CN114695892A - Diamine cross-linked polyimide for negative binder and preparation method thereof - Google Patents
Diamine cross-linked polyimide for negative binder and preparation method thereof Download PDFInfo
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- CN114695892A CN114695892A CN202210202784.0A CN202210202784A CN114695892A CN 114695892 A CN114695892 A CN 114695892A CN 202210202784 A CN202210202784 A CN 202210202784A CN 114695892 A CN114695892 A CN 114695892A
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- diamine
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 120
- 229920001721 polyimide Polymers 0.000 title claims abstract description 120
- 150000004985 diamines Chemical class 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011230 binding agent Substances 0.000 title description 9
- 239000011883 electrode binding agent Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 aliphatic diamine Chemical class 0.000 claims description 31
- 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 17
- 239000002798 polar solvent Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 238000004132 cross linking Methods 0.000 claims description 12
- 239000002994 raw material Substances 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
- 150000004984 aromatic diamines Chemical class 0.000 claims description 7
- 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002883 imidazolyl group Chemical group 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
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- BWAPJIHJXDYDPW-UHFFFAOYSA-N 2,5-dimethyl-p-phenylenediamine Chemical compound CC1=CC(N)=C(C)C=C1N BWAPJIHJXDYDPW-UHFFFAOYSA-N 0.000 claims description 2
- MJAVQHPPPBDYAN-UHFFFAOYSA-N 2,6-dimethylbenzene-1,4-diamine Chemical compound CC1=CC(N)=CC(C)=C1N MJAVQHPPPBDYAN-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
- 150000002009 diols Chemical class 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 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 27
- 229910052710 silicon Inorganic materials 0.000 abstract description 27
- 239000010703 silicon Substances 0.000 abstract description 27
- 239000007773 negative electrode material Substances 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 13
- 230000008961 swelling Effects 0.000 abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 23
- 229920001223 polyethylene glycol Polymers 0.000 description 23
- 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 description 13
- 238000000034 method Methods 0.000 description 13
- NABYEWFUAONMMH-UHFFFAOYSA-N 1,8-diaminooctane-3,6-dione Chemical compound NCCC(=O)CCC(=O)CCN NABYEWFUAONMMH-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 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 description 10
- 238000007599 discharging Methods 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 9
- 150000002513 isocyanates Chemical group 0.000 description 9
- 239000002981 blocking agent Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 8
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- 238000006243 chemical reaction Methods 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
- 230000000903 blocking effect Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000011160 research 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
- 239000000853 adhesive Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 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
- 229910001290 LiPF6 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 239000003013 cathode binding agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 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
- 125000000524 functional group Chemical group 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
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 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
- 239000011856 silicon-based particle Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003756 stirring Methods 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-linked polyimide for a negative electrode binder and a preparation method thereof, wherein 60-100 parts of linear polyimide, 100 parts of water and 150 parts of diamine solution are adopted, and from the preparation of the linear polyimide, diamine is adopted to cross-link the linear polyimide, so that the provided diamine cross-linked polyimide has higher mechanical strength and lower swelling degree, has stronger binding effect with a silicon-based negative electrode material, ensures the cycle performance under the high-current density charge-discharge condition, meets the actual use requirement of the high-capacity silicon-based negative electrode material, and has very high actual 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 binder and a preparation method thereof.
Background
The binder is an important component of the lithium ion battery, and functions to bind the active material and the conductive agent together and to the current collector, so that electrons can flow out 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 reduction resistance, good thermal stability, easy dispersion and the like. Chinese patent CN107004844A discloses a prelithiated silicon anode containing PVDF binder, which can prolong the cycle life to a certain extent, but the weak van der waals force between the silicon anode and the silicon particles cannot buffer the huge volume expansion effect during charging and discharging, which easily causes pulverization of the electrode material or falling off from the current collector, and finally affects the electrochemical performance of the electrode. 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 be directly used in a high-capacity silicon-based negative electrode material, huge volume change is generated in the charging and discharging process, and the pole piece is difficult to maintain integrity, so that the cycle performance is poor under the high-current-density charging and discharging condition; chinese patent CN111777984A discloses a sulfonated polyimide binder, an electrode sheet and a lithium ion battery, which can enhance the performance of the lithium ion battery to a certain extent, but the sulfonated polyimide is subject to swelling in the 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 taken as a main raw material, and the diamine is adopted to cross-link the linear polyimide, so that the provided diamine cross-linked polyimide has higher mechanical strength and lower swelling degree, has stronger binding effect with a silicon-based negative electrode material, ensures the cycle performance under the condition of high current density charge-discharge, meets the actual use requirement of the high-capacity silicon-based negative electrode material, and has very high practical popularization and application values.
Disclosure of Invention
The invention provides diamine cross-linked polyimide for a negative electrode binder, which at least 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 preferred technical scheme, the preparation raw materials of the linear polyimide at least comprise 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 according to parts by weight;
as a preferred technical solution, 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 a diamine solution for reaction to obtain a short-chain hard segment, and adding a blocking agent for blocking;
(3) then adding flexible compound to make polymerization reaction so as to obtain the invented linear polyimide.
As a preferred embodiment, the diamine is a combination of an aliphatic diamine and an aromatic diamine;
preferably, the aliphatic diamine is 1, 8-octanediamine or 3, 6-dioxo-1, 8-octanediamine;
preferably, the aromatic diamine structure contains at least one of an imidazole group, a fluoroalkyl group, and a 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 the 3, 6-dioxo-1, 8-octanediamine to the 2- (4-aminophenyl) -5-aminobenzimidazole is (1-2): (0.8-1.5).
In a preferred embodiment, the dianhydride is at least one selected from the group consisting of 4, 4-oxophthalic anhydride, 3,4, 4-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, and 1,4,5, 8-naphthalene tetracarboxylic dianhydride;
preferably, the dianhydride is 4, 4-oxophthalic 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 solution, 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 propane 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 molar ratio of (1-2): (0.8-1.5) reacting 3, 6-dioxo-1, 8-octanediamine and 2- (4-aminophenyl) -5-aminobenzimidazole with 4, 4-oxophthalic anhydride, and then blocking by hexamethylene diisocyanate to obtain short-chain hard segments, so that the linear polyimide has good thermal stability and chemical stability, and the mechanical property and the adhesive property of the polyimide are ensured; the inventor speculates that the application stability of the fully aromatic polyimide is low due to strong interaction force among molecules, and under the molar ratio, the introduction of the 3, 6-dioxo-1, 8-octanediamine properly reduces the strong interaction force among molecules in the aromatic polyimide structure, improves and endows the linear polyimide with excellent thermal stability and chemical stability on the basis of ensuring the mechanical property of the polyimide, is beneficial to subsequent processing, and simultaneously imidazole groups in the molecular chain structure of the linear polyimide can show good adhesion with a silicon-based negative electrode 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 be directly used in a high-capacity silicon-based negative electrode material, huge volume change is generated in the charging and discharging process, and the integrity of a pole piece is difficult to maintain, so that the cycle performance under the high-current-density charging and discharging condition is poor, and the inventor finds that a flexible compound is introduced into a reaction system of the linear polyimide in the research process, particularly when the mass ratio of the flexible compound is (4-6): (0.5-1.5) when the propane diamine and the polyethylene glycol are combined, the propane diamine and the polyethylene glycol play a synergistic effect to the greatest extent, so that the electrochemical performance of the battery is effectively improved when the propane diamine and the polyethylene glycol are used as a silicon-based negative electrode binder, and the capacity cycle attenuation is reduced; the inventor speculates that the reason may be that under the mass ratio, the small molecule flexible chain segment propane diamine and the polyethylene glycol are introduced into the molecular structure of the linear polyimide, so that the flexibility of the linear polyimide is obviously improved, the damage to a pole piece caused by volume change when the linear polyimide is subsequently applied to a battery is avoided, the electrochemical performance of the battery when the linear polyimide is used as a silicon-based negative electrode binder is effectively improved, and the poor cycle performance under the high-current-density charging and discharging conditions is ensured. The inventor unexpectedly finds 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 processability of the linear polyimide is effectively improved. The inventor speculates that the reason is that when the weight average molecular weight of the polyethylene glycol is 400-600, the polyethylene glycol can be sufficiently 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 solution, the diamine solution at least comprises a diamine compound, a solvent; preferably, the mass ratio of the diamine compound to the solvent is (5-7): (3-5).
As a preferable embodiment, the diamine compound includes at least one of 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 ', 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 preferable embodiment, the diamine compound further comprises 1, 3-bis (3-aminopropyl) tetramethyldisiloxane; as a preferable technical scheme, the molar ratio of the 2, 2-bis (4-aminophenoxyphenyl) propane to the 1, 3-bis (3-aminopropyl) tetramethyldisiloxane 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, due to the huge volume expansion effect in the charge and discharge process, the final electrochemical performance is determined to a certain extent by the combination action between the silicon-based negative electrode material and the polyimide binder, and the polyimide swells in the electrolyte to cause the electrode material to fall off from the current collector, so that the electrochemical performance of the battery is reduced, and the service life of the battery is shortened. The invention adopts diamine to crosslink the provided linear polyimide, so as to improve the bonding effect between the polyimide binder and the silicon-based negative electrode material, ensure the electrochemical performance and prolong the service life of the battery, and the inventor finds that the provided diamine crosslinking type polyimide has higher mechanical strength and stronger bonding effect with the silicon-based negative electrode material by crosslinking the linear polyimide by adopting 2, 2-bis (4-aminophenoxyphenyl) propane in the research process; the inventor speculates that the 2, 2-bis (4-aminophenoxyphenyl) propane and the linear polyimide provided by the invention have good crosslinking effect, the 2, 2-bis (4-aminophenoxyphenyl) propane opens the structure of the linear polyimide in the crosslinking process, 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 negative electrode material, and the formed crosslinking structure has higher mechanical strength, has buffering and protecting effects on the huge volume expansion effect of the subsequent battery in the charging and discharging processes, avoids pulverization and falling of the electrode material and improves the electrochemical performance of the electrode;
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 deteriorated due to swelling of a polyimide binder in an electrolyte cannot be effectively solved, and the inventors have found through creative research experiments that the molar ratio of the 2, 2-bis (4-aminophenoxyphenyl) propane to the 1, 3-bis (3-aminopropyl) tetramethyldisiloxane is controlled to be (2-4): and (1-2), on the basis of ensuring the mechanical property of the provided diamine cross-linked polyimide, the strong bonding effect between the diamine cross-linked polyimide and the silicon-based negative electrode material is further improved, so that the provided diamine cross-linked polyimide has low swelling degree, the cycle performance of the battery under the high-current-density charging and discharging condition is ensured, and the actual use requirement of the high-capacity silicon-based negative electrode material is met. The inventors speculate that the reason may be that the molar ratio of 2, 2-bis (4-aminophenoxyphenyl) propane and 1, 3-bis (3-aminopropyl) tetramethyldisiloxane introduced is controlled to be (2-4): (1-2), the existence of the siloxane structure promotes the crosslinking of the 2, 2-bis (4-aminophenoxyphenyl) propane on the linear polyimide, the synergistic effect among the crosslinking agents is best, so that the crosslinked diamine crosslinked polyimide structure has lower swelling degree in the electrolyte, and the problem that the electrochemical performance of the 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 cathode binder, which is characterized in that linear polyimide is dissolved in water, and diamine solution is added for cross-linking to obtain the diamine cross-linked polyimide.
Advantageous effects
1. The invention provides diamine cross-linked polyimide for a negative electrode binder and a preparation method thereof, wherein linear polyimide is taken as a main raw material, and diamine is adopted to cross-link the linear polyimide, so that the provided diamine cross-linked polyimide has higher mechanical strength and lower swelling degree, has stronger binding effect with a silicon-based negative electrode material, ensures the cycle performance under the condition of high current density charge-discharge, meets the actual use requirement of the high-capacity silicon-based negative electrode material, and has very high practical popularization and application values.
2. The invention starts from the preparation of polyimide by adopting the molar ratio of (1-2): (0.8-1.5) 3, 6-dioxo-1, 8-octanediamine and 2- (4-aminophenyl) -5-aminobenzimidazole react with 4, 4-oxophthalic anhydride, and then are blocked by hexamethylene diisocyanate, so that short-chain hard segments can be obtained, good thermal stability and chemical stability are endowed to the linear polyimide, and the mechanical property and the adhesive property of the polyimide are ensured.
3. In the invention, the flexible compound is introduced into a reaction system of linear polyimide, particularly when the mass ratio of the flexible compound is (4-6): (0.5-1.5) when the propylene diamine and the polyethylene glycol are combined, the propylene diamine and the polyethylene glycol play a synergistic effect to the greatest extent, so that the electrochemical performance of the battery is effectively improved when the propylene diamine and the polyethylene glycol are 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 provided diamine crosslinked polyimide has higher mechanical strength and stronger bonding effect with a silicon-based negative electrode material.
5. By introducing 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, the molar ratio of the 2, 2-bis (4-aminophenoxyphenyl) propane to the 1, 3-bis (3-aminopropyl) tetramethyldisiloxane is controlled to be (2-4): and (1-2), on the basis of ensuring the mechanical property of the provided diamine cross-linked polyimide, the strong bonding effect between the diamine cross-linked polyimide and the silicon-based negative electrode material is further improved, so that the provided diamine cross-linked polyimide has low swelling degree, the cycle performance of the battery under the high-current-density charging and discharging condition is ensured, and the actual use requirement of the high-capacity silicon-based negative electrode material is met.
Detailed Description
Example 1
In one aspect, 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.
According to parts by weight, the preparation raw materials of the linear polyimide 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 a diamine solution for reaction to obtain a short-chain hard segment, and adding a blocking agent for blocking;
(3) then adding a flexible compound to carry out 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-oxophthalic 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 propane diamine to the polyethylene glycol is 5: 1; 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 includes 2, 2-bis (4-aminophenoxyphenyl) propane.
The diamine compound further includes 1, 3-bis (3-aminopropyl) tetramethyldisiloxane; the molar ratio of the 2, 2-bis (4-aminophenoxyphenyl) propane to the 1, 3-bis (3-aminopropyl) tetramethyldisiloxane 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, in which linear polyimide is dissolved in water, and a diamine solution is added to the linear polyimide for cross-linking.
Example 2
In an aspect, 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 preparation raw materials of the linear polyimide comprise, by weight, 15 parts of diamine, 25 parts of dianhydride, 6 parts of a capping agent, 10 parts of a flexible compound and 6 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 a diamine solution for reaction to obtain a short-chain hard segment, and adding a blocking agent for blocking;
(3) then adding flexible compound to make polymerization reaction so as to obtain the invented 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-oxophthalic 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 propane 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 includes 2, 2-bis (4-aminophenoxyphenyl) propane.
The diamine compound further includes 1, 3-bis (3-aminopropyl) tetramethyldisiloxane; the molar ratio of the 2, 2-bis (4-aminophenoxyphenyl) propane to the 1, 3-bis (3-aminopropyl) tetramethyldisiloxane 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, in which linear polyimide is dissolved in water, and a diamine solution is added to the linear polyimide for cross-linking.
Example 3
In one aspect, 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.
According to parts by weight, the preparation raw materials of the linear polyimide comprise 10 parts of diamine, 15 parts of dianhydride, 3 parts of end-capping reagent, 5 parts of flexible compound and 4 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 a diamine solution for reaction to obtain a short-chain hard segment, and adding a blocking agent for blocking;
(3) then adding flexible compound to make polymerization reaction so as to obtain the invented 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-oxophthalic 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 propane 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 includes 2, 2-bis (4-aminophenoxyphenyl) propane.
The diamine compound further includes 1, 3-bis (3-aminopropyl) tetramethyldisiloxane; the molar ratio of the 2, 2-bis (4-aminophenoxyphenyl) propane to the 1, 3-bis (3-aminopropyl) tetramethyldisiloxane 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, in which linear polyimide is dissolved in water, and a diamine solution is added to the linear polyimide for cross-linking.
Comparative example 1
Comparative example 1 of the present invention provides a diamine-crosslinked polyimide for a negative electrode binder, and the specific embodiment thereof is the same as example 1, except that the linear polyimide is polyetherimide.
Comparative example 2
Comparative example 2 of the present invention provides a diamine-crosslinked polyimide for a negative electrode binder, which is prepared in the same manner as in example 1, except 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, and the specific embodiment thereof is the same as example 1, except 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 specifically embodied in the same manner as in example 1 except 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 specifically embodied in the same manner as in example 1 except that the diamine compound does not include 1, 3-bis (3-aminopropyl) tetramethyldisiloxane.
Performance test method
The diamine cross-linked polyimide prepared in the examples and the comparative examples is prepared into a silicon-based negative electrode plate according to the following method, the silicon-based negative electrode plate is assembled into a battery, the peel strength of the silicon-based negative electrode plate, the swelling ratio of the plate and the electrochemical performance of the battery are tested, and the performance test results are shown in table 1.
Preparing a negative pole piece: adding 5 parts by weight of diamine cross-linked polyimide, 15 parts by weight of silicon-carbon active material and 5 parts by weight of acetylene black into 100 parts by weight of N-methyl-2-pyrrolidone, uniformly stirring to obtain negative electrode slurry, coating the negative electrode slurry on copper foil, drying for 12 hours at 80 ℃, and performing punch forming to obtain the silicon-based negative electrode plate.
Assembling the negative pole piece and the LFP positive pole piece into a battery, wherein the battery electrolyte is LiPF6A mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate.
In the comparative example, a battery was assembled as described above using PVDF as a negative electrode binder.
Claims (10)
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.
2. The diamine cross-linked polyimide for the negative electrode binder of claim 1, wherein the linear polyimide is prepared from, by weight, at least 10-15 parts of diamine, 15-25 parts of dianhydride, 3-6 parts of a capping agent, 5-10 parts of a flexible compound, and 4-6 parts of a polar solvent.
3. The diamine-crosslinked polyimide for a negative electrode binder according to claim 2, wherein the diamine is a combination of an aliphatic diamine and an aromatic diamine.
4. The diamine-crosslinked polyimide for a negative electrode binder according to claim 3, wherein the aromatic diamine structure contains at least one of an imidazole group, a fluoroalkyl group, and a hydroxyl group.
5. The diamine-crosslinked polyimide for a negative electrode binder according to claim 2, wherein the dianhydride is at least one selected from the group consisting of 4, 4-oxophthalic anhydride, 3,4, 4-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, and 1,4,5, 8-naphthalene tetracarboxylic anhydride.
6. The diamine-crosslinked polyimide for a negative electrode binder according to claim 2, wherein the polar solvent is at least one selected from the group consisting of dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, N-methylformamide, dimethylacetamide, and dimethylsulfoxide.
7. The diamine-crosslinked polyimide for a negative electrode binder according to claim 2, wherein the flexible compound is at least one of a water-soluble diamine, a water-soluble dianhydride, and a water-soluble diol.
8. The diamine-crosslinked polyimide for a negative electrode binder according to claim 1, wherein the diamine solution contains at least a diamine compound and a solvent.
9. The diamine-crosslinked polyimide for a negative electrode binder according to claim 8, the diamine compound includes at least one of 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 ', 6,6 ' -tetramethyl-4, 4 ' -diaminobiphenyl, 2 ' -diphenyl-4, 4 ' -diaminobiphenyl, 2, 4-diaminotoluene, m-xylene-2, 5-diamine, and p-xylene-2, 5-diamine.
10. A method for producing a diamine-crosslinked polyimide for a negative electrode binder according to any one of claims 1 to 9, wherein the diamine-crosslinked polyimide is obtained by dissolving a linear polyimide in water and adding a diamine solution to the linear polyimide for crosslinking.
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