CN114122398B - Integrated conductive adhesive and preparation method and application thereof - Google Patents
Integrated conductive adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN114122398B CN114122398B CN202111275925.3A CN202111275925A CN114122398B CN 114122398 B CN114122398 B CN 114122398B CN 202111275925 A CN202111275925 A CN 202111275925A CN 114122398 B CN114122398 B CN 114122398B
- Authority
- CN
- China
- Prior art keywords
- conductive adhesive
- mixed solution
- reaction
- integrated conductive
- polypyrrole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 62
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 44
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 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
- 229920001983 poloxamer Polymers 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 16
- 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
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims abstract description 13
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 8
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 17
- 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
- 230000035484 reaction time Effects 0.000 claims description 9
- 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
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 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
- 239000011267 electrode slurry Substances 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 239000006256 anode slurry Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002482 conductive additive Substances 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 3
- 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
- 230000000052 comparative effect Effects 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 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 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229920002125 Sokalan® Polymers 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
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000007664 blowing Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 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
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 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
- 230000002776 aggregation Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect 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
- 239000000126 substance Substances 0.000 description 2
- 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
- 238000004220 aggregation Methods 0.000 description 1
- 230000002238 attenuated effect Effects 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
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000005562 fading Methods 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 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
- 230000002829 reductive effect Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution 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
- 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
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 pluronic and catalyst in CH 2 Cl 2 Stirring the solution uniformly 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 polypyrrole; dissolving modified polypyrrole in water, and then adding acrylic acid and an initiator to obtain a polypyrrole-acrylic acid copolymer; and blending the CNT and the polypyrrole-acrylic copolymer, and performing ultrasonic dispersion in an ice bath to obtain the integrated conductive adhesive. The conductive additive is not required to be added in the preparation process of the pole piece, and the conductive additive and the polymer are better bonded and dispersed through dispersion treatment, so that the conductive performance of the adhesive is improved, and the negative electrode prepared from the adhesive shows excellent cycle performance.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to an integrated conductive adhesive, a preparation method and application thereof.
Background
Along with the increasing prominence of energy problems and environmental problems, lithium ion batteries have been used in the novel high-technology fields of 3C products (mobile phones, notebook computers, digital cameras), electric automobiles, unmanned aerial vehicles, aerospace and the like due to the advantages of light weight, small volume, high specific capacity and the like. The theoretical specific capacity of silicon in the fully lithium intercalation state (Li4.4Si) is 4200mAh g -1 Is more than 10 times of the graphite cathode material used in commercialization. Furthermore, it has a relatively low safe lithium intercalation operating voltage (. Apprxeq.0.2-0.4V vs. Li/Li) comparable to that of graphite cathodes + ) And the safety problems of lithium precipitation and the like of the cathode material are avoided. Meanwhile, the method has the advantages of very abundant element reserves (the second most abundant element in the crust), low cost, easy obtainment and environmental friendliness. Silicon has become the most promising alternative material to replace graphite-based negative electrodes to increase 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, and the like are typically added during the pulping process to enhance the conductivity between the silicon particles and the binder. The silicon negative electrode can expand by 400% in volume in the process of lithium ion intercalation and deintercalation, and the common electrode adhesive polyacrylic acid only contains hydrophilic chain segments, so that the silicon negative electrode can be well adhered to silicon, but the adhesion force is insufficient for the carbon material of a hydrophobic interface, so that the active substance and the conductive additive lose electrical connection in the process of large volume expansion, the electrochemical performance of the battery is reduced, and the current commercialization of the battery is a big bottleneck. Therefore, it is necessary to design and develop an adhesive having both silicon-bonding and carbon-bonding functions, which has 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 adhesion between electrode polyacrylic acid and a conductive additive in the prior art.
The invention is realized by the following technical scheme:
a method for preparing an integrated conductive adhesive, comprising the steps of:
step 1, preparing modified polypyrrole:
1.1, the molar ratio is 1:1 to 3 pluronic and catalyst are dissolved in CH 2 Cl 2 Stirring the solution uniformly 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 pluronic to acryloyl chloride is 1: (1-3);
1.3, adding an acid 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 polypyrrole;
step 2, preparing a polyprenock-acrylic acid copolymer:
dissolving modified polypyrrole in water, adding acrylic acid and an initiator, and carrying out polymerization reaction to obtain a polypyrrole-acrylic acid copolymer; the mole ratio of the modified poly pluronic to the acrylic acid is (1-3): (7-9);
step 3, the CNT and the polypyrrole-acrylic copolymer are mixed according to the proportion of 1: (1-4) blending the materials according to the mass ratio, and performing ultrasonic dispersion in ice bath to obtain the integrated conductive adhesive.
Further, in the reaction in step 1.1 and step 2, a protective gas is blown into the reaction solution.
In step 1.1, triethylamine is used as a catalyst, and the molar ratio of the addition amount of the triethylamine to the polypyrrole is (1-3): 1, the concentration of the catalyst is 10-20wt%.
Further, in step 1.2, the reaction time of pluronic and acryloyl chloride is 8 to 12 hours.
In step 1.3, dilute HCl is adopted as the acid regulator, the reaction temperature is room temperature, and the reaction time is 6-8 h.
Further, in step 1.4, the freeze-drying time is greater than 8 hours.
Further, in step 2, the polymerization conditions are: the reaction temperature is 60-80 ℃ and the reaction time is 60-80 min;
the initiator is ammonium persulfate, and the mass percentage of the initiator accounts for (0.6-1.2) weight percent of the total mass of the reactants.
In the step 3, the ultrasonic dispersion time is 40-80 min.
The invention also discloses an integrated conductive adhesive, which is prepared by adopting 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:
the negative electrode active material and the conductive binder are mixed according to (60-90): mixing the materials in the mass ratio of (1-40) to obtain a mixture, and uniformly dispersing the mixture in deionized water through ball milling to obtain uniformly mixed anode slurry;
and uniformly coating the negative electrode slurry on a copper foil, and vacuum drying 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 polypyrrole, copolymerizing the modified polypyrrole and an acrylic acid monomer, blending the obtained polypyrrole-acrylic acid copolymer with CNT, and performing dispersion treatment under ice bath through a cell dispersion instrument under the common hydrophobic effect between the CNT and a molecular chain of the polypyrrole so as to uniformly compound the CNT and the adhesive, thereby preparing the integrated conductive adhesive with excellent conductive performance. The modified poly pluronic and acrylic monomer can be subjected to chemical reaction, chemical bond connection generated by the reaction is also formed besides a physical network formed by intertwining molecular chains, and the physical-chemical double-network structure enables the polymer to have better mechanical property and can solve the problem of volume expansion of the silicon cathode during circulation. In addition, the adhesive has a hydrophilic chain segment in acrylic acid and a hydrophobic chain segment in the polypyrrole, and can be respectively bonded with silicon and carbon materials; the hydrophobic effect between the polypyrrole and the CNT enables the CNT to be more uniformly dispersed in the adhesive, so that the conductivity of the adhesive is improved, and meanwhile, the polypyrrole contains a large amount 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, a conductive additive is not required to be added in the preparation process of the pole piece, and the conductive additive and the polymer are better bonded and dispersed through dispersion treatment, so that the conductive performance of the adhesive is improved, and the negative electrode prepared from the adhesive shows excellent cycle performance.
Further, in step 1.1 and step 2, a protective gas is blown into the solution to remove oxygen in the solution and prevent the inhibition of the polymerization reaction by the oxygen.
The invention also discloses application of the integrated conductive adhesive, and provides lithium ion battery negative electrode slurry, a lithium ion battery negative electrode and a lithium ion battery prepared based on the adhesive.
Drawings
FIG. 1 is a graph showing a comparison of the dispersibility of a polypyrrole-acrylic acid copolymer and acrylic acid to CNTs according to the present invention; (a) a polypyrrole-acrylic acid and CNT dispersion map; (b) an acrylic and CNT dispersion map;
FIG. 2 is a schematic view showing the distribution of binder A1 and comparative example B1 as binder negative electrode elements in example 1;
fig. 3 is the rate performance of the lithium ion battery of the binder A1 and the comparative example B1 of example 1;
fig. 4 is the impedance properties of the lithium ion battery of the binder A1 and the comparative example B1 of example 1;
(a) A lithium ion battery impedance performance test chart of the adhesive A1; (B) impedance Performance test chart of lithium ion battery of comparative example B1.
Detailed Description
The invention will now be described in further detail with reference to specific examples, which are intended to illustrate, but not to limit, the invention.
The invention discloses a preparation method of an integrated conductive adhesive, which comprises the following steps:
(1) Preparation of modified polypyrrole:
1.1, pluronic and triethylamine were combined in 1:1 to 3, is dissolved in CH 2 Cl 2 The solution with the reaction concentration of 10 to 20 weight percent is stirred uniformly to obtain a mixed solution A;
1.2, adding acryloyl chloride into the mixed solution A, and reacting for 8-12 hours at room temperature to obtain a mixed solution B; the molar ratio of pluronic to acryloyl chloride is 1: (1-3);
1.3 adding to the mixed solution B a molar ratio to triethylamine of 1:1, stirring and reacting for 6-8 hours at room temperature to obtain a mixed solution C; adding dilute HCl to regulate pH, and simultaneously, the hydrochloric acid can also react excessive 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 polypyrrole;
(2) Preparation of a polypyrrole-acrylic copolymer:
dissolving modified polypyrrole in water, and adding acrylic acid and an initiator, wherein the molar ratio of the modified polypyrrole to 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 the poly pluronic-acrylic acid copolymer;
(3) Preparing a conductive adhesive: CNT and polypyrrole-acrylic acid copolymer were mixed in a 1: blending with the mass ratio of 1-4, and carrying out ultrasonic dispersion for 40-80 min by using a cell dispersion instrument under ice bath.
More preferably, in step 1.1, N is blown into the mixed solution A 2 The gas is deoxidized to prevent the inhibition of the reaction by oxygen.
In the step (2), a protective gas (nitrogen or argon) is blown into the system to remove oxygen, so that the inhibition of the polymerization reaction by the oxygen is prevented.
The adhesive can be used for preparing a lithium ion battery cathode and a corresponding lithium ion battery, and comprises the following steps:
(1) The negative electrode active material Si or SiC and a binder are mixed according to (60-90): and (1-40) uniformly dispersing the components in deionized water by ball milling to obtain uniformly mixed cathode slurry.
(2) The slurry in (1) is uniformly coated on copper foil with the thickness of 12 mu m by an automatic film coater, and the coating thickness is 150-300 mu m, and the solvent is removed by drying in an empty drying oven. After the drying is finished, the place coated with the sizing agent is cut into a negative pole piece with the diameter of 12mm by a manual cutting machine.
(3) Transferring the prepared negative electrode plate into a glove box filled with argon, and assembling the 2032 button type half cell. Pure lithium sheets were used as counter electrodes and Celgard2325 polypropylene-polyethylene-polypropylene (PP-PE-PP) films were used as separators. The electrolyte is a mixed solution of Ethylene Carbonate (EC) and diethyl carbonate (DEC) (volume ratio of 1:1) containing 1M lithium hexafluorophosphate (LiPF 6).
The assembled button cell was allowed to stand for 6 hours, and then was cycled at 0.05C for one week at a rate in a voltage range of 0.01 to 1.5V at room temperature, followed by charge and discharge cycles at 0.5C. Wherein 1C is 4200mAh/g.
Example 1
The invention discloses a preparation method of an integrated conductive adhesive, which comprises the following steps:
(1) 0.2M and 0.6M pluronic and triethylamine were dissolved in 20ml of CH 2 Cl 2 Fully and uniformly stirring the solution to obtain a mixed solution A;
(2) Introducing nitrogen for 60min to remove oxygen;
(3) Adding 0.2M of 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 dilute HCl into the mixed solution B, and stirring for 6h to obtain a mixed solution C;
(5) And (3) dialyzing the mixed solution C, freezing, transferring to a freeze drying box, and drying to constant weight to obtain the pure modified polypyrrole.
(6) Dissolving 0.2M modified polyprenone in water, adding 16mg of 1.8M acrylic acid and ammonium persulfate, then blowing protective nitrogen into the system to deoxidize, and heating to 60 ℃ for reaction time of 60min to obtain a polyprenone-acrylic acid copolymer;
(7) 2.5g of a polypyrrole-acrylic copolymer and 2.5g of CNTs were mixed, and ultrasonically dispersed under an ice bath for 80 minutes with a cell disperser to obtain a conductive adhesive, the resulting adhesive being labeled A1.
And applying the prepared adhesive A1 to a negative electrode according to the method, assembling a lithium ion battery, and testing the cycle performance of the battery.
Example 2
The invention discloses a preparation method of an integrated conductive adhesive, which comprises the following steps:
(1) 0.2M and 0.4M pluronic and triethylamine were dissolved in 20ml of CH 2 Cl 2 Fully and uniformly stirring 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 dilute HCl into the mixed solution B, and stirring for 7h to obtain a mixed solution C;
(5) And (3) dialyzing the mixed solution C, freezing, transferring to a freeze drying box, and drying to constant weight to obtain the pure modified polypyrrole.
(6) Dissolving 0.2M modified polyprenone in water, adding 24mg of 1.6M acrylic acid and ammonium persulfate, then blowing protective nitrogen into the system to deoxidize, and heating to 70 ℃ for 40min to obtain a polyprenone-acrylic acid copolymer;
(7) 2.5g of a polypyrrole-acrylic copolymer and 1.25g of CNT were mixed, and ultrasonically dispersed under ice bath for 60 minutes by a cell disperser to obtain a conductive adhesive, and the obtained adhesive was labeled A2.
Example 3
The invention discloses a preparation method of an integrated conductive adhesive, which comprises the following steps:
(1) 0.2M and 0.2M pluronic and triethylamine were dissolved in 20ml of CH 2 Cl 2 Fully and uniformly stirring the solution to obtain a mixed solution A;
(2) Introducing nitrogen for 60min to remove oxygen;
(3) Adding 0.2M of 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 dilute 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 box, and drying to constant weight to obtain the pure modified polypyrrole.
(6) Dissolving 0.2M modified polyprenone in water, adding 30mg of 0.467M acrylic acid and ammonium persulfate, then blowing protective nitrogen into the system to deoxidize, and heating to 80 ℃ for 20min to obtain a polyprenone-acrylic acid copolymer;
(7) 2.5g of a polypyrrole-acrylic copolymer and 0.625g of CNT were mixed and ultrasonically dispersed under ice bath for 60 minutes by a cell disperser to obtain a conductive adhesive, which was labeled A3.
Comparative example 1
(1) 0.2M and 0.6M pluronic and triethylamine were dissolved in 20ml of CH 2 Cl 2 And (5) fully and uniformly stirring the solution.
(2) Introducing nitrogen for 60min to remove oxygen;
(3) 0.2M of acryloyl chloride was added to the solution prepared in step (2), and the reaction was carried out at room temperature for 8 hours.
(4) Adding 0.6M dilute HCl into the solution prepared in the step (3), and stirring for 6 hours;
(5) Dialyzing the reaction product, freezing, transferring to a freeze drying box, and drying to constant weight to obtain pure modified polypyrrole.
(6) 0.2M modified polyprenone is dissolved in water, 1.8M acrylic acid and 16mg of initiator ammonium persulfate are added, then protective nitrogen is blown into the system to remove oxygen, the temperature is raised to 60 ℃ for reaction time of 60min, and the polyprenone-acrylic acid copolymer is obtained, and the obtained adhesive is marked as B1.
When the prepared adhesive B1 is applied to a negative electrode according to the method, CNT is required to be directly added in the ball milling process, the prepared electrode is assembled into a lithium ion battery, and the battery cycle performance is tested as shown in table 1.
Comparative example 2
PAA is adopted as an adhesive;
when the prepared binder PAA is applied to a negative electrode according to the method, CNT is required to be directly added in the ball milling process, the prepared electrode is assembled into a lithium ion battery, and the battery cycle performance is tested as shown in table 1.
TABLE 1
| Numbering device | 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 efficiency of the lithium ion battery negative electrode adhesive provided by the invention is above 80%, and the capacity retention rate after 200 cycles is above 78%, but the capacity retention rate after 200 cycles is below 50% of the comparative adhesive. From this, it can be seen that. The adhesive prepared by the invention remarkably improves the cycle stability of the lithium ion battery.
From the results of fig. 1, the polyprenone-acrylic acid and the CNT have better dispersibility, the dispersed solution has no obvious dispersed particles, and after standing for 7 days, the solution is still dispersed uniformly, and no sedimentation occurs; after the acrylic acid and the CNT of the control sample are subjected to ultrasonic dispersion and standing for 1min, obvious sedimentation appears; the method shows that the pluronic-acrylic acid and the CNT have a common hydrophobic effect, so that the pluronic-acrylic acid and the CNT can achieve better uniformity after ultrasonic dispersion.
From the results of fig. 2, the electrode sheet prepared from the conductive adhesive has more uniform distribution of carbon elements and less agglomeration, while the electrode sheet prepared from the comparative adhesive has partial aggregation of carbon element distribution, which indicates 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, the Si negative electrode specific capacity of the binder of comparative example B1 was continuously decreased and the attenuation amplitude was continuously increased with the increase of the current density as the rate of the lithium ion battery was gradually increased from 0.1C to 1.5C, and the capacity was attenuated to 1236mAh g at the highest 1.5C rate -1 The method comprises the steps of carrying out a first treatment on the surface of the While the Si negative electrode of the example A1 binder always had a higher specific discharge capacity at different rates than the electrode of the comparative example B1 binder, and the capacity fading was significantly slower, providing a higher specific capacity (1685 mAh.g -1 ). The result shows that the CNT in the conductive adhesive can be more uniformly distributed in the electrode under the condition of high current, and the conductivity of the pole piece is improved, so that the rate performance of the battery is improved.
From the results of fig. 4, the impedance of the battery using the binder of example A1 in the high frequency region was 49 Ω after the 1 st cycle, and the impedance of the battery using the binder of comparative example B1 in the high frequency region was 75 Ω, and after 50 weeks of the cycle, the semicircle 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 interface resistance of the silicon anode using the binder of example A1 was lower. This result shows that the conductive adhesive helps to improve the electrode interface stability, effectively reducing the interface resistance, and therefore the battery has better rate performance.
Claims (10)
1. A method for preparing an integrated conductive adhesive, comprising the steps of:
step 1, preparing modified polypyrrole:
1.1, the molar ratio is 1:1 to 3 pluronic and catalyst are dissolved in CH 2 Cl 2 Stirring the solution uniformly 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 pluronic to acryloyl chloride is 1: (1-3);
1.3, adding an acid 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 polypyrrole;
step 2, preparing a polyprenock-acrylic acid copolymer:
dissolving modified polypyrrole in water, adding acrylic acid and an initiator, and carrying out polymerization reaction to obtain a polypyrrole-acrylic acid copolymer; the mole ratio of the modified poly pluronic to the acrylic acid is (1-3): (7-9);
step 3, the CNT and the polypyrrole-acrylic copolymer are mixed according to the proportion of 1: (1-4) blending the materials according to the mass ratio, and performing ultrasonic dispersion in ice bath to obtain the integrated conductive adhesive.
2. The method for producing an integrated conductive adhesive according to claim 1, wherein a protective gas is blown into the reaction solution at the time of the reaction in step 1.1 and step 2.
3. The method for preparing an integrated conductive adhesive according to claim 1, wherein in step 1.1, triethylamine is used as a catalyst, and the molar ratio of the amount of triethylamine to pluronic is (1-3): 1, the concentration of the catalyst is 10-20wt%.
4. The method for preparing an integrated conductive adhesive according to claim 1, wherein in step 1.2, the reaction time of pluronic and acryl chloride is 8 to 12 hours.
5. The method for preparing an integrated conductive adhesive according to claim 1, wherein in step 1.3, the acidic regulator is diluted HCl, the reaction temperature is room temperature, and the reaction time is 6-8 hours.
6. The method of claim 1, wherein the freeze-drying time is greater than 8 hours in step 1.4.
7. The method for preparing an integrated conductive adhesive according to claim 1, wherein in the step 2, 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 percentage of the initiator accounts for (0.6-1.2) weight percent of the total mass of the reactants.
8. The method for preparing an integrated conductive adhesive according to claim 1, wherein in the step 3, the ultrasonic dispersion time is 40min to 80min.
9. An integrated conductive adhesive, characterized in that the adhesive 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 adhesive of claim 9 for preparing a negative electrode for a battery, comprising the steps of:
the negative electrode active material and the conductive binder are mixed according to (60-90): mixing the materials in the mass ratio of (1-40) to obtain a mixture, and uniformly dispersing the mixture in deionized water through ball milling to obtain uniformly mixed anode slurry;
and uniformly coating the negative electrode slurry on a copper foil, and vacuum drying to obtain the battery negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111275925.3A CN114122398B (en) | 2021-10-29 | 2021-10-29 | Integrated conductive adhesive and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111275925.3A CN114122398B (en) | 2021-10-29 | 2021-10-29 | Integrated conductive adhesive and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114122398A CN114122398A (en) | 2022-03-01 |
| CN114122398B true CN114122398B (en) | 2023-12-19 |
Family
ID=80379872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111275925.3A Active CN114122398B (en) | 2021-10-29 | 2021-10-29 | Integrated conductive adhesive and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114122398B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015067638A (en) * | 2013-09-26 | 2015-04-13 | 日本ゼオン株式会社 | Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet-shaped molded product, method for producing the same, and electronic equipment |
| CN105001829A (en) * | 2015-07-02 | 2015-10-28 | 东莞优邦材料科技有限公司 | Priming coat type acrylic acid ester conductive adhesive and preparation method thereof |
| CN105131182A (en) * | 2015-09-06 | 2015-12-09 | 山东大学 | Pluronic-poly(beta-amino ester) polymer and synthesis and application methods |
| CN111154120A (en) * | 2020-01-15 | 2020-05-15 | 西安工程大学 | Conductive hydrogel based on reactive micelle and preparation method and application thereof |
| CN113113605A (en) * | 2021-03-22 | 2021-07-13 | 西安交通大学 | Network structure ion conductive adhesive and preparation method and application thereof |
-
2021
- 2021-10-29 CN CN202111275925.3A patent/CN114122398B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015067638A (en) * | 2013-09-26 | 2015-04-13 | 日本ゼオン株式会社 | Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet-shaped molded product, method for producing the same, and electronic equipment |
| CN105001829A (en) * | 2015-07-02 | 2015-10-28 | 东莞优邦材料科技有限公司 | Priming coat type acrylic acid ester conductive adhesive and preparation method thereof |
| CN105131182A (en) * | 2015-09-06 | 2015-12-09 | 山东大学 | Pluronic-poly(beta-amino ester) polymer and synthesis and application methods |
| CN111154120A (en) * | 2020-01-15 | 2020-05-15 | 西安工程大学 | Conductive hydrogel based on reactive micelle and preparation method and application thereof |
| CN113113605A (en) * | 2021-03-22 | 2021-07-13 | 西安交通大学 | Network structure ion conductive adhesive and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Dispersion of carbon nanoparticle in water with poly(acrylic acid)-poly(amideimide) copolymers";Akane Kubotera等;《Colloid Polym Sci》;第294卷;第941-946页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114122398A (en) | 2022-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108475788B (en) | Copolymer for binder for nonaqueous battery electrode, slurry for nonaqueous battery electrode, and nonaqueous battery | |
| CN110061238B (en) | Water-soluble self-healing binder, preparation method thereof and lithium ion battery | |
| CN111662418B (en) | Lithiation functional polymer for lithium ion cell and its prepn and application | |
| CN107204446B (en) | Lithium ion battery anode material and preparation method thereof | |
| CN108780892B (en) | Binder composition for nonaqueous secondary battery electrode, slurry composition for nonaqueous secondary battery electrode, electrode for nonaqueous secondary battery, and nonaqueous secondary battery | |
| CN110350196B (en) | Composite binder, silicon-based negative plate and preparation method thereof | |
| CN113113605B (en) | Network structure ion conductive adhesive and preparation method and application thereof | |
| TW201721945A (en) | Binder for negative electrodes of lithium ion secondary batteries, slurry composition for negative electrodes, negative electrode, and lithium ion secondary battery | |
| CN112500563B (en) | Synthesis method of three-dimensional conjugated conductive polyaniline and application of three-dimensional conjugated conductive polyaniline as negative electrode binder of lithium ion battery | |
| CN111647345B (en) | Lithium ion battery negative electrode polymer protective coating and preparation method and application thereof | |
| CN113193195A (en) | Nitrogen-doped carbon-coated nano silicon composite material with adjustable nitrogen content and preparation method thereof | |
| CN111668485B (en) | Binder for lithium ion battery and preparation method and application thereof | |
| CN112133916A (en) | Silicon-based negative electrode material binder of lithium ion battery and preparation method and application thereof | |
| CN115295802A (en) | Adhesive, preparation method thereof and application thereof in lithium ion battery | |
| CN114122398B (en) | Integrated conductive adhesive and preparation method and application thereof | |
| CN109728303B (en) | Water-based conductive binder suitable for silicon-based negative electrode material of lithium ion battery and preparation method thereof | |
| CN111406331B (en) | Method for producing slurry for nonaqueous battery electrode | |
| CN112670566B (en) | Polymer solid electrolyte membrane and preparation method and application thereof | |
| CN111712952A (en) | Slurry composition for lithium ion secondary battery and electrode for lithium ion secondary battery | |
| CN112467086A (en) | Preparation method of silicon-based negative electrode material based on polyamide-acid-based electrode binder | |
| CN117089017A (en) | Non-fluorine binder for positive electrode of lithium ion battery, positive electrode using same and battery | |
| CN109721713B (en) | High-conductivity lithium ion battery positive electrode slurry and preparation method thereof | |
| KR20160019704A (en) | Binder Having Higher Performance and Lithium Secondary Battery Comprising the Same | |
| CN111224184A (en) | Preparation method and application of solid electrolyte interface additive of lithium ion battery | |
| CN116731635A (en) | Conductive adhesive and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |