CN111682213A - Preparation method of binder for lithium battery - Google Patents
Preparation method of binder for lithium battery Download PDFInfo
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- CN111682213A CN111682213A CN202010513335.9A CN202010513335A CN111682213A CN 111682213 A CN111682213 A CN 111682213A CN 202010513335 A CN202010513335 A CN 202010513335A CN 111682213 A CN111682213 A CN 111682213A
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- aromatic
- binder
- lithium battery
- butadiene rubber
- polyamide
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- 239000011230 binding agent Substances 0.000 title claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 37
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 32
- 229920002396 Polyurea Polymers 0.000 claims abstract description 30
- 239000004760 aramid Substances 0.000 claims abstract description 14
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 8
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims abstract description 3
- 239000004952 Polyamide Substances 0.000 claims description 21
- 229920002647 polyamide Polymers 0.000 claims description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000007773 negative electrode material Substances 0.000 abstract description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 239000000725 suspension Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000011267 electrode slurry Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 239000005543 nano-size silicon particle Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- -1 polyethylene Polymers 0.000 description 6
- 235000010288 sodium nitrite Nutrition 0.000 description 6
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 6
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 6
- 235000012141 vanillin Nutrition 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 229940113088 dimethylacetamide Drugs 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- C08G18/60—Polyamides or polyester-amides
- C08G18/603—Polyamides
-
- 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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a binder for a lithium battery, which mainly comprises the following steps: (1) synthesis of aromatic polyamide: mixing and heating excessive aromatic diamine and dibasic acid to react to generate aromatic polyamide with amino at two ends; (2) carrying out solution polymerization on aromatic diisocyanate and aromatic polyamide to obtain a polyurea polymer; (3) and (3) dissolving styrene butadiene rubber with a certain molecular weight, adding the polyurea polymer prepared in the step (2) into a styrene butadiene rubber solution, and stirring and dispersing uniformly to obtain the binder for the lithium battery. The prepared binder for the lithium battery, disclosed by the invention, contains the polyurea polymer containing the rigid group and a large number of secondary amino groups, can well inhibit the volume effect of a lithium battery negative electrode material and has better binding performance; the contained flexible styrene-butadiene rubber is beneficial to improving the dispersion of rigid polyurea polymers and improving the energy density of the negative pole piece.
Description
Technical Field
The invention belongs to the field of high polymer materials, and relates to a preparation method of a binder for a lithium battery.
Background
The silicon used as the lithium battery cathode material has the theoretical capacity of up to 4200mAh/g and has good development prospect. However, due to the characteristics of silicon, silicon has a relatively large volume change in the charging and discharging process, which greatly damages the structure of the negative electrode material, resulting in poor practical use effect. Therefore, the selection of a proper binder will effectively improve the volume effect of the silicon material.
CN110364734A discloses a high-performance water-based lithium ion battery negative electrode binder, a preparation method and application thereof, wherein the binding effect of the binder is improved by the composite use of polyacrylic acid-glycinamide. However, this does not well solve the problem of expansion and contraction of the negative electrode active material during charge and discharge. CN110137497A discloses a polycarbonate modified acrylate binder, which inhibits the expansion of the negative electrode material of the lithium battery by rigid polycarbonate, thereby improving the cycle performance of the battery. However, the bonding effect of the bonding agent prepared by the scheme is poor, the pole piece active material is easy to fall off, and the dispersion is difficult. CN110085867A discloses a preparation method of a composite binder of polyacrylic acid, metal oxide and lithium hydroxide, wherein polyacrylic acid provides cohesiveness, rigid metal oxide inhibits volume expansion of active material, and metal oxide improves conductive capability. However, the metal oxide in the composite binder prepared by the scheme is easy to fall off, enters into the electrolyte and is deposited on the diaphragm, so that the conductivity of the battery is greatly reduced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a binder for a lithium battery cathode aiming at the defects in the prior art, wherein a polyurea polymer containing a rigid group and a large number of secondary amino groups can well inhibit the volume effect of a lithium battery cathode material and has better binding performance; the contained flexible styrene-butadiene rubber is beneficial to improving the dispersion of rigid polyurea polymers and improving the energy density of the negative pole piece.
The technical scheme adopted by the invention for solving the problems is as follows:
a preparation method of a binder for a lithium battery mainly comprises the following steps:
(1) mixing and heating excessive aromatic diamine and dibasic acid to react to generate aromatic polyamide with amino at two ends;
(2) carrying out solution polymerization on aromatic diisocyanate and aromatic polyamide with amino at two ends in an organic solvent to obtain a polyurea polymer;
(3) and (3) adding the polyurea polymer prepared in the step (2) into styrene butadiene rubber, and uniformly stirring and dispersing in an organic solvent to obtain the binder for the lithium battery.
According to the scheme, the aromatic diisocyanate is any one of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, naphthalene diisocyanate and the like; the aromatic diamine is one or more of diethyl toluene diamine, p-phenylenediamine and the like; the dibasic acid is any one of oxalic acid, adipic acid and the like.
According to the scheme, the organic solvent adopted in the step (2) and the step (3) is any one of N-methyl pyrrolidone, N-dimethylformamide, dimethylacetamide and the like.
According to the scheme, the molar ratio of the aromatic diamine to the dibasic acid in the step (1) is 2 (1.2-1.8) according to the functional group.
According to the scheme, the step (1) is specifically as follows: reacting aromatic diamine and dibasic acid at 60-80 ℃ for 1-2h by taking water as a solvent to obtain the aromatic polyamide with amino at two ends. Wherein the total solid content of the aromatic diamine and the dibasic acid in the water is 5-15%.
According to the scheme, the step (2) is specifically as follows: at the temperature of 100-115 ℃, the polyamide organic solution is dripped into the aromatic diisocyanate organic solution until the isocyanate reaction is completed, and the aromatic polyurea polymer is obtained. Wherein, the polyamide organic solution and the aromatic diisocyanate organic solution are generally mixed according to the volume ratio of (1.2-1.5) to 1, and the mass fractions of the polyamide organic solution and the aromatic diisocyanate organic solution are both about 10 percent.
According to the scheme, the step (3) is specifically as follows: dispersing a polyurea polymer in an organic solvent to ensure that the solid content of the polymer is 10-15 wt%; dispersing styrene butadiene rubber in an organic solvent, wherein the mass fraction is 5-15 wt%; and then adding the polyurea polymer organic solution into the styrene butadiene rubber organic solution, and uniformly stirring and dispersing to obtain the binder for the lithium battery. Wherein the mass ratio of the polyurea polymer to the styrene butadiene rubber is (2-4) to (3-6); the number average molecular weight of the styrene-butadiene rubber is 50000-80000.
The invention provides a preparation method of a more preferable binder for a lithium battery, which comprises the following specific steps:
(1) adding aromatic diamine and dibasic acid into deionized water according to the molar ratio of functional groups of 2 (1.2-1.8) to ensure that the solid content of solute is about 10 wt%, and heating to 60-80 ℃ in a device with condensation reflux to react for 1-2h to obtain aromatic polyamide suspension; centrifuging the obtained suspension, washing with deionized water, drying at 60 deg.C for 6-12h to obtain polyamide, and detecting amino group as terminal group with vanillin.
(2) Respectively preparing an aromatic diisocyanate organic solution and a polyamide organic solution with the mass fraction of about 10 wt%; at the temperature of 100-115 ℃, the polyamide organic solution is dripped into the aromatic diisocyanate organic solution, and the sodium nitrite solution is used for detecting isocyanic acid radical until the diisocyanate reaction is complete, so as to obtain the aromatic polyurea polymer solution.
(3) Adding an organic solvent into the aromatic polyurea polymer solution obtained in the step (2) to ensure that the solid content of the polymer is 10-15 wt%; preparing a styrene butadiene rubber organic solution with the mass fraction of 10 wt%; and (3) uniformly mixing the two organic solutions according to the mass ratio of (2-4) to (4-8) to obtain a polyurea-styrene butadiene rubber solution, namely the binder for the lithium battery.
According to the scheme, when the vanillin solution meets amino, the solution is yellow; when the sodium nitrite solution meets the isocyanate, the solution can be orange to reddish brown, and the color shade depends on the concentration of the isocyanate.
Compared with the prior art, the invention has the beneficial effects that:
the prepared binder for the lithium battery, namely the polyurea-styrene butadiene rubber solution, wherein the polyurea polymer containing rigid groups and a large number of secondary amino groups can well inhibit the volume effect of the lithium battery cathode material and has better binding performance; the contained flexible styrene-butadiene rubber is beneficial to improving the dispersion of rigid polyurea polymers and improving the energy density of the negative pole piece.
Drawings
Fig. 1 is a cycle chart at 0.2C rate for button cell a prepared in example 1 and comparative 1.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
A preparation method of a binder for a lithium battery comprises the following specific steps:
(1) adding diethyl toluenediamine and oxalic acid into deionized water according to the mol ratio of 2:1.2 to ensure that the solid content of solute is 10 wt%, and heating the mixture to 60 ℃ in a device with condensation reflux for reacting for 1.5h to obtain aromatic polyamide suspension; centrifuging the obtained suspension, washing with deionized water, drying at 60 deg.C for 6-12h to obtain polyamide, and detecting amino group as terminal group with vanillin.
(2) Preparing an N-methylpyrrolidone solution of 2, 4-toluene diisocyanate with the mass fraction of 10 wt%; preparing an N-methyl pyrrolidone solution of polyamide with the mass fraction of 10 wt%; at 110 ℃, dripping a polyamide organic solution into an aromatic diisocyanate organic solution, and detecting isocyanate by using a sodium nitrite solution until diisocyanate is completely reacted to obtain an aromatic polyurea polymer solution.
(3) Adding N-methyl pyrrolidone into the aromatic polyurea polymer solution obtained in the step (2) to ensure that the solid content of the polymer is 10 wt%; preparing an N-methyl pyrrolidone solution of styrene butadiene rubber with the mass fraction of 10 wt%; and uniformly mixing the two organic solutions according to the mass ratio of 3:2 to obtain a polyurea-styrene butadiene rubber organic solution, namely the binder for the lithium battery.
Mixing and grinding nano silicon and graphite for 1 hour according to the mass ratio of 10:80, and adding the mixed powder into the binder prepared in the embodiment 1 to obtain electrode slurry, wherein the mass ratio of the nano silicon to the graphite to the binder is 10: 80: 100; adding N-methyl pyrrolidone into the electrode slurry to enable the solid content of the slurry system to reach 20-30 wt%, uniformly stirring, coating on the carbon-coated copper foil, and drying at 80 ℃ and 0.1Mpa for 12h to obtain a negative electrode slice; the obtained negative electrode sheet, a polyethylene diaphragm, a lithium sheet and an LBC301 type electrolyte were assembled into a CR2016 type button cell, which was designated as sample a.
The sodium carboxymethylcellulose-styrene butadiene rubber (the mass ratio of the sodium carboxymethylcellulose to the styrene butadiene rubber is 3:2) is used as a binder, deionized water is used as a solvent, a negative electrode electrolyte sheet is prepared according to the method, and the negative electrode electrolyte sheet, a polypropylene diaphragm, a lithium sheet and electrolyte are assembled into a CR2016 type button cell which is marked as a comparison sample 1.
The cycling test pattern of the assembled button cell is shown in fig. 1. At 0.2C magnification, after 200 cycles, the capacity retention of sample a was 98.57%, with little attenuation. However, the capacity retention of comparative sample 1 was only 92.2%, and there was a significant capacity fade. And from the trend of the capacity variation of fig. 1, the capacity of the sample a remains stable, while the comparative sample 1 will continuously decay.
Example 2
A preparation method of a binder for a lithium battery comprises the following specific steps:
(1) adding p-phenylenediamine and oxalic acid into deionized water according to the mol ratio of 2:1.5 to ensure that the solid content of solute is 10 wt%, and heating the mixture to 60 ℃ in a device with condensation reflux for reaction for 1-2h to obtain aromatic polyamide suspension; centrifuging the obtained suspension, washing with deionized water, drying at 60 deg.C for 6-12h to obtain polyamide, and detecting amino group as terminal group with vanillin.
(2) Respectively preparing an N-methylpyrrolidone solution of 2, 4-toluene diisocyanate with the mass fraction of 10 wt% and an N-methylpyrrolidone solution of polyamide; at 110 ℃, dripping the polyamide organic solution into the aromatic diisocyanate organic solution, and detecting isocyanate by using a sodium nitrite solution until the diisocyanate is completely reacted to obtain the aromatic polyurea polymer solution.
(3) Adding N-methyl pyrrolidone into the aromatic polyurea polymer solution obtained in the step (2) to ensure that the solid content of the polymer is 10 wt%; preparing an N-methyl pyrrolidone solution of styrene butadiene rubber with the mass fraction of 10 wt%; and uniformly mixing the two organic solutions according to the mass ratio of 2:4 to obtain the polyurea-styrene butadiene rubber solution.
The prepared polyurea-styrene butadiene rubber organic solution is directly used as a binder. Mixing and grinding nano silicon and graphite according to a mass ratio of 10:80 for 1h, and adding the mixed powder into the cross-linked polyurethane organic solution prepared in the embodiment 2 to obtain electrode slurry, wherein the mass ratio of the nano silicon to the graphite to the binder solution is 10: 80: 100; adding N-methyl pyrrolidone into the electrode slurry to enable the solid content of the slurry system to reach 20-30 wt%, uniformly stirring, coating on the carbon-coated copper foil, and drying at 80 ℃ and 0.1Mpa for 12h to obtain a negative electrode slice; the obtained negative electrode plate, a polyethylene diaphragm, a lithium sheet and an electrolyte are assembled into a CR2016 type button cell, and the CR2016 type button cell is marked as a sample B.
Example 3
A preparation method of a binder for a lithium battery comprises the following specific steps:
(1) adding diethyl toluenediamine and oxalic acid into deionized water according to the mol ratio of 2:1.8 to ensure that the solid content of solute is 10 wt%, and heating the mixture to 70 ℃ in a device with condensation reflux for reacting for 1-2h to obtain aromatic polyamide suspension; centrifuging the obtained suspension, washing with deionized water, drying at 60 deg.C for 6-12h to obtain polyamide, and detecting amino group as terminal group with vanillin.
(2) Respectively preparing an N-methylpyrrolidone solution of 2, 6-toluene diisocyanate with the mass fraction of 10 wt% and an N-methylpyrrolidone solution of polyamide; at 115 ℃, dripping the polyamide organic solution into the aromatic diisocyanate organic solution, and detecting isocyanic acid radical by using a sodium nitrite solution until the diisocyanate is completely reacted to obtain the aromatic polyurea polymer solution.
(3) Adding N-methyl pyrrolidone into the aromatic polyurea polymer solution obtained in the step (2) to ensure that the solid content of the polymer is 10 wt%; preparing an N-methyl pyrrolidone solution of styrene butadiene rubber with the mass fraction of 10 wt%; and uniformly mixing the two organic solutions according to the mass ratio of 2:5 to obtain the polyurea-styrene butadiene rubber solution.
The prepared polyurea-styrene butadiene rubber organic solution is directly used as a binder. Mixing and grinding nano silicon and graphite according to a mass ratio of 10:80 for 1h, and adding the mixed powder into the cross-linked polyurethane organic solution prepared in the embodiment 3 to obtain electrode slurry, wherein the mass ratio of the nano silicon to the graphite to the binder solution is 10: 80: 100; adding N-methyl pyrrolidone into the electrode slurry to enable the solid content of the slurry system to reach 20-30 wt%, uniformly stirring, coating on the carbon-coated copper foil, and drying at 80 ℃ and 0.1Mpa for 12h to obtain a negative electrode slice; and assembling the obtained negative electrode plate, a polyethylene diaphragm, a lithium sheet and electrolyte into a CR2016 type button cell, and marking as a sample C.
Example 4
A preparation method of a binder for a lithium battery comprises the following specific steps:
(1) adding diethyl toluenediamine and adipic acid into deionized water according to the mol ratio of 2:1.5 to ensure that the solid content of solute is 10 wt%, and heating to 80 ℃ in a device with condensation reflux to react for 1-2h to obtain aromatic polyamide suspension; centrifuging the obtained suspension, washing with deionized water, drying at 60 deg.C for 6-12h to obtain polyamide, and detecting amino group as terminal group with vanillin.
(2) Respectively preparing an N-methyl pyrrolidone solution of 2, 4-toluene diisocyanate with the mass fraction of 10 wt% and a dimethylacetamide solution of polyamide; at 115 ℃, dripping the polyamide organic solution into the aromatic diisocyanate organic solution, and detecting isocyanic acid radical by using a sodium nitrite solution until the diisocyanate is completely reacted to obtain the aromatic polyurea polymer solution.
(3) Adding dimethylacetamide into the aromatic polyurea polymer solution obtained in the step (2) to ensure that the solid content of the polymer is 10 wt%; preparing an N-methyl pyrrolidone solution of styrene butadiene rubber with the mass fraction of 10 wt%; and uniformly mixing the two organic solutions according to the mass ratio of 1:3 to obtain the polyurea-styrene butadiene rubber solution.
The prepared polyurea-styrene butadiene rubber organic solution is directly used as a binder. Mixing and grinding nano silicon and graphite according to a mass ratio of 10:80 for 1h, and adding the mixed powder into the cross-linked polyurethane organic solution prepared in the embodiment 4 to obtain electrode slurry, wherein the mass ratio of the nano silicon to the graphite to the binder solution is 10: 80: 100; adding dimethyl acetamide into the electrode slurry to enable the solid content of the slurry system to reach 20-30 wt%, uniformly stirring, coating on a carbon-coated copper foil, and drying at 80 ℃ and 0.1Mpa for 12h to obtain a negative electrode plate; the obtained negative electrode plate, a polyethylene diaphragm, a lithium sheet and an electrolyte are assembled into a CR2016 type button cell, and the CR2016 type button cell is marked as a sample D.
The sodium carboxymethylcellulose-styrene butadiene rubber is used as a binder, the dimethylacetamide is used as a solvent, the negative electrode electrolyte sheet is prepared according to the method, and the negative electrode electrolyte sheet, the polypropylene diaphragm, the lithium sheet and the electrolyte are assembled into the CR2016 type button cell which is marked as a comparison sample 2.
In the above embodiment, the assembled lithium battery samples a to D and the comparative samples 1 to 2 are tested by a blue testing system for cycle stability, the testing current density is 0.2C, and the testing results are shown in table 1, and the capacity retention rate of the button cell prepared in the embodiments 1 to 4 is significantly higher than that of the comparative samples 1 and 2 at 200 cycles.
TABLE 1
| Sample (I) | 0.2C initial discharge Capacity | Capacity retention after 200 cycles at 0.2C |
| Comparative sample 1 | 556mAh/g | 92.2％ |
| Comparative sample 2 | 543mAh/g | 92.3％ |
| Sample A | 562mAh/g | 98.57％ |
| Sample B | 561mAh/g | 96.5％ |
| Sample C | 558mAh/g | 97.8％ |
| Sample D | 556mAh/g | 97.2％ |
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (10)
1. A preparation method of a binder for a lithium battery is characterized by mainly comprising the following steps:
(1) mixing and heating excessive aromatic diamine and dibasic acid to react to generate aromatic polyamide with amino at two ends;
(2) carrying out solution polymerization on aromatic diisocyanate and aromatic polyamide with amino at two ends in an organic solvent to obtain a polyurea polymer;
(3) and (3) adding the polyurea polymer prepared in the step (2) into styrene butadiene rubber, and uniformly stirring and dispersing in an organic solvent to obtain the binder for the lithium battery.
2. The method of claim 1, wherein the aromatic diamine and the dibasic acid in the step (1) have a functional group molar ratio of 2 (1.2-1.8).
3. The method for preparing a binder for a lithium battery according to claim 1, wherein the step (1) is specifically: reacting aromatic diamine and dibasic acid at 60-80 ℃ for 1-2h by taking water as a solvent to obtain the aromatic polyamide with amino at two ends.
4. The method of claim 3, wherein the aromatic diamine and the dibasic acid have a total solid content of 5 to 15% in water.
5. The method for preparing a binder for a lithium battery according to claim 1, wherein the step (2) is specifically: at the temperature of 100-115 ℃, the polyamide organic solution is dripped into the aromatic diisocyanate organic solution until the isocyanate reaction is completed, and the aromatic polyurea polymer is obtained.
6. The method of claim 5, wherein the polyamide organic solution and the aromatic diisocyanate organic solution are mixed in a volume ratio of (1.2-1.5):1, and the mass fractions of the polyamide organic solution and the aromatic diisocyanate organic solution are 8-12%.
7. The method of claim 1, wherein the aromatic diisocyanate is any one of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, and naphthalene diisocyanate; the aromatic diamine is one or more of diethyl toluene diamine and p-phenylenediamine; the dibasic acid is any one of oxalic acid and adipic acid.
8. The method of claim 1, wherein the organic solvent used in step (2) and step (3) is any one of N-methylpyrrolidone, N-dimethylformamide, and dimethylacetamide.
9. The method for preparing a binder for a lithium battery according to claim 1, wherein the step (3) is specifically: dispersing a polyurea polymer in an organic solvent to ensure that the solid content of the polymer is 10-15 wt%; dispersing styrene butadiene rubber in an organic solvent, wherein the mass fraction is 5-15 wt%; and then adding the polyurea polymer organic solution into the styrene butadiene rubber organic solution, and uniformly stirring and dispersing to obtain the binder for the lithium battery.
10. The method of claim 9, wherein the mass ratio of the polyurea polymer to the styrene-butadiene rubber is (2-4) to (3-6); the number average molecular weight of the styrene-butadiene rubber is 50000-80000.
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