CN114122398A - Integrated conductive adhesive and preparation method and application thereof - Google Patents
Integrated conductive adhesive and preparation method and application thereof Download PDFInfo
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- CN114122398A CN114122398A CN202111275925.3A CN202111275925A CN114122398A CN 114122398 A CN114122398 A CN 114122398A CN 202111275925 A CN202111275925 A CN 202111275925A CN 114122398 A CN114122398 A CN 114122398A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 55
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 43
- 229920001983 poloxamer Polymers 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 15
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 239000011230 binding agent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000006257 cathode slurry Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000011267 electrode slurry Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000002482 conductive additive Substances 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 19
- 229910001416 lithium ion Inorganic materials 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000002041 carbon nanotube Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229920006243 acrylic copolymer Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000011883 electrode binding agent Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910002981 Li4.4Si Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
Images
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
- H01M4/62—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
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of battery materials, and discloses a preparation method of an integrated conductive adhesive, which comprises the following steps: dissolving the poly-pluronic and the catalyst in CH2Cl2Uniformly stirring the solution to obtain a mixed solution A; adding acryloyl chloride into the mixed solution A for reaction to obtain a mixed solution B; adding an acid regulator into the mixed solution B for reaction to obtain a mixed solution C; dialyzing the mixed solution C to obtain modified poly-pluronic; dissolving the modified poly-pluronic in water, and adding acrylic acid and an initiator to obtain a poly-pluronic-acrylic acid copolymer; blending CNT and poly-pluronic-acrylic acid copolymer, and performing ultrasonic dispersion under ice bath to obtain the productAn integral conductive adhesive. The conductive additive is not required to be added in the preparation process of the pole piece, the conductive additive and the polymer are better bonded and dispersed through dispersion treatment, the conductivity of the adhesive is improved, and the cathode prepared from the adhesive has excellent cycle performance.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to an integrated conductive adhesive as well as a preparation method and application thereof.
Background
With the increasing prominence of energy problems and environmental problems, the lithium ion battery is composed ofThe composite material has the advantages of light weight, small volume, high specific capacity and the like, and is used in novel high-tech fields of 3C products (mobile phones, notebook computers and digital cameras), electric automobiles, unmanned planes, aerospace and the like. The theoretical specific capacity of silicon in the fully lithium-intercalated state (Li4.4Si) is 4200mAh g-1More than 10 times of graphite cathode material used in commercialization. Moreover, it has a lower safe lithium intercalation working voltage (0.2-0.4V vs. Li/Li) comparable to graphite negative electrodes+) And the safety problems of lithium precipitation of the cathode material and the like are avoided. Meanwhile, the element reserves are very abundant (the second most abundant element in the earth crust), cheap and easily available, and environment-friendly. Silicon has become the most promising candidate to replace graphite-based negative electrodes to boost the energy density of lithium ion batteries.
Because of the poor conductivity of silicon, conductive additives, such as conductive carbon black, carbon tubes, carbon fibers, etc., are typically added during the pulping process to enhance the conductivity between the silicon particles and the binder. The volume expansion of the silicon negative electrode can reach 400 percent in the process of lithium ion intercalation and deintercalation, and the common electrode binder polyacrylic acid only contains a hydrophilic chain segment and can realize better adhesion to silicon, but has insufficient adhesion to a carbon material at a hydrophobic interface, so that the active substance and the conductive additive lose electric connection in the process of large volume expansion, the electrochemical performance of the battery is reduced, and the battery becomes a great bottleneck of the current commercialization. Therefore, it is necessary to design and develop a binder having both silicon-binding and carbon-binding functions while having good conductivity to solve the problem of poor conductivity of the silicon-based negative electrode.
Disclosure of Invention
The invention aims to provide an integrated conductive adhesive, a preparation method and application thereof, and solves the problem of insufficient adhesive force between electrode polyacrylic acid and a conductive additive in the prior art.
The invention is realized by the following technical scheme:
a preparation method of an integrated conductive adhesive comprises the following steps:
1.1, mixing the components in a molar ratio of 1: 1-3 of poly-pluronic and catalyst solutionIn CH2Cl2Uniformly stirring the solution to obtain a mixed solution A;
1.2, adding acryloyl chloride into the mixed solution A for reaction to obtain a mixed solution B; the molar ratio of the polyprenick to the acryloyl chloride is 1: (1-3);
1.3, adding an acidic regulator into the mixed solution B for reaction to obtain a mixed solution C;
1.4, dialyzing the mixed solution C to obtain a reaction product, and freeze-drying the reaction product to obtain modified poly-pluronic;
dissolving the modified poly-pluronic in water, adding acrylic acid and an initiator, and carrying out polymerization reaction to obtain a poly-pluronic-acrylic acid copolymer; the molar ratio of the modified pluronic to the acrylic acid is (1-3): (7-9);
step 3, mixing CNT and poly-pluronic-acrylic acid copolymer according to the weight ratio of 1: and (3) blending at a mass ratio of 1-4, and performing ultrasonic dispersion under an ice bath to obtain the integrated conductive adhesive.
Further, in step 1.1 and step 2, a protective gas was bubbled into the reaction solution during the reaction.
Further, in step 1.1, triethylamine is used as a catalyst, and the molar ratio of the added amount of triethylamine to the poly-pluronic is 1-3: 1, the concentration of the catalyst is 10-20 wt%.
Further, in the step 1.2, the reaction time of the pluronic and the acryloyl chloride is 8-12 hours.
Further, in the step 1.3, dilute HCl is adopted as an acidity regulator, the reaction temperature is room temperature, and the reaction time is 6-8 hours.
Further, in step 1.4, the freeze-drying time is more than 8 h.
Further, in step 2, the polymerization conditions are as follows: the reaction temperature is 60-80 ℃, and the reaction time is 60-80 min;
the initiator is ammonium persulfate, and the mass percent of the initiator accounts for (0.6-1.2) wt% of the total mass of the reactants.
Further, in the step 3, the ultrasonic dispersion time is 40-80 min.
The invention also discloses an integrated conductive adhesive prepared by the preparation method of the integrated conductive adhesive.
The invention also discloses an application of the integrated conductive adhesive in preparing a battery cathode, which comprises the following steps:
mixing a negative electrode active material and a conductive adhesive according to the ratio of (60-90): (1-40) to obtain a mixture, and uniformly dispersing the mixture in deionized water by ball milling to obtain uniformly mixed cathode slurry;
and uniformly coating the negative electrode slurry on a copper foil, and drying in vacuum to obtain the battery negative electrode.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a preparation method of an integrated conductive adhesive, which comprises the steps of firstly preparing modified poly-pluronics, then copolymerizing the modified poly-pluronics and acrylic monomers, blending the obtained poly-pluronics-acrylic copolymers and CNTs, and then dispersing the poly-pluronics-acrylic copolymers and CNTs by a cell dispersing instrument under ice bath through the common hydrophobic effect between the CNTs and the molecular chains of the poly-pluronics, so that the CNTs and the adhesive are uniformly compounded, and the integrated conductive adhesive with excellent conductivity is prepared. The modified poly-pluronic and the acrylic acid monomer can have chemical reaction, chemical bonds generated by reaction exist in a physical network formed by entanglement of molecular chains, and the polymer has better mechanical property due to a physical-chemical double-network structure, so that the problem of volume expansion during circulation of the silicon cathode can be solved. In addition, the adhesive has a hydrophilic chain segment in acrylic acid and a hydrophobic chain segment in the poly-pluronic at the same time, and can be respectively bonded with silicon and a carbon material; due to the hydrophobic effect between the poly-pluronic and the CNT, the CNT can be more uniformly dispersed in the adhesive, the conductivity of the adhesive is improved, and meanwhile, the poly-pluronic contains a large number of ethoxy and ether bonds, so that the transmission capability of lithium ions can be improved. According to the preparation method of the integrated conductive adhesive, the conductive additive is not required to be added in the preparation process of the pole piece, the conductive additive and the polymer are better bonded and dispersed through dispersion treatment, the conductive performance of the adhesive is improved, and the negative electrode prepared from the adhesive has excellent cycle performance.
Further, in step 1.1 and step 2, a protective gas is bubbled into the solution to remove oxygen from the solution and prevent inhibition of the polymerization reaction by oxygen.
The invention also discloses application of the integrated conductive adhesive, and provides the lithium ion battery cathode slurry, the lithium ion battery cathode and the lithium ion battery prepared based on the adhesive.
Drawings
FIG. 1 is a graph comparing the dispersibility of the poly-pluronic-acrylic acid copolymer and acrylic acid to CNT's of the present invention; (a) a poly pluronic-acrylic acid and CNT dispersion plot; (b) acrylic and CNT dispersion map;
FIG. 2 is a schematic diagram of the elemental distribution of the binder for binder A1 and comparative example B1 in example 1;
FIG. 3 is a plot of the lithium ion battery rate performance of adhesive A1 of example 1 and comparative example B1;
FIG. 4 is a graph of the lithium ion battery resistance performance of adhesive A1 of example 1 and comparative example B1;
(a) a lithium ion battery impedance performance test chart of adhesive a 1; (b) lithium ion battery impedance performance test chart of comparative example B1.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention discloses a preparation method of an integrated conductive adhesive, which comprises the following steps:
(1) preparing modified poly-pluronic:
1.1, mixing the polyprenick and triethylamine in a ratio of 1: 1 to 3 in CH2Cl2The solution with the reaction concentration of 10-20 wt% is obtained after uniform stirringMixing the solution A;
1.2, adding acryloyl chloride into the mixed solution A, and reacting at room temperature for 8-12 h to obtain a mixed solution B; the molar ratio of the polyprenick to the acryloyl chloride is 1: (1-3);
1.3, adding triethylamine into the mixed solution B in a molar ratio of 1: 1, stirring and reacting for 6-8 h at room temperature to obtain a mixed solution C; dilute HCl is added to adjust the pH, and the hydrochloric acid can also react off excess triethylamine;
1.4 dialyzing the mixed solution C to obtain a reaction product, and freeze-drying the reaction product for more than 8 hours to obtain modified poly-pluronic;
(2) preparation of a poly-pluronic-acrylic acid copolymer:
dissolving modified pluronic in water, adding acrylic acid and an initiator, wherein the molar ratio of the reaction of the modified pluronic and the acrylic acid is (1-3): (7-9), wherein the mass of the initiator is 0.6% -1.2% of the total mass of the two monomers;
heating to 60-80 ℃ to initiate monomer polymerization, wherein the polymerization reaction time is 20-60 min, and obtaining a poly-pluronic-acrylic acid copolymer;
(3) preparing a conductive adhesive: CNT and poly pluronic-acrylic copolymer were mixed as 1: 1-4, and ultrasonically dispersing for 40-80 min by using a cell dispersion instrument under ice bath.
More preferably, in step 1.1, N is bubbled into the mixed solution A2The gas is used for removing oxygen and preventing the inhibition of the reaction by the oxygen.
In the step (2), a protective gas (nitrogen or argon) is blown into the system to remove oxygen and prevent the inhibition of the polymerization reaction by oxygen.
The adhesive can be used for preparing the lithium ion battery cathode and the corresponding lithium ion battery, and comprises the following steps:
(1) mixing a negative electrode active material Si or SiC and a binder according to the ratio of (60-90): (1-40), and uniformly dispersing the mixture in deionized water by ball milling to obtain uniformly mixed cathode slurry.
(2) And (3) uniformly coating the slurry in the step (1) on a copper foil with the thickness of 12 microns by using an automatic coating machine, and drying in an air drying oven with the coating thickness of 150-. After drying, the part coated with the slurry is cut into a negative pole piece with the diameter of 12mm by a manual sheet cutting machine.
(3) And transferring the prepared negative pole piece into a glove box filled with argon to assemble a 2032 button half cell. A pure lithium sheet was used as the counter electrode and a Celgard2325 polypropylene-polyethylene-polypropylene (PP-PE-PP) membrane was used as the separator. The electrolyte solution used was a mixed solution of Ethylene Carbonate (EC) and diethyl carbonate (DEC) (volume ratio 1: 1) containing 1M lithium hexafluorophosphate (LiPF 6).
And standing the assembled button cell for 6 hours, and then cycling at the rate of 0.05C for one week at the voltage range of 0.01-1.5V at room temperature, and then performing charge-discharge cycling at the rate of 0.5C. Wherein 1C is 4200 mAh/g.
Example 1
The invention discloses a preparation method of an integrated conductive adhesive, which comprises the following steps:
(1) dissolving 0.2M and 0.6M polyprenick and triethylamine in 20ml of CH2Cl2Fully and uniformly stirring the mixture in the solution to obtain a mixed solution A;
(2) introducing nitrogen for 60min to remove oxygen;
(3) adding 0.2M acryloyl chloride into the mixed solution A, and reacting for 8 hours at room temperature to obtain a mixed solution B;
(4) adding 0.6M diluted HCl into the mixed solution B, and stirring for 6 hours to obtain a mixed solution C;
(5) and (3) dialyzing the mixed solution C, freezing, transferring to a freeze drying oven, and drying to constant weight to obtain pure modified poly-pluronic.
(6) Dissolving 0.2M modified poly-pluronic in water, adding 16mg of 1.8M acrylic acid and ammonium persulfate, blowing protective nitrogen into the system to remove oxygen, heating to 60 ℃, and reacting for 60min to obtain a poly-pluronic-acrylic acid copolymer;
(7) 2.5g of poly-pluronic-acrylic acid copolymer and 2.5g of CNT were mixed and ultrasonically dispersed with a cell disperser for 80min under ice bath to obtain a conductive adhesive, which was labeled A1.
The prepared binder A1 was applied to the negative electrode and assembled into a lithium ion battery according to the above method, and the battery cycle performance was tested.
Example 2
The invention discloses a preparation method of an integrated conductive adhesive, which comprises the following steps:
(1) dissolving 0.2M and 0.4M polyprenick and triethylamine in 20ml of CH2Cl2Fully and uniformly stirring the mixture in the solution to obtain a mixed solution A;
(2) introducing nitrogen for 60min to remove oxygen;
(3) adding 0.4M acryloyl chloride into the mixed solution A, and reacting for 10 hours at room temperature to obtain a mixed solution B;
(4) adding 0.4M diluted HCl into the mixed solution B, and stirring for 7 hours to obtain a mixed solution C;
(5) and (3) dialyzing the mixed solution C, freezing, transferring to a freeze drying oven, and drying to constant weight to obtain pure modified poly-pluronic.
(6) Dissolving 0.2M modified poly-pluronic in water, adding 1.6M acrylic acid and 24mg of ammonium persulfate, blowing protective nitrogen into the system to remove oxygen, heating to 70 ℃, and reacting for 40min to obtain a poly-pluronic-acrylic acid copolymer;
(7) 2.5g of poly-pluronic-acrylic acid copolymer and 1.25g of CNT were mixed and ultrasonically dispersed with a cell disperser for 60min under ice bath to obtain a conductive adhesive, which was labeled A2.
Example 3
The invention discloses a preparation method of an integrated conductive adhesive, which comprises the following steps:
(1) dissolving 0.2M and 0.2M polyprenick and triethylamine in 20ml of CH2Cl2Fully and uniformly stirring the mixture in the solution to obtain a mixed solution A;
(2) introducing nitrogen for 60min to remove oxygen;
(3) adding 0.2M acryloyl chloride into the mixed solution A, and reacting for 12 hours at room temperature to obtain a mixed solution B;
(4) adding 0.2M diluted HCl into the mixed solution B, and stirring for 6 hours to obtain a mixed solution C;
(5) and (3) dialyzing the mixed solution C, freezing, transferring to a freeze drying oven, and drying to constant weight to obtain pure modified poly-pluronic.
(6) Dissolving 0.2M modified poly-pluronic in water, adding 0.467M acrylic acid and 30mg of ammonium persulfate, blowing protective nitrogen into the system to remove oxygen, heating to 80 ℃ and reacting for 20min to obtain a poly-pluronic-acrylic acid copolymer;
(7) 2.5g of poly-pluronic-acrylic acid copolymer and 0.625g of CNT were mixed and ultrasonically dispersed with a cell disperser for 60min under ice bath to obtain a conductive adhesive, which was labeled A3.
Comparative example 1
(1) Dissolving 0.2M and 0.6M polyprenick and triethylamine in 20ml of CH2Cl2Fully and uniformly stirring the solution.
(2) Introducing nitrogen for 60min to remove oxygen;
(3) 0.2M acryloyl chloride was added to the solution prepared in step (2), and reacted at room temperature for 8 hours.
(4) Adding 0.6M diluted HCl into the solution prepared in the step (3), and stirring for 6 hours;
(5) and (3) dialyzing the reaction product, freezing, transferring to a freeze drying box, and drying to constant weight to obtain pure modified poly-pluronic.
(6) Dissolving 0.2M modified poly-pluronic in water, adding 16mg of 1.8M acrylic acid and initiator ammonium persulfate, blowing protective nitrogen into the system to remove oxygen, heating to 60 ℃ and reacting for 60min to obtain a poly-pluronic-acrylic acid copolymer, wherein the obtained adhesive is marked as B1.
When the prepared binder B1 was applied to the negative electrode according to the above method, CNT was directly added during the ball milling process, and the prepared electrode was assembled into a lithium ion battery and tested for cycle performance as shown in Table 1.
Comparative example 2
PAA was used as binder;
when the prepared PAA is applied to a negative electrode according to the method, the CNT is required to be directly added in the ball milling process, and the prepared electrode is assembled into a lithium ion battery and the cycle performance of the battery is tested, as shown in Table 1.
TABLE 1
| Numbering | First week efficiency | Capacity maintenance rate after 200 weeks |
| Example 1 | 84.6 | 82 |
| Example 2 | 84.2 | 80.8 |
| Example 3 | 82.3 | 78.4 |
| Comparative example 1 | 83.4 | 37.5 |
| Comparative example 2 | 82.6 | 42.2 |
From the results in table 1, the first cycle efficiencies of the lithium ion negative electrode binders provided by the present invention are all above 80%, and the capacity retention rates after 200 cycles are all above 78%, but the capacity retention rates after 200 cycles of the comparative example binders are all below 50%. This is why. The adhesive prepared by the invention obviously improves the cycle stability of the lithium ion battery.
From the results of fig. 1, the poly-pluronic-acrylic acid and the CNTs have better dispersibility, no obvious dispersed particles are seen in the dispersed solution, and the solution is still uniformly dispersed and no sedimentation occurs after standing for 7 days; carrying out ultrasonic dispersion on the control sample acrylic acid and CNT for 1min, and then, generating obvious sedimentation; the common hydrophobic effect of the pluronic-acrylic acid and the CNT is shown, so that the pluronic-acrylic acid and the CNT can achieve better uniformity after ultrasonic dispersion.
From the results of fig. 2, the distribution of carbon elements in the electrode sheet prepared by the conductive adhesive is more uniform, and the agglomeration phenomenon is less likely to occur, while the distribution of carbon elements in the electrode sheet prepared by the comparative adhesive is partially aggregated, which shows that the integrated conductive adhesive design can better disperse and compound the conductive matrix, so that the electrode structure has better conductivity.
From the results of fig. 3, it can be seen that the specific capacity of the Si negative electrode of the binder of comparative example B1 decreases and the attenuation amplitude increases with increasing current density as the rate of the lithium ion battery increases from 0.1C to 1.5C, and the capacity attenuates to 1236mAh g at the highest rate of 1.5C-1(ii) a While the Si negative electrode of the binder of example A1 always had a higher specific discharge capacity at different rates than the electrode of the binder of comparative example B1, and the capacity fade was significantly slower, providing a higher specific capacity (1685mAh g) even at 1.5C rate-1). The result shows that under the condition of large current, the CNT in the conductive adhesive can be more uniformly distributed in the electrode, so that the conductivity of the pole piece is improved, and the rate capability of the battery is improved.
From the results of fig. 4, the impedance of the cell using the binder of example a1 in the high frequency region after cycle 1 was 49 Ω, while the impedance of the cell using the binder of comparative example B1 was 75 Ω in the high frequency region, and after 50 cycles, the semicircular radius of the binder electrode of example a1 in the high frequency region was much smaller than that of the binder electrode of comparative example B1, indicating that the interfacial resistance of the silicon negative electrode using the binder of example a1 was lower. This result indicates that the conductive adhesive contributes to improvement of interfacial stability of the electrode, thereby effectively reducing interfacial resistance, and thus the battery has better rate performance.
Claims (10)
1. The preparation method of the integrated conductive adhesive is characterized by comprising the following steps of:
step 1, preparing modified poly-pluronic:
1.1, mixing the components in a molar ratio of 1: 1-3 of poly-pluronic and catalyst dissolved in CH2Cl2Uniformly stirring the solution to obtain a mixed solution A;
1.2, adding acryloyl chloride into the mixed solution A for reaction to obtain a mixed solution B; the molar ratio of the polyprenick to the acryloyl chloride is 1: (1-3);
1.3, adding an acidic regulator into the mixed solution B for reaction to obtain a mixed solution C;
1.4, dialyzing the mixed solution C to obtain a reaction product, and freeze-drying the reaction product to obtain modified poly-pluronic;
step 2, preparing a poly-pluronic-acrylic acid copolymer:
dissolving the modified poly-pluronic in water, adding acrylic acid and an initiator, and carrying out polymerization reaction to obtain a poly-pluronic-acrylic acid copolymer; the molar ratio of the modified pluronic to the acrylic acid is (1-3): (7-9);
step 3, mixing CNT and poly-pluronic-acrylic acid copolymer according to the weight ratio of 1: and (3) blending at a mass ratio of 1-4, and performing ultrasonic dispersion under an ice bath to obtain the integrated conductive adhesive.
2. The method of claim 1, wherein a protective gas is bubbled into the reaction solution during the reaction in step 1.1 and step 2.
3. The preparation method of the integrated conductive adhesive according to claim 1, wherein in the step 1.1, triethylamine is used as a catalyst, and the molar ratio of the added amount of the triethylamine to the poly-pluronic is 1-3: 1, the concentration of the catalyst is 10-20 wt%.
4. The method for preparing the integrated conductive adhesive according to claim 1, wherein in the step 1.2, the reaction time of the pluronic and the acryloyl chloride is 8-12 hours.
5. The preparation method of the integrated conductive adhesive according to claim 1, wherein in the step 1.3, dilute HCl is adopted as the acidity regulator, the reaction temperature is room temperature, and the reaction time is 6-8 h.
6. The method of claim 1, wherein the freeze-drying time of step 1.4 is greater than 8 hours.
7. The method for preparing an integrated conductive adhesive according to claim 1, wherein in the step 2, the polymerization reaction conditions are as follows: the reaction temperature is 60-80 ℃, and the reaction time is 60-80 min;
the initiator is ammonium persulfate, and the mass percent of the initiator accounts for (0.6-1.2) wt% of the total mass of the reactants.
8. The method for preparing the integrated conductive adhesive according to claim 1, wherein in the step 3, the ultrasonic dispersion time is 40min to 80 min.
9. An integrated conductive adhesive, which is prepared by the preparation method of the integrated conductive adhesive according to any one of claims 1 to 8.
10. Use of the integrated conductive binder of claim 9 in the preparation of a battery anode, comprising the process of:
mixing a negative electrode active material and a conductive adhesive according to the ratio of (60-90): (1-40) to obtain a mixture, and uniformly dispersing the mixture in deionized water by ball milling to obtain uniformly mixed cathode slurry;
and uniformly coating the negative electrode slurry on a copper foil, and drying in vacuum to obtain the battery negative electrode.
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| CN114976002A (en) * | 2022-04-28 | 2022-08-30 | 清华大学山西清洁能源研究院 | Adhesive, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
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