CN114479002A - Difunctional elastic polyurea adhesive and preparation method and application thereof - Google Patents
Difunctional elastic polyurea adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN114479002A CN114479002A CN202111449996.0A CN202111449996A CN114479002A CN 114479002 A CN114479002 A CN 114479002A CN 202111449996 A CN202111449996 A CN 202111449996A CN 114479002 A CN114479002 A CN 114479002A
- Authority
- CN
- China
- Prior art keywords
- adhesive
- bifunctional
- diisocyanate
- polyethylene glycol
- elastic
- 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.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 109
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 109
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 62
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 40
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 40
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 35
- 239000004970 Chain extender Substances 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000011230 binding agent Substances 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000007773 negative electrode material Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 5
- MERLDGDYUMSLAY-UHFFFAOYSA-N 4-[(4-aminophenyl)disulfanyl]aniline Chemical compound C1=CC(N)=CC=C1SSC1=CC=C(N)C=C1 MERLDGDYUMSLAY-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002329 infrared spectrum Methods 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 230000009471 action Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 60
- 229910001416 lithium ion Inorganic materials 0.000 description 60
- 239000005543 nano-size silicon particle Substances 0.000 description 30
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 229920002125 Sokalan® Polymers 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000006245 Carbon black Super-P Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000002482 conductive additive Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000004584 polyacrylic acid Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000000879 optical micrograph Methods 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007888 film coating Substances 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
Abstract
The invention discloses a bifunctional elastic polyurea adhesive, a preparation method and application thereof, wherein the adhesive is prepared by a one-pot method and has quick self-repairing performance and ionic conductivity, polyethylene glycol and diisocyanate undergo polyaddition reaction under the action of a catalyst to obtain a prepolymer, and then a chain extender is added to perform chain extension reaction to obtain a final product. The whole preparation process has simple flow, short reaction time and high preparation efficiency; in addition, the adhesive has the advantages of easily obtained raw materials, low cost and good repeatability, and can be widely applied to actual production.
Description
Technical Field
The invention belongs to the technical field of energy batteries, and particularly relates to a bifunctional elastic polyurea adhesive as well as a preparation method and application thereof.
Background
As a novel green chargeable and dischargeable energy storage device, the lithium ion battery has the advantages of high energy density, high operating voltage, low self-discharge rate, long service life, environmental friendliness, high safety and the like, and is widely applied to portable electronic devices such as mobile phones, notebook computers and digital cameras. In recent years, with the rapid development of scientific technology, in the novel fields of electric vehicles, unmanned aerial vehicles and the like, lithium ion batteries are widely used as power supplies and energy storage systems, and higher requirements are provided for the performance of the lithium ion batteries.
The selection of the anode and cathode materials with high specific capacity is a key factor for improving the energy density of the lithium ion battery. However, alloy negative electrode materials such as silicon, tin, antimony and the like generally have higher theoretical specific capacity, and thus have received much attention. Among them, silicon is the lithium ion battery negative electrode material with the highest known specific capacity (4200mAh/g), and is far higher than the graphite negative electrode material (372mAh/g) which is widely commercialized at present. The silicon is abundant in the earth crust, the cost is low, and the environment is protected; the lithium ion battery has moderate lithium insertion/removal potential (about 0.4V) and better safety performance, and is an ideal lithium ion battery cathode material. However, these materials undergo a severe volume change during lithium intercalation/deintercalation, and a strong volume effect causes problems of electrode pulverization, exfoliation, etc., while a new Solid Electrolyte Interface (SEI) film is continuously formed, resulting in a drastic decrease in battery performance and poor cycle stability.
Conventional electrodes are composed of an active material, a conductive additive, and a polymer binder, which is a key component for maintaining the electrode structure. Compared with the material modification with complex process and high cost, the polymer adhesive with controllable design structure and performance is selected to adapt to the huge volume effect of the electrode material, so that the electrochemical performance of the electrode material can be effectively improved, and the method is a simple and effective way for improving the cycling stability of the electrode. The traditional linear polymer adhesive is difficult to adapt to various challenges caused by large-volume expansion of alloy negative electrode materials due to the structural characteristics of the traditional linear polymer adhesive, so that a novel functional adhesive is urgently needed to be developed to solve the key technical problem, and the application of the alloy negative electrode materials in lithium ion batteries is promoted.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a bifunctional elastic polyurea adhesive, a preparation method and application thereof, so as to solve the problem caused by difficulty in adapting the conventional adhesive to the volume expansion of an alloy negative electrode material.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a method of preparing a bi-functional elastic polyurea adhesive comprising the steps of:
step 2, after the oil bath temperature of the reactant A is reduced, adding a diisocyanate solution into the reactant A to obtain a reaction system B;
step 3, adding a catalyst into the reaction system B, and heating and reacting under the protection of nitrogen to obtain a prepolymer;
and 4, mixing the chain extender solution with the prepolymer, stirring under the protection of nitrogen to react, wherein the molar ratio of the polyethylene glycol to the diisocyanate to the chain extender is (1-3): (2-4): 1; when the absorption peak of the isocyanate functional group is not detected by the infrared spectrum, the reaction is stopped to obtain the bifunctional elastic polyurea adhesive.
The invention is further improved in that:
preferably, in the step 1, the oil bath temperature is 110 ℃, and the reduced pressure distillation time is 2 h.
Preferably, in step 2, the solute in the diisocyanate solution is isophorone diisocyanate, and the solvent is N, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide.
Preferably, in step 3, the reaction temperature is 75 ℃ and the reaction time is 2 h.
Preferably, in step 3, the catalyst is one or a mixture of two of an organotin catalyst and an amine catalyst.
Preferably, in step 3, the amount of the catalyst is 0.05-1% of the total mass of the polyethylene glycol and the diisocyanate.
Preferably, in step 4, the solute of the chain extender solution is bis (4-aminophenyl) disulfide, biuret, or ethylenediamine, and the solvent is N, N-dimethylformamide, N-dimethylacetamide, or dimethylsulfoxide.
A bifunctional elastic polyurea adhesive prepared by any one of the above-mentioned preparation methods.
Use of a bifunctional elastic polyurea binder as described above in a negative electrode material for a lithium battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a bifunctional elastic polyurea adhesive, which is an elastic polyurea adhesive prepared by a one-pot method and having quick self-repairing performance and ionic conductivity, wherein polyethylene glycol and diisocyanate undergo polyaddition reaction under the action of a catalyst to obtain a prepolymer, then a chain extender is added to perform chain extension reaction to obtain a final product, a large amount of carbamido groups are contained in a synthesized polymer chain by selecting a proper chain extender, multiple hydrogen bonds can be generated among polymer molecules, dynamic self-identification is realized through the interaction of the hydrogen bonds among the carbamido groups, in addition, a synergistic self-repairing function can be realized through introducing a dynamic disulfide bond, and thus excellent self-repairing performance is realized at room temperature. The whole preparation process has simple flow, short reaction time and high preparation efficiency; in addition, the adhesive has the advantages of easily obtained raw materials, low cost and good repeatability, and can be widely applied to actual production.
The invention also discloses a bifunctional elastic polyurea adhesive which is prepared by carrying out polyaddition reaction on diisocyanate and polyethylene glycol (PEG) under the action of a catalyst to obtain a prepolymer, and then adding a chain extender to carry out chain extension reaction; the synthetic polymer chain contains a large number of carbamido groups by selecting a proper chain extender, multiple hydrogen bonds can be generated among polymer molecules, dynamic self-recognition is realized through the mutual action of the hydrogen bonds among the carbamido groups, and in addition, the synergistic self-repairing function can be realized by introducing dynamic disulfide bonds, so that the excellent self-repairing performance is realized at room temperature; meanwhile, the adhesive combines the good ionic conductivity of polyethylene glycol; when being applied to the lithium ion battery cathode, the lithium ion battery cathode can effectively improve the difficult problem of electrode structure degradation in the charging and discharging process, and improves the electrochemical performance of the electrode: the good elasticity enables the electrode to effectively adapt to the volume expansion of the electrode in the charging and discharging process, and internal stress generated by the volume effect is relieved; the strong self-repairing capability can rapidly repair cracks generated in the electrode in the circulating process, so that the completeness of the electrode is ensured, and the structural stability and the electrochemical stability of the electrode are improved; meanwhile, the ion conductivity provides a lithium ion migration channel for the electrode, so that the lithium ion transportation is effectively realized, and the method has important significance for improving the rate capability of the electrode. In addition, based on the hydrogen bond self-recognition function of carbamido in the polyurea chain segment, an interaction is formed between the polymer chain and the negative electrode material, and a thin and stable artificial Solid Electrolyte Interface (SEI) film is formed on the surface of the negative electrode, so that the side reaction between the negative electrode material and the electrolyte is prevented, and the structural stability and the electrochemical stability of the negative electrode are further improved. The adhesive has excellent rapid self-repairing performance and ion conductivity, and has high elasticity; the composite material is applied to a lithium ion battery cathode, can effectively adapt to volume expansion of an electrode in the charging and discharging processes, maintains the integrity of the electrode, forms a thin and stable artificial Solid Electrolyte Interface (SEI) film on the surface of the cathode, prevents side reaction with electrolyte, and improves the structural stability and electrochemical performance of the electrode.
Furthermore, the adhesive enables a synthesized polymer chain to contain a large number of carbamido groups by selecting a special chain extender, multiple hydrogen bonds can be generated between polymer molecules, dynamic self-recognition is realized through the interaction of the hydrogen bonds among the carbamido groups, and in addition, the dynamic disulfide bonds can be introduced to realize synergistic self-repair through the exchange effect of the dynamic disulfide bonds, so that the synthesized polyurea adhesive realizes rapid self-repair at room temperature and shows extremely strong self-repair performance. Meanwhile, polyethylene glycol is a well-known ion conducting material and is often used for research on polymer-based solid electrolytes in lithium ion batteries, lithium ions are coordinated and combined with oxygen atoms containing lone-pair electrons in polyethylene glycol chain segments to form a lithium ion migration channel, and the transportation of the lithium ions is effectively realized, so that the polyethylene glycol is used as a raw material for synthesizing the polyurea adhesive and is subjected to soft forging in the polyurea chain after reaction, and the synthesized polyurea adhesive also has good ion conducting capacity. In addition, the polyurea molecular chain has the performance of an elastomer due to the microphase separation of soft and hard sections, the hard sections form micro areas and are distributed in a matrix consisting of the soft sections, and when stress is applied, the hard sections play a skeleton role and are dispersed in the whole system, so that the synthesized polyurea adhesive shows good elasticity.
The invention also discloses application of the bifunctional elastic polyurea adhesive, and the adhesive can be used in a lithium ion battery cathode. When the synthesized polyurea adhesive is applied to the negative electrode of a lithium ion battery, the electrode can effectively adapt to the volume change of the electrode in the charging and discharging process due to good elasticity, and the internal stress generated by the volume effect is relieved; the strong self-repairing capability can rapidly repair cracks generated in the charging and discharging processes of the electrode, so that the completeness of the electrode is ensured, and the structural stability and the electrochemical stability of the electrode are improved; meanwhile, the ion conductivity provides a lithium ion migration channel for the electrode, so that the lithium ion transportation is effectively realized, and the method has important significance for improving the rate capability of the electrode. In addition, based on the hydrogen bond self-recognition function of carbamido in the polyurea chain segment, an interaction is formed between the polymer chain and the negative electrode material, and a thin and stable artificial Solid Electrolyte Interface (SEI) film is formed on the surface of the negative electrode, so that the side reaction between the negative electrode material and the electrolyte is prevented, and the structural stability and the electrochemical stability of the negative electrode are further improved. Verification shows that the charge-discharge cycle performance of the lithium ion battery cathode using the adhesive is obviously improved, and the specific expression is that the capacity of the battery is still stable along with the increase of the number of cycles, and meanwhile, the rate performance of the battery is greatly improved. The structure of the electrode is still complete after 50 cycles, cracks are hardly generated, the thickness change of the electrode is small, and the binder is fully shown to limit the volume expansion of the electrode in the lithium intercalation process, so that the stability of the electrode structure is effectively maintained.
Drawings
FIG. 1 is an optical microscope image of a film prepared from the synthetic bifunctional elastic polyurea adhesive of example 1 of the present invention at various time periods after being scratched with a scalpel; wherein: FIG. 1(a) is an optical microscope image of a polyurea film after being scratched for 0 h; FIG. 1(b) is an optical microscope image of the polyurea film after being scratched for 0.5 h; fig. 1(c) is an optical microscope image of the polyurea film after being scratched for 1 hour.
Fig. 2 is a graph comparing the cycle performance and coulombic efficiency of the lithium ion batteries prepared in comparative example 1 and example 1 according to the present invention.
Fig. 3 is a graph comparing rate performance of the lithium ion batteries prepared in comparative example 1 and example 1 according to the present invention.
Fig. 4 is a scanning electron microscope image of electrode sheets prepared in comparative example 1 and example 1 of the present invention after 50 weeks of circulation; (a) example 1, (b) comparative example 1;
fig. 5 is a graph of the cycle performance of the lithium ion battery prepared in example 2 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples: .
The invention discloses a bifunctional elastic polyurea adhesive which is prepared by carrying out polyaddition reaction on polyethylene glycol and diisocyanate under the action of a catalyst to obtain a prepolymer, and then adding a chain extender to carry out chain extension reaction, wherein the molar ratio of the polyethylene glycol to the diisocyanate to the chain extender is (1-3): (2-4): 1;
the catalyst is one or a mixture of two of an organic tin catalyst or an amine catalyst, and the dosage of the catalyst is 0.05-1% of the total mass of the polyethylene glycol and the diisocyanate;
the chain extender is selected from chain extenders containing amino groups capable of forming a large number of carbamido groups in a polymer chain, and specifically is at least one of bis (4-aminophenyl) disulfide, biuret and ethylenediamine.
The preparation method of the bifunctional elastic polyurea adhesive comprises the following steps:
dissolving diisocyanate in a solvent to obtain a diisocyanate solution; reducing the oil bath temperature of the reactant A to 75 ℃, and dropwise adding a diisocyanate solution into the reactor to obtain a reaction system B; the diisocyanate is isophorone diisocyanate (IPDI).
Step 3, adding a catalyst, and heating and reacting under the protection of nitrogen to obtain a prepolymer, wherein the reaction temperature is 75 ℃, and the reaction time is 2 hours; the added catalyst is one or a mixture of two of an organic tin catalyst or an amine catalyst, and the dosage of the catalyst is 0.05-1% of the total mass of the polyethylene glycol and the diisocyanate.
Step 4, dissolving the chain extender into a solvent to obtain a chain extender solution; and (3) reducing the oil bath temperature of the prepolymer in the reactor to 40 ℃, dropwise adding the chain extender solution into the reactor, carrying out chain extension reaction under the protection of nitrogen and stirring until no absorption peak of isocyanate functional groups is detected under infrared spectrum test, and stopping the reaction to obtain the bifunctional elastic polyurea adhesive.
The solvent in the steps 2 and 4 is any one of N, N-dimethylformamide DMF, N-Dimethylacetamide (DMAC) and dimethyl sulfoxide (DMSO), and the dosage is determined according to the concentration of the required polymer solution.
The polyurea adhesive can be used for preparing a negative electrode material of a lithium battery, and the preparation process comprises the following steps: and mixing the negative active material, the conductive additive and the polyurea adhesive to obtain uniformly dispersed slurry, uniformly coating the slurry on a copper foil current collector, and drying to obtain the electrode.
The negative active material is silicon-based material and composite material thereof; the conductive additive is carbon black, carbon nano tubes, carbon fibers or a composite conductive additive consisting of the carbon black, the carbon nano tubes and the carbon fibers; the mass ratio of the negative electrode active material to the conductive additive to the binder is (70-95): (15-4): (15-1).
Example 1
The invention discloses a bifunctional elastic polyurea adhesive, a preparation method and application thereof, wherein the preparation of the adhesive specifically comprises the following steps:
step 2, cooling the oil bath to 75 ℃, weighing diisocyanate, dissolving the diisocyanate in an N, N-Dimethylformamide (DMF) solvent, and dropwise adding the diisocyanate into a three-necked bottle;
step 3, adding dibutyltin dilaurate (DBTDL) catalyst, wherein the dosage of the catalyst is 0.1 percent of the total mass of the polyethylene glycol and the diisocyanate, and heating the mixed solution for reaction for 2 hours at the reaction temperature of 75 ℃ under the protection of nitrogen and magnetic stirring to obtain a prepolymer;
and 4, cooling the oil bath to 40 ℃, weighing a biuret chain extender by using an electronic balance, dissolving the biuret chain extender into a DMF solvent, dropwise and slowly adding the solution into the reactor, carrying out chain extension reaction under the protection of nitrogen and magnetic stirring until no absorption peak of isocyanate functional groups is detected under infrared spectrum test, and stopping the reaction, thereby preparing the bifunctional elastic polyurea adhesive solution. The chain extension reaction lasted about 1.5 h. Wherein the molar ratio of the polyethylene glycol to the diisocyanate to the chain extender is 1: 2: 1.
the polyurea adhesive thus prepared is designated as A1, and the synthesis steps and structural formula are shown as the following formula.
The adhesive is a bifunctional elastic polyurea adhesive, has excellent self-repairing performance and ion conductivity, and can realize rapid self-repairing at room temperature. FIG. 1 is an optical micrograph of a film made of a synthetic polyurea adhesive at various time periods after scratching, where the polyurea film was initially scratched severely and visibly scratched (FIG. 1 a); after being placed for 0.5h at room temperature, the scratch becomes shallow, the wound becomes narrow, and certain self-repairing property is shown (figure 1 b); after 1h at room temperature, the scratch disappeared completely and the resulting lesion healed substantially completely (fig. 1 c). The polyurea adhesive exhibits significant self-healing capabilities.
The lithium ion battery negative electrode can be prepared on the basis of the bifunctional elastic polyurea adhesive, and comprises a copper foil current collector, and a negative electrode active material, a conductive additive and an adhesive which are attached to the current collector. When the negative electrode is used for assembling a lithium ion half cell for testing, the electrode is made of lithium metal; the electrolyte is a mixed solution of lithium hexafluorophosphate, dimethyl carbonate and diethyl carbonate, and contains 10 vol% of fluoroethylene carbonate (FEC) as an additive; the diaphragm is a polypropylene microporous diaphragm.
The preparation method of the negative electrode and the lithium ion button cell comprises the following steps:
dispersing nano silicon particles and Super-P conductive carbon black into a synthesized bifunctional elastic polyurea adhesive A1 solution, carrying out ball milling in a planetary ball mill for 1h to obtain uniformly mixed slurry, uniformly coating the slurry on a copper foil current collector by using an automatic film coating machine, wherein the coating thickness is 25 mu m, and carrying out vacuum drying at 120 ℃ for 2h to obtain a final electrode; wherein the mass ratio of the nano silicon to the conductive carbon black to the adhesive A1 is 70:15: 15. and cutting the electrode by using a manual punching machine to obtain the silicon negative electrode slice with the diameter of 12 mm.
And transferring the silicon cathode electrode plate prepared by using the bifunctional elastic polyurea adhesive A1 into a super-purification glove box filled with argon gas, assembling a 2032 type button half cell, and using a metal lithium foil as a counter electrode and a polypropylene microporous diaphragm as a diaphragm. And (3) standing the prepared 2032 button half-cell for 6h, and then carrying out constant-current charge-discharge cycle test by using a blue battery test system under the voltage range of 0.01-1.5V.
Comparative example 1
Preparing a lithium ion battery nano silicon negative electrode by using a polyacrylic acid adhesive (the theoretical specific capacity is 4000 mAh/g): dispersing the nano silicon particles and the Super-P conductive carbon black into a polyacrylic acid (PAA) aqueous solution with the mass concentration of 5%, and carrying out ball milling in a planetary ball mill for 1h to fully mix the nano silicon particles and the Super-P conductive carbon black to obtain uniformly dispersed negative electrode slurry. Wherein the mass ratio of the nano silicon to the conductive carbon black to the polyacrylic acid adhesive is 70:15: 15. And coating the slurry on a copper foil current collector by using an automatic film coating agent, wherein the coating thickness is 25 mu m, and drying the copper foil current collector for 2h under vacuum at 100 ℃ to obtain the final electrode. And cutting the electrode by using a manual punching machine to obtain a silicon negative electrode plate with the diameter of 12 mm.
The lithium ion battery assembled by the nano silicon cathode prepared above was tested, and all the steps were the same as in example 1.
Referring to fig. 2 and table 1, testing of the electrode-assembled button cells prepared in comparative example 1 and example 1 revealed that the capacity retention was less than 60% after 100 weeks cycling of the electrodes prepared using the conventional polyacrylic acid binder. The nano silicon cathode prepared by using the bifunctional elastic polyurea adhesive A1 synthesized by the invention shows very excellent charge and discharge performance, and is particularly characterized in that the capacity of the battery is kept stable along with the increase of the cycle number, and the capacity is hardly lost after 100 weeks of cycle; meanwhile, the first-week coulombic efficiency is improved to 89.75%, and the electrochemical stability is very strong.
Referring to fig. 3, the button cells prepared in comparative example 1 and example 1 were subjected to rate capability tests, and it can be seen that the electrode using the synthetic bifunctional elastic polyurea adhesive a1 exhibited more excellent rate capability as the current density increased: the discharge specific capacity of the lithium ion battery can be stably maintained at 3090, 2798, 2299, 1891 and 1309mAh/g under the current densities of 0.3C, 0.5C, 0.75C, 1C and 1.5C respectively; when the current density is recovered to 0.3C, the specific discharge capacity is also stably recovered to 2707 mAh/g. The improvement of the rate capability is closely related to the good ionic conductivity of the polyurea adhesive.
Referring to fig. 4, after the electrodes prepared in comparative example 1 and example 1 were subjected to a 50-week charge-discharge cycle test, they were characterized using a scanning electron microscope to find: the nano silicon cathode prepared by the bifunctional elastic polyurea adhesive synthesized by the invention has a relatively flat surface after 50 weeks of circulation, no crack is generated, and the electrode structure is kept complete; and the electrode prepared by using the traditional adhesive generates cracks of about 1 mu m on the surface of the electrode after 50 weeks of circulation, and the electrode structure is subjected to irreversible damage. These significant differences can be attributed to the excellent self-healing properties and good elasticity of the polyurea adhesive, which allows for rapid repair when the electrode is damaged due to volume changes, thereby maintaining the structural integrity and stability of the electrode.
Example 2
A bifunctional elastic polyurea adhesive A1 having self-healing properties and ion-conducting properties was synthesized, all in the same manner as in example 1.
The synthesized polyurea adhesive A1 was used to prepare a silicon carbon negative electrode of a lithium ion battery by the following procedure: dispersing silicon carbon particles and Super-P conductive carbon black into a synthesized polyurea adhesive A1 solution, and performing ball milling in a planetary ball mill for 1h to fully mix the silicon carbon particles and the Super-P conductive carbon black to obtain uniformly mixed cathode slurry. And coating the slurry on a copper foil current collector by using an automatic coating machine, wherein the coating thickness is 50 mu m, and drying the copper foil current collector in vacuum at 120 ℃ for 2h to obtain a final electrode. Wherein the mass ratio of the silicon-carbon material to the conductive carbon black to the adhesive A1 is 80:10: 10. and cutting the electrode by using a manual punching machine to obtain the silicon-carbon negative electrode plate with the diameter of 12 mm.
And transferring the silicon-carbon negative electrode plate prepared by using the bifunctional elastic polyurea adhesive A1 into a super-purification glove box filled with argon gas, assembling a 2032 type button half cell, and using a metal lithium foil as a counter electrode and a polypropylene microporous diaphragm as a diaphragm. And (3) standing the prepared 2032 button half-cell for 6h, and then carrying out constant-current charge-discharge cycle test by using a blue battery test system under the voltage range of 0.01-2V.
Comparative example 2
Preparing a lithium ion battery silicon-carbon negative electrode by using a polyacrylic acid adhesive (the theoretical specific capacity is 500 mAh/g): dispersing a silicon carbon material and Super-P conductive carbon black into a polyacrylic acid (PAA) aqueous solution with the mass concentration of 5%, and performing ball milling in a planetary ball mill for 1h to fully mix the materials to obtain uniformly dispersed negative electrode slurry. Wherein the mass ratio of the silicon carbon material to the conductive carbon black to the polyacrylic acid adhesive is 80:10: 10. And coating the slurry on a copper foil current collector by using an automatic film coating agent, wherein the coating thickness is 50 mu m, and drying the copper foil current collector for 2h at 100 ℃ in vacuum to obtain the final electrode. And cutting the electrode by using a manual punching machine to obtain the silicon-carbon negative electrode plate with the diameter of 12 mm.
The lithium ion battery assembled by the nano silicon cathode prepared above was tested, and all the steps were the same as in example 2.
Referring to fig. 5 and table 1, the silicon carbon negative electrode prepared in example 2 using the synthesized bifunctional elastic polyurea binder a1 of the present invention also exhibited good cycle stability performance. Almost no capacity fade after 100 charge-discharge cycles; the capacity retention rate reaches over 90 percent after 200 charge-discharge cycles. Compared with the silicon-carbon cathode prepared by using the traditional polyacrylic acid binder in the comparative example 2, the electrochemical performance is obviously improved.
Example 3
A bifunctional elastic polyurea adhesive A1 having self-healing properties and ion-conducting properties was synthesized, all in the same manner as in example 1.
The specific preparation method of the lithium ion battery nano silicon negative electrode prepared by using the synthesized bifunctional elastic polyurea adhesive A1 is the same as that in example 1, except that the mass ratio of the nano silicon to the conductive carbon black to the synthesized polyurea adhesive A1 is 80:10: 10.
A nano-silicon negative assembled lithium ion battery prepared using the bi-functional elastic polyurea binder a1 was tested, all in the same manner as in example 1.
Referring to table 1, in example 3, the charge and discharge performance of the nano-silicon negative electrode prepared by using the polyurea bifunctional elastic binder a1 synthesized by the present invention is significantly improved, specifically, the capacity of the battery is kept stable with the increase of the cycle number, and the capacity retention rate is increased to more than 80% after 100 charge and discharge cycles; the first week coulomb efficiency is greatly improved and approaches to 90 percent.
Example 4
A bifunctional elastic polyurea adhesive A1 having self-healing properties and ion-conducting properties was synthesized, all in the same manner as in example 1.
The specific preparation method of the lithium ion battery silicon-carbon negative electrode prepared by using the synthesized bifunctional elastic polyurea adhesive A1 is the same as that in example 2, except that the mass ratio of the nano silicon to the conductive carbon black to the synthesized polyurea adhesive A1 is 95:4: 1.
The nano-silicon negative assembled lithium ion battery prepared using the bifunctional elastic polyurea binder a1 was tested, all in the same manner as in example 2.
Example 5
The specific preparation method of the bifunctional elastic polyurea adhesive of this example is the same as the preparation of the adhesive a1 in example 1, except that the molar ratio of the polyethylene glycol, the diisocyanate and the chain extender is 2: 3: 1, the polyurea adhesive thus prepared is designated a 2.
The synthesized bifunctional elastic polyurea binder a2 was used to prepare a lithium ion battery nanosilicon negative electrode, all in the same manner as in example 1.
A nano-silicon negative assembled lithium ion battery prepared using the bi-functional elastic polyurea binder a2 was tested, all in the same manner as in example 1.
Example 6
The specific procedure for preparing the dual function elastomeric polyurea adhesive of this example was the same as the adhesive A1 of example 1, except that bis (4-aminophenyl) disulfide was used as the chain extender, and the polyurea adhesive thus prepared was designated A3.
The synthesized bifunctional elastic polyurea binder a3 was used to prepare a lithium ion battery nanosilicon negative electrode, all in the same manner as in example 1.
The nano-silicon negative assembled lithium ion battery prepared by using the bifunctional elastic polyurea adhesive A3 was tested, and all the procedures were the same as in example 1.
Example 7
A bifunctional elastic polyurea adhesive A3 having self-healing properties and ion-conducting properties was synthesized, all in the same manner as in example 6.
A lithium ion battery silicon carbon negative electrode was prepared using the synthetic bifunctional elastic polyurea binder a3, all in the same manner as in example 2.
A lithium ion battery assembled from a silicon carbon negative electrode prepared using the bifunctional elastic polyurea binder a3 was tested, all in the same manner as in example 2.
Example 8
The specific preparation method of the bifunctional elastic polyurea adhesive of this example is the same as the preparation of adhesive a1 in example 1, except that ethylene diamine is used as the chain extender, and the polyurea adhesive thus prepared is designated as a 4.
The synthesized bifunctional elastic polyurea adhesive A4 was used to prepare a lithium ion battery nanosilicon negative electrode, all in the same manner as in example 1.
A nano-silicon negative assembled lithium ion battery prepared using the bi-functional elastic polyurea binder a4 was tested, all in the same manner as in example 1.
Example 9
A bifunctional elastic polyurea adhesive A4 having self-healing properties and ion-conducting properties was synthesized, all in the same manner as in example 8.
A lithium ion battery silicon carbon negative electrode was prepared using the synthetic bifunctional elastic polyurea binder a4, all in the same manner as in example 2.
A lithium ion battery assembled from a silicon carbon negative electrode prepared using the bifunctional elastic polyurea binder a4 was tested, all in the same manner as in example 2.
Example 10
The bifunctional elastic polyurea adhesive of this example was prepared in a specific manner similar to the adhesive a1 of example 1, except that the molecular weight Mw of the polyethylene glycol was 1000, and the polyurea adhesive thus prepared was designated as a 5.
The synthesized bifunctional elastic polyurea binder a5 was used to prepare a lithium ion battery nanosilicon negative electrode, all in the same manner as in example 1.
A nano-silicon negative assembled lithium ion battery prepared using the bi-functional elastic polyurea binder a5 was tested, all in the same manner as in example 1.
Example 11
The bifunctional elastic polyurea adhesive of this example was prepared in a specific manner similar to the adhesive a1 of example 1, except that the molecular weight of the polyethylene glycol, Mw, was 4000, and the polyurea adhesive thus prepared was designated as a 6.
The synthesized bifunctional elastic polyurea binder a6 was used to prepare a lithium ion battery nanosilicon negative electrode, all in the same manner as in example 1.
A nano-silicon negative assembled lithium ion battery prepared using the bi-functional elastic polyurea binder a6 was tested, all in the same manner as in example 1.
Example 12
The bifunctional elastic polyurea adhesive of this example was prepared in a specific manner similar to the adhesive a1 of example 1, except that the molecular weight of the polyethylene glycol, Mw, was 6000, and the polyurea adhesive thus prepared was designated as a 7.
The synthesized bifunctional elastic polyurea binder a7 was used to prepare a lithium ion battery nanosilicon negative electrode, all in the same manner as in example 1.
The nano-silicon negative assembled lithium ion battery prepared by using the bifunctional elastic polyurea adhesive A7 was tested, and all the procedures were the same as in example 1.
Example 13
The specific method of making the bifunctional elastic polyurea adhesive of this example was the same as the adhesive a1 of example 1, except that the molecular weight of the polyethylene glycol, Mw, was 10000, and the polyurea adhesive thus obtained was designated as A8.
The synthesized bifunctional elastic polyurea binder A8 was used to prepare a lithium ion battery nanosilicon negative electrode, all in the same manner as in example 1.
A nano-silicon negative assembled lithium ion battery prepared using the bi-functional elastic polyurea binder A8 was tested, all in the same manner as in example 1.
The measured properties of the lithium ion battery in some of the examples are shown in table 1.
Table 1 test results of lithium ion batteries manufactured according to examples of the present invention and comparative examples
| Numbering | Initial specific discharge capacity (mAh/g) | First week efficiency (%) | Capacity retention ratio at 100 weeks (%) |
| Example 1 | 3588.0 | 89.75 | 96.96 |
| Comparative example 1 | 3502.0 | 80.21 | 58.95 |
| Example 2 | 632.8 | 72.34 | 96.80 |
| Comparative example 2 | 697.8 | 69.95 | 64.99 |
| Example 3 | 3592.7 | 89.06 | 81.79 |
| Example 4 | 668.2 | 70.03 | 74.63 |
| Example 5 | 3600.7 | 87.05 | 82.10 |
| Example 6 | 3814.7 | 88.65 | 84.15 |
| Example 7 | 611.7 | 72.20 | 94.81 |
| Example 8 | 3107.5 | 90.50 | 82.95 |
| Example 9 | 624.8 | 71.84 | 92.88 |
| Example 10 | 3358.2 | 87.44 | 89.23 |
| Example 11 | 3169.7 | 85.63 | 86.82 |
From the above table, it can be seen that the lithium ion battery cathodes prepared by using the bifunctional elastic polyurea binder synthesized by the invention all show good electrochemical performance, and tests on the lithium ion batteries prepared in the embodiments show that the capacity retention rate is basically over 80% after 100 cycles. Compared with a comparative example, the first week coulombic efficiency and the cycle stability are both obviously improved.
Example 14
The specific preparation method of the bifunctional elastic polyurea adhesive of this example is the same as the preparation of the adhesive a1 in example 1, except that the molar ratio of the polyethylene glycol, the diisocyanate and the chain extender is 3: 4:1, the dosage of the catalyst is 0.05 percent of the total mass of the polyethylene glycol and the diisocyanate.
Example 15
The specific preparation method of the bifunctional elastic polyurea adhesive of this example is the same as the preparation of the adhesive a1 in example 1, except that the molar ratio of the polyethylene glycol, the diisocyanate and the chain extender is 2: 3: 1, the dosage of the catalyst is 1 percent of the total mass of the polyethylene glycol and the diisocyanate.
Example 16
The specific preparation method of the bifunctional elastic polyurea adhesive of this example is the same as the preparation of the adhesive a1 in example 1, except that the molar ratio of the polyethylene glycol, the diisocyanate and the chain extender is 1: 2: 1, the dosage of the catalyst is 0.5 percent of the total mass of the polyethylene glycol and the diisocyanate.
Example 17
The specific preparation method of the bifunctional elastic polyurea adhesive of this example is the same as the preparation of the adhesive a1 in example 1, except that the molar ratio of the polyethylene glycol, the diisocyanate and the chain extender is 3: 4:1, the dosage of the catalyst is 0.8 percent of the total mass of the polyethylene glycol and the diisocyanate.
Example 18
The specific preparation method of the bifunctional elastic polyurea adhesive of this example is the same as the preparation of the adhesive a1 in example 1, except that the molar ratio of the polyethylene glycol, the diisocyanate and the chain extender is 2: 3: 1, the dosage of the catalyst is 0.1 percent of the total mass of the polyethylene glycol and the diisocyanate.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A method of preparing a bi-functional elastic polyurea adhesive comprising the steps of:
step 1, placing polyethylene glycol with the weight-average molecular weight of 1000-10000 in a reaction container, and distilling under reduced pressure under oil bath and magnetic stirring to remove the moisture of the polyethylene glycol to obtain a reactant A;
step 2, after the oil bath temperature of the reactant A is reduced, adding a diisocyanate solution into the reactant A to obtain a reaction system B;
step 3, adding a catalyst into the reaction system B, and heating and reacting under the protection of nitrogen to obtain a prepolymer;
and 4, mixing the chain extender solution with the prepolymer, stirring under the protection of nitrogen to react, wherein the molar ratio of the polyethylene glycol to the diisocyanate to the chain extender is (1-3): (2-4): 1; when the absorption peak of the isocyanate functional group is not detected by the infrared spectrum, the reaction is stopped to obtain the bifunctional elastic polyurea adhesive.
2. The production process according to claim 1, wherein in the step 1, the oil bath temperature is 110 ℃ and the distillation time under reduced pressure is 2 hours.
3. The method according to claim 1, wherein in the step 2, the solute in the diisocyanate solution is isophorone diisocyanate, and the solvent is N, N-dimethylformamide, N-dimethylacetamide or dimethylsulfoxide.
4. The method according to claim 1, wherein the reaction temperature in step 3 is 75 ℃ and the reaction time is 2 hours.
5. The method according to claim 1, wherein in the step 3, the catalyst is one or a mixture of two of an organotin catalyst and an amine catalyst.
6. The process according to claim 1, wherein in the step 3, the amount of the catalyst is 0.05 to 1% by mass based on the sum of the mass of the polyethylene glycol and the mass of the diisocyanate.
7. The method according to claim 1, wherein in step 4, the solute of the chain extender solution is bis (4-aminophenyl) disulfide, biuret, or ethylenediamine, and the solvent is N, N-dimethylformamide, N-dimethylacetamide, or dimethylsulfoxide.
8. A bifunctional elastic polyurea adhesive prepared by the preparation process according to any one of claims 1 to 7.
9. Use of the bifunctional elastic polyurea binder according to claim 8, wherein the bifunctional elastic polyurea binder is used in a negative electrode material for a lithium battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111449996.0A CN114479002A (en) | 2021-11-30 | 2021-11-30 | Difunctional elastic polyurea adhesive and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111449996.0A CN114479002A (en) | 2021-11-30 | 2021-11-30 | Difunctional elastic polyurea adhesive and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114479002A true CN114479002A (en) | 2022-05-13 |
Family
ID=81492455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111449996.0A Pending CN114479002A (en) | 2021-11-30 | 2021-11-30 | Difunctional elastic polyurea adhesive and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114479002A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116505066A (en) * | 2023-05-08 | 2023-07-28 | 深圳飞扬骏研新材料股份有限公司 | Polyurea-based solid electrolyte and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10302798A (en) * | 1997-04-22 | 1998-11-13 | Toyobo Co Ltd | Production of negative and positive electrodes for secondary battery |
| CN109181621A (en) * | 2018-09-11 | 2019-01-11 | 浙江奔富新能源股份有限公司 | A kind of dual-component polyurethane Resin adhesive and preparation method thereof for polymer Li-ion battery flexible packaging film |
| CN111647345A (en) * | 2020-04-21 | 2020-09-11 | 万向一二三股份公司 | Lithium ion battery negative electrode polymer protective coating and preparation method and application thereof |
| CN112687854A (en) * | 2020-12-17 | 2021-04-20 | 广东微电新能源有限公司 | Silicon monoxide composite negative electrode material of lithium ion battery and preparation method and application thereof |
-
2021
- 2021-11-30 CN CN202111449996.0A patent/CN114479002A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10302798A (en) * | 1997-04-22 | 1998-11-13 | Toyobo Co Ltd | Production of negative and positive electrodes for secondary battery |
| CN109181621A (en) * | 2018-09-11 | 2019-01-11 | 浙江奔富新能源股份有限公司 | A kind of dual-component polyurethane Resin adhesive and preparation method thereof for polymer Li-ion battery flexible packaging film |
| CN111647345A (en) * | 2020-04-21 | 2020-09-11 | 万向一二三股份公司 | Lithium ion battery negative electrode polymer protective coating and preparation method and application thereof |
| CN112687854A (en) * | 2020-12-17 | 2021-04-20 | 广东微电新能源有限公司 | Silicon monoxide composite negative electrode material of lithium ion battery and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHANYU JIA，ET AL.: "Polypyrrole/PU hybrid hydrogels: electrically conductive and fast self-healing for potential applications in body-monitor sensors", 《NEW J. CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116505066A (en) * | 2023-05-08 | 2023-07-28 | 深圳飞扬骏研新材料股份有限公司 | Polyurea-based solid electrolyte and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108878959A (en) | A kind of preparation and its application of organo-mineral complexing solid electrolyte | |
| CN111261874B (en) | Lithium ion battery cathode and preparation method and application thereof | |
| CN111769278B (en) | Water system rechargeable zinc ion battery based on aromatic organic matter positive electrode material and application thereof | |
| CN110112417B (en) | Elastic lithium metal negative electrode surface modification layer, preparation method thereof and lithium metal negative electrode | |
| JP2005259641A (en) | Electrolytic solution and electrode for lithium secondary battery, lithium secondary battery, and manufacturing method of those | |
| CN111433248B (en) | Elastic and stretchable gel polymer electrolytes | |
| US20180076458A1 (en) | Porous Silicon Materials and Conductive Polymer Binder Electrodes | |
| CN110627997A (en) | Thermoplastic polyurethane adhesive for lithium ion battery and preparation method and application thereof | |
| CN111647345B (en) | Lithium ion battery negative electrode polymer protective coating and preparation method and application thereof | |
| CN105703003A (en) | Comb-shaped polymer, electrolyte and composite electrode for lithium battery, and applications of electrolyte and composite electrode | |
| CN115425292A (en) | High-temperature-resistant electrolyte, secondary battery and application thereof | |
| JP2017045503A (en) | Additive for nonaqueous electrolyte secondary battery, electrode for nonaqueous electrolyte secondary battery, electrolyte for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery | |
| Zhao et al. | Construction of high elastic artificial SEI for air-stable and long-life lithium metal anode | |
| CN108565397B (en) | Surface oxidation composite protective layer structure of lithium metal electrode and preparation method | |
| CN114479002A (en) | Difunctional elastic polyurea adhesive and preparation method and application thereof | |
| CN112687854B (en) | Silicon monoxide composite negative electrode material of lithium ion battery and preparation method and application thereof | |
| CN111900335B (en) | Silicon-based negative electrode with self-repairing property and preparation method and application thereof | |
| CN107834072B (en) | Lithium ion battery binder | |
| CN111969242B (en) | Lithium metal battery and preparation method thereof | |
| CN115188945A (en) | Coated positive electrode material and preparation method and application thereof | |
| CN106033806B (en) | A kind of selenizing high molecular polymer positive electrode and preparation method thereof | |
| CN110980672B (en) | Lithium ion battery negative electrode active material, preparation method thereof and lithium ion battery | |
| CN114142034A (en) | Negative self-healing adhesive and preparation method and application thereof | |
| CN109980226B (en) | Zinc cathode with polyamide brightener layer and preparation method and application thereof | |
| CN113471398A (en) | Electrode slurry based on halide solid electrolyte, solid electrode and all-solid-state battery |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220513 |