisocyanate.
The flexible compound is a combination of propylene diamine and polyethylene glycol; the mass ratio of the propylene diamine to the polyethylene glycol is 5:1, a step of; the weight average molecular weight of the polyethylene glycol is 600;
the diamine solution at least comprises a diamine compound and a solvent; the mass ratio of the diamine compound to the solvent is 6:4.
The diamine compound comprises 2, 2-bis (4-aminophenoxyphenyl) propane.
The diamine compound further comprises 1, 3-bis (3-aminopropyl) tetramethyl disiloxane; the molar ratio of the 2, 2-bis (4-aminophenoxy phenyl) propane to the 1, 3-bis (3-aminopropyl) tetramethyl disiloxane is 3:1.5.
The solvent is N-methyl pyrrolidone.
In another aspect, embodiment 1 of the present invention provides a method for preparing diamine cross-linked polyimide for a negative electrode binder, wherein the method comprises the steps of dissolving linear polyimide in water, and adding diamine solution for cross-linking.
Example 2
In one aspect, the embodiment 2 of the present invention provides a diamine cross-linked polyimide for a negative electrode binder, which is prepared from the following raw materials in parts by weight: 100 parts of linear polyimide, 150 parts of water and 50 parts of diamine solution.
The linear polyimide is prepared from the following raw materials in parts by weight, namely 15 parts of diamine, 25 parts of dianhydride, 6 parts of end-capping agent, 10 parts of flexible compound and 6 parts of polar solvent;
The preparation method of the linear polyimide comprises the following steps:
(1) Dissolving diamine in a polar solvent to obtain a diamine solution;
(2) Adding dianhydride into diamine solution to react to obtain short-chain hard segments, and adding a blocking agent to block;
(3) And then adding a flexible compound to perform polymerization reaction to obtain the linear polyimide.
The diamine is a combination of aliphatic diamine and aromatic diamine;
the diamine is a combination of 3, 6-dioxo-1, 8-octanediamine and 2- (4-aminophenyl) -5-aminobenzimidazole; the molar ratio of the 3, 6-dioxo-1, 8-octanediamine to the 2- (4-aminophenyl) -5-aminobenzimidazole is 2:1.5.
The dianhydride is 4, 4-oxo-phthalic anhydride;
the polar solvent is dimethylformamide;
the blocking agent is isocyanate; the isocyanate is hexamethylene diisocyanate.
The flexible compound is a combination of propylene diamine and polyethylene glycol; the mass ratio of the propylene diamine to the polyethylene glycol is 6:1.5; the weight average molecular weight of the polyethylene glycol is 600;
the diamine solution at least comprises a diamine compound and a solvent; the mass ratio of the diamine compound to the solvent is 7:5.
The diamine compound comprises 2, 2-bis (4-aminophenoxyphenyl) propane.
The diamine compound further comprises 1, 3-bis (3-aminopropyl) tetramethyl disiloxane; the molar ratio of the 2, 2-bis (4-aminophenoxy phenyl) propane to the 1, 3-bis (3-aminopropyl) tetramethyl disiloxane is 2:1.
The solvent is N-methyl pyrrolidone.
In another aspect, embodiment 2 of the present invention provides a method for preparing diamine cross-linked polyimide for a negative electrode binder, wherein the method comprises the steps of dissolving linear polyimide in water, and adding diamine solution for cross-linking.
Example 3
In one aspect, the embodiment 1 of the present invention provides a diamine cross-linked polyimide for a negative electrode binder, which is prepared from the following raw materials in parts by weight: 60 parts of linear polyimide, 100 parts of water and 30 parts of diamine solution.
The linear polyimide comprises, by weight, 10 parts of diamine, 15 parts of dianhydride, 3 parts of a blocking agent, 5 parts of a flexible compound and 4 parts of a polar solvent;
The preparation method of the linear polyimide comprises the following steps:
(1) Dissolving diamine in a polar solvent to obtain a diamine solution;
(2) Adding dianhydride into diamine solution to react to obtain short-chain hard segments, and adding a blocking agent to block;
(3) And then adding a flexible compound to perform polymerization reaction to obtain the linear polyimide.
The diamine is a combination of aliphatic diamine and aromatic diamine;
The diamine is a combination of 3, 6-dioxo-1, 8-octanediamine and 2- (4-aminophenyl) -5-aminobenzimidazole; the molar ratio of the 3, 6-dioxo-1, 8-octanediamine to the 2- (4-aminophenyl) -5-aminobenzimidazole is 1:0.8.
The dianhydride is 4, 4-oxo-phthalic anhydride;
the polar solvent is dimethylformamide;
the blocking agent is isocyanate; the isocyanate is hexamethylene diisocyanate.
The flexible compound is a combination of propylene diamine and polyethylene glycol; the mass ratio of the propylene diamine to the polyethylene glycol is 4:0.5; the weight average molecular weight of the polyethylene glycol is 600;
the diamine solution at least comprises a diamine compound and a solvent; the mass ratio of the diamine compound to the solvent is 5:3.
The diamine compound comprises 2, 2-bis (4-aminophenoxyphenyl) propane.
The diamine compound further comprises 1, 3-bis (3-aminopropyl) tetramethyl disiloxane; the molar ratio of the 2, 2-bis (4-aminophenoxy phenyl) propane to the 1, 3-bis (3-aminopropyl) tetramethyl disiloxane is 2:1.
The solvent is N-methyl pyrrolidone.
In another aspect, embodiment 3 of the present invention provides a method for preparing diamine cross-linked polyimide for a negative electrode binder, wherein the method comprises the steps of dissolving linear polyimide in water, and adding diamine solution for cross-linking.
Comparative example 1
Comparative example 1 of the present invention provides a diamine cross-linked polyimide for a negative electrode binder, which is different from example 1 in that the linear polyimide is polyetherimide.
Comparative example 2
Comparative example 2 of the present invention provides a diamine cross-linked polyimide for a negative electrode binder, which is different from example 1 in that the diamine is an aliphatic diamine, and the aliphatic diamine is 1, 8-octanediamine.
Comparative example 3
Comparative example 3 of the present invention provides a diamine cross-linked polyimide for a negative electrode binder, which is different from example 1 in that the flexible compound is maleic anhydride.
Comparative example 4
Comparative example 4 of the present invention provides a diamine cross-linked polyimide for a negative electrode binder, which is different from example 1 in that the diamine compound does not include 2, 2-bis (4-aminophenoxyphenyl) propane.
Comparative example 5
Comparative example 5 of the present invention provides a diamine cross-linked polyimide for a negative electrode binder, which is different from example 1 in that the diamine compound does not include 1, 3-bis (3-aminopropyl) tetramethyldisiloxane.
Performance test method
The diamine cross-linked polyimide prepared in examples and comparative examples was prepared into a silicon-based negative electrode sheet in the following manner, and assembled into a battery, and the peel strength of the silicon-based negative electrode sheet, the swelling rate of the sheet, and the electrochemical performance of the battery were tested, and the performance test results are shown in table 1.
Preparing a negative electrode plate: according to the weight portions, 5 portions of diamine cross-linked polyimide, 15 portions of silicon carbon active material and 5 portions of acetylene black are added into 100 portions of N-methyl-2-pyrrolidone, the mixture is stirred uniformly to obtain negative electrode slurry, the negative electrode slurry is coated on copper foil, and the negative electrode slurry is dried for 12 hours at 80 ℃, and then the silicon-based negative electrode plate is obtained through stamping forming.
And assembling the negative electrode plate and the LFP positive electrode plate into a battery, wherein the battery electrolyte is a mixed solvent of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate of LiPF 6.
The battery was assembled as described above using PVDF as the negative electrode binder in the comparative example.
Claims (4)
1. The diamine cross-linked polyimide for the negative electrode binder is characterized by comprising the following preparation raw materials in parts by weight: 60-100 parts of linear polyimide, 100-150 parts of water and 30-50 parts of diamine solution; the preparation raw materials of the linear polyimide at least comprise, by weight, 10-15 parts of diamine, 15-25 parts of dianhydride, 3-6 parts of end capping agent, 5-10 parts of flexible compound and 4-6 parts of polar solvent; the diamine is 3, 6-dioxo-1, 8-octanediamine and 2- (4-aminophenyl) -5-aminobenzimidazole with the mol ratio of (1-2) (0.8-1.5); the flexible compound is a combination of propylene diamine and polyethylene glycol with the mass ratio of (4-6) (0.5-1.5); the diamine solution at least comprises a diamine compound and a solvent; the diamine compound has a molar ratio of (2-4): 2, 2-bis (4-aminophenoxyphenyl) propane and 1, 3-bis (3-aminopropyl) tetramethyldisiloxane of (1-2).
2. The diamine cross-linked polyimide for a negative electrode binder according to claim 1, wherein the dianhydride is at least one selected from the group consisting of 4, 4-oxo-phthalic anhydride, 3, 4-benzophenone-tetracarboxylic dianhydride, pyromellitic dianhydride, and 1,4,5, 8-naphthalene-tetracarboxylic anhydride.
3. The diamine cross-linked polyimide for a negative electrode binder according to claim 2, wherein the polar solvent is at least one selected from dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, N-methylformamide, dimethylacetamide and dimethylsulfoxide.
4. A method for producing a diamine cross-linked polyimide for a negative electrode binder according to any one of claims 1 to 3, characterized in that the linear polyimide is dissolved in water and cross-linked by adding a diamine solution.
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| CN115548259A (en) * | 2022-11-28 | 2022-12-30 | 中创新航技术研究中心(深圳)有限公司 | Negative plate and battery using same |
| KR20250133059A (en) * | 2024-02-29 | 2025-09-05 | 삼성에스디아이 주식회사 | Electrode of lithium rechargeable battery and rechargeable lithium battery including the same |
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| CN113480442A (en) * | 2021-08-20 | 2021-10-08 | 吉林大学 | Cross-linkable diamine monomer, preparation method and application thereof in preparation of polyimide |
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| KR101230418B1 (en) * | 2011-04-05 | 2013-02-06 | 한국화학연구원 | Cross-linked Polyimide film and Preparation method for the same |
| JP5784993B2 (en) * | 2011-06-14 | 2015-09-24 | 新日鉄住金化学株式会社 | Crosslinked polyimide resin, production method thereof, adhesive resin composition, cured product thereof, coverlay film, and circuit board |
| JP2013197069A (en) * | 2012-03-22 | 2013-09-30 | National Institute Of Advanced Industrial & Technology | Negative electrode material for lithium secondary battery and manufacturing method thereof, negative electrode for lithium secondary battery and manufacturing method thereof, lithium secondary battery, and electric device with lithium secondary battery |
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