CN112500563A - Synthesis method of three-dimensional conjugated conductive polyaniline and application of three-dimensional conjugated conductive polyaniline as lithium ion battery cathode binder - Google Patents
Synthesis method of three-dimensional conjugated conductive polyaniline and application of three-dimensional conjugated conductive polyaniline as lithium ion battery cathode binder Download PDFInfo
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 103
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000001308 synthesis method Methods 0.000 title abstract description 7
- 239000003013 cathode binding agent Substances 0.000 title abstract description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000002002 slurry Substances 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 239000010406 cathode material Substances 0.000 claims abstract description 4
- 239000012065 filter cake Substances 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000005543 nano-size silicon particle Substances 0.000 claims description 30
- 239000011230 binding agent Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000007773 negative electrode material Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 16
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 7
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- -1 1,3, 5-triphenylanilinobenzene Chemical compound 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000002019 doping agent Substances 0.000 claims description 5
- 229910021385 hard carbon Inorganic materials 0.000 claims description 5
- 229910021384 soft carbon Inorganic materials 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- GFEQMMJEHGAWGE-UHFFFAOYSA-N 4-phenylcyclohexa-1,5-diene-1,4-diamine Chemical group C1=CC(N)=CCC1(N)C1=CC=CC=C1 GFEQMMJEHGAWGE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000006182 cathode active material Substances 0.000 claims description 4
- 150000003841 chloride salts Chemical group 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 16
- 230000001070 adhesive effect Effects 0.000 abstract description 16
- 239000006258 conductive agent Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 14
- 239000000178 monomer Substances 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 230000000379 polymerizing effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229910001290 LiPF6 Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000000748 compression moulding Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000661 sodium alginate Substances 0.000 description 3
- 235000010413 sodium alginate Nutrition 0.000 description 3
- 229940005550 sodium alginate Drugs 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000006257 cathode slurry Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002153 silicon-carbon composite material Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011868 silicon-carbon composite negative electrode material Substances 0.000 description 1
- XUGSDIOYQBRKGF-UHFFFAOYSA-N silicon;hydrochloride Chemical compound [Si].Cl XUGSDIOYQBRKGF-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a synthesis method of three-dimensional conjugated conductive polyaniline and application of the three-dimensional conjugated conductive polyaniline as a lithium ion battery cathode binder. The synthesis of the three-dimensional conjugated conductive polyaniline comprises the following contents: preparing protonic acid aqueous solution or mixed aqueous solution of a codopant and protonic acid, and dissolving aniline and a comonomer in the protonic acid aqueous solution to form solution which is marked as component A; dissolving an initiator in deionized water, and marking as a component B; slowly dripping the component B into the component A at the temperature of 0-4 ℃ in an ice bath, and continuously stirring for polymerization for 4-8 h; and then washing with ethanol and deionized water until the filtrate is neutral, and drying the filter cake to obtain the three-dimensional conjugated conductive polyaniline. The invention also provides an in-situ preparation method of the cathode material/three-dimensional conjugated conductive polyaniline composite slurry based on the method. The polyaniline prepared by the method has good bonding capability and conductivity, can be used as a conductive agent and an adhesive at the same time, and can remarkably improve the cycle stability of a lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of electrode binder materials, and particularly relates to synthesis and electrode application of a three-dimensional conjugated conductive polyaniline binder for a lithium ion battery cathode.
Background
With the development of society, lithium ion batteries are widely used in a plurality of fields such as mobile electronic equipment, electric vehicles, power grid energy storage and the like due to the advantages of high energy density, high working voltage, long cycle life and the like. However, the rapid development of new energy industry also puts higher requirements on the performance of lithium ion batteries, and the current commercialized negative electrode material is gradually transited from graphite, hard carbon and soft carbon to the development of a silicon-carbon composite negative electrode material system so as to further meet the battery performance requirements of higher specific energy and longer cycle life. The negative active material is usually matched with a conductive agent (generally one or more of carbon black, ketjen black, carbon nanotube, graphene, etc.) and a binder (generally one or more of styrene butadiene rubber latex SBR, carboxymethyl cellulose CMC, polyacrylic acid PAA, etc.) to be coated and formed by matching with electrode paste and promote electron transmission in the electrode sheet [ Journal of Power Sources,2014,257: 421-. With the gradual increase of the specific gram capacity of the negative electrode material, especially the introduction of high-gram capacity components such as silicon, a large volume expansion effect is caused in the cycle process of the negative electrode [ Advanced Energy Materials,2018,8(11):1702314 ]. The high-performance negative electrode adhesive is developed, the tolerance capability of the negative electrode sheet to large-volume deformation is improved, and the high-performance negative electrode adhesive has very important application value.
As an important part of the electrode, the properties of the binder have a crucial influence on the electrochemical performance of the electrode sheet. The traditional SBR-CMC bonding system is easy to cause rapid capacity attenuation and short cycle life when applied to a silicon cathode due to the larger brittleness and insulativity; meanwhile, the bonding system is an electronic insulator and needs to be matched with a certain content of conductive agent for use, the use of the conductive agent can reduce the energy density of the battery, and the cost is increased. Songjie et al have disclosed a polymer composite binder, which utilizes the mutual compounding of linear polymer and sheet layer polymer to establish a three-dimensional network structure around the silicon negative electrode material through hydrogen bonds, thereby buffering the volume change [ CN108428869B ]; the traditional sodium alginate binder is modified by graphene quantum dots by Zhangijia and the like, so that the traditional sodium alginate binder has higher mechanical property and elastic property, the swelling property of the traditional sodium alginate binder is enhanced, and the volume change of a negative electrode material is effectively relieved; and the graphene quantum dots have conductivity, and meanwhile, the conductivity of the binder is improved [ CN108565406B ]. In general, the adhesion or conductivity can be effectively improved by using a novel polymer composite binder or modifying a conventional binder, however, these methods have disadvantages in that: (1) most polymer composite binders have good binding capacity but show insulativity, and when the polymer composite binders are applied to lithium ion battery cathode slurry, a conductive agent needs to be additionally added; (2) the modification of the traditional adhesive can effectively improve the adhesive capacity and the electrical conductivity, but increases the preparation steps, so that the application of the traditional adhesive in the industry is limited, and the production cost is increased.
Disclosure of Invention
The invention aims to provide a synthetic method of three-dimensional conjugated conductive polyaniline and application of the three-dimensional conjugated conductive polyaniline as a lithium ion battery cathode binder aiming at the defects of the prior art, wherein the polyaniline has good bonding capability and conductivity, and further the cycle stability of a lithium ion battery is remarkably improved.
The invention provides a method for synthesizing three-dimensional conjugated conductive polyaniline, which comprises the following steps:
preparing protonic acid aqueous solution or mixed aqueous solution of a codopant and protonic acid, and dissolving aniline and a comonomer in the protonic acid aqueous solution to form solution which is marked as component A; dissolving an initiator in deionized water, and marking as a component B; slowly dripping the component B into the component A at the temperature of 0-4 ℃ in an ice bath, and continuously stirring for polymerization for 4-8 h; and then washing with ethanol and deionized water until the filtrate is neutral, and drying the filter cake to obtain the three-dimensional conjugated conductive polyaniline.
In the above method, the comonomer is at least one of m-phenylenediamine, o-phenylenediamine, 1,3, 5-triphenylanilino-benzene, 1,3, 5-triaminobenzene, and p-diaminobiphenyl. The structural formula of each comonomer is as follows:
in the above method, further, the co-dopant is a chloride salt, preferably hydrogen chloride and lithium chloride.
In the above method, the molar ratio of aniline to comonomer is 1: (0.1-3), wherein the molar ratio of aniline to protonic acid is 1: (0.05-3), wherein the molar ratio of the aniline to the codoping agent is 1: (0.05-3).
In the above method, further, the initiator is at least one of ammonium persulfate, sodium persulfate and potassium persulfate; the molar ratio of aniline to initiator is 1: (0.05-1).
In the above method, the protonic acid is at least one of hydrochloric acid, sulfuric acid and phosphoric acid.
In the method, the filter cake is further dried under vacuum at 120 ℃ for 12-24 hours.
The invention provides the three-dimensional conjugated conductive polyaniline prepared by the method. The conductive polyaniline adhesive has a three-dimensional macromolecular structure with intramolecular conjugation such as branching, crosslinking and the like, and has good adhesion and conductivity which can reach 1 x 10-6～1×10-2S/cm。
The invention also provides application of the three-dimensional conjugated conductive polyaniline binder in a lithium ion battery cathode.
In the above application, further, the negative electrode of the lithium ion battery includes a graphite negative electrode, a hard carbon negative electrode, a soft carbon negative electrode, a silicon carbon negative electrode and a silicon negative electrode.
The above use, further, is as both a conductive agent and an adhesive.
The invention provides an in-situ preparation method of a negative electrode material/three-dimensional conjugated conductive polyaniline composite slurry, which comprises the following steps:
adding a negative electrode active material, aniline and a comonomer into a protonic acid aqueous solution or a mixed aqueous solution of a co-doping agent and protonic acid, and marking as a component A, wherein the using amount of the negative electrode active material is 50-90 wt% of the total solid content of the negative electrode active material and polyaniline; dissolving an initiator in deionized water, and marking as a component B; slowly dripping the component B into the component A at the temperature of 0-4 ℃ in an ice bath, and continuously stirring for polymerization for 4-8 h; the viscosity of the slurry is regulated and controlled by controlling the concentration of the component A, so that the cathode active material/three-dimensional conjugated conductive polyaniline composite slurry is obtained.
In the above method, the comonomer is at least one of m-phenylenediamine, o-phenylenediamine, 1,3, 5-triphenylanilino-benzene, 1,3, 5-triaminobenzene, and p-diaminobiphenyl.
In the above method, further, the co-dopant is a chloride salt, preferably hydrogen chloride and lithium chloride.
In the above method, the molar ratio of aniline to comonomer is 1: (0.1-3), wherein the molar ratio of aniline to protonic acid is 1: (0.05-3), wherein the molar ratio of the aniline to the codoping agent is 1: (0.05-3).
In the above method, further, the initiator is at least one of ammonium persulfate, sodium persulfate and potassium persulfate; the molar ratio of aniline to initiator is 1: (0.05-1).
In the above method, the protonic acid is at least one of hydrochloric acid, sulfuric acid and phosphoric acid.
In the above method, the negative active material is at least one of graphite powder, hard carbon powder, soft carbon powder, silicon carbon powder, and nano silicon powder.
The invention provides a preparation method of a lithium ion battery cathode based on the three-dimensional conjugated conductive polyaniline adhesive, which comprises the steps of coating the cathode material/three-dimensional conjugated conductive polyaniline composite slurry prepared by the invention on a copper foil, carrying out vacuum drying at 120 ℃ for 12-24 h to obtain a cathode active material/three-dimensional conjugated conductive polyaniline pole piece, washing the pole piece with ethanol and water to remove residual acid and unreacted monomers, and obtaining the pole piece.
The invention provides a lithium ion battery cathode prepared by the method.
The invention has the beneficial effects that:
1. the invention adopts an in-situ chemical oxidation method as a main method to prepare the conductive polyaniline adhesive with an intramolecular conjugated three-dimensional conjugated macromolecular structure. Compared with the traditional electrode bonding system, the conductive polyaniline binder prepared by the invention has the following advantages when used as the lithium ion battery cathode binder: (1) the good adhesive property between the active substance and the current collector is effectively improved, the conductivity of the negative electrode material and the binding force between the negative electrode material and the current collector are improved, the tolerance of the negative electrode plate to volume expansion and strain is improved by the three-dimensional conjugated structure, and the pole plate pulverization and the falling-off of the active substance are inhibited; the characteristics of high capacity, long service life and high cycle stability are displayed; (2) the electrode plate can be endowed with good electronic conductivity under the condition of not using any conductive additive, and simultaneously has double roles of a conductive agent and a binder, so that the use of the conductive agent is completely avoided, and meanwhile, the active material and a current collector can form strong bonding force, the structural stability in the electrode circulation process is improved, the battery circulation life is prolonged, and the capacity retention rate is improved; (3) in the synthesis process, the composite material is compounded with the cathode active material in situ and prepared into slurry, so that the experimental steps are simplified, and the cycling stability of the cathode material is improved.
2. The material prepared by the method can be compatible and universal with the traditional pole piece manufacturing and battery assembling process equipment in the subsequent pole piece manufacturing, battery assembling and other processes, and is suitable for large-scale industrial application.
3. The method disclosed by the invention is simple to operate, high in yield and capable of realizing industrial large-scale preparation.
Drawings
Fig. 1 is a general molecular structural view of three-dimensional conjugated polyaniline;
fig. 2(a) is a charge-discharge curve of the electrode sheet formed in situ of graphite and three-dimensional conjugated conductive polyaniline in example 1; fig. 2(b) is a charge-discharge curve of the electrode sheet prepared from the three-dimensional conjugated polyaniline and the nano-silicon in example 5;
fig. 3 is an SEM image of the three-dimensional conjugated conductive polyaniline powder of example 5;
fig. 4 is a cycle characteristic diagram of the three-dimensional conjugated polyaniline/nano-silicon electrode sheet and the conventional nano-silicon electrode sheet in example 5;
FIG. 5 is a photograph of the current collectors of the three-dimensional conjugated polyaniline/nano-silicon electrode sheet (a) and the conventional CMC-CB nano-silicon electrode sheet (b) of example 5 before and after the peel strength test
Detailed Description
The present invention is further illustrated by the following specific examples. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention.
Example 1
The synthesis method of the three-dimensional conjugated conductive polyaniline for the graphite cathode comprises the following steps:
weighing 9.3g of aniline, 2.7g of p-phenylenediamine and 6.15g of 1,3, 5-triaminobenzene monomer, dissolving in 40ml of 0.5mol/L hydrochloric acid aqueous solution, magnetically stirring for 1h at the constant temperature of 4 ℃, and performing proper ultrasonic dispersion to obtain a component A; weighing 11.4g of ammonium persulfate, dissolving in 20ml of deionized water to obtain a component B, slowly adding the component B into the component A dropwise, continuing stirring and polymerizing for 4 hours after the dropwise addition is finished, finally centrifugally separating a product, washing the product with ethanol and deionized water until filtrate is neutral, and performing vacuum drying for 12 hours at 120 ℃ to obtain the three-dimensional conjugated conductive polyaniline powder. The powder is subjected to compression molding to obtain a polyaniline sheet, and the conductivity of the polyaniline sheet is 3.0 multiplied by 10 through a four-probe conductivity test-3S/cm. The structural formula of the prepared three-dimensional conjugated polyaniline is shown in figure 1, and the structural formula is characterized in that aniline structural units are mutually interwoven to form a large-ring-shaped three-dimensional conjugated molecular structure, so that the electron delocalization conjugation range is greatly improved, the formation of a high-conductivity polyaniline adhesive is promoted, and the capacity exertion of a pole piece is improved.
Preparing graphite/three-dimensional conjugated conductive polyaniline composite slurry:
weighing 9.3g of aniline, 2.7g of p-phenylenediamine and 6.15g of 1,3, 5-triaminobenzene monomer, dissolving in 40ml of 0.5mol/L hydrochloric acid aqueous solution, adding 100g of negative graphite powder, placing at the constant temperature of 4 ℃, magnetically stirring for 1 hour, and performing proper ultrasonic dispersion to obtain a component A; weighing 11.4g of ammonium persulfate, dissolving in 20ml of deionized water to obtain a component B, slowly adding the component B into the component A dropwise, continuing stirring and polymerizing for 4 hours after the dropwise addition is finished, and controlling the consistency of the slurry to obtain the graphite/three-dimensional conjugated conductive polyaniline composite slurry.
Uniformly coating the prepared graphite/three-dimensional conjugated conductive polyaniline composite slurry on a copper foil, carrying out vacuum drying for 12h in a vacuum drying oven at 120 ℃, and cutting a pole piece into pieces
After the wafer is soaked and washed by ethanol, the wafer is put into a glove box filled with argon, and the water content and the oxygen content of the wafer are less than 0.1ppm, and the wafer is taken as a working electrode, and a metal lithium sheet is taken as a counter electrode and a reference electrode to assemble a battery. The electrolyte used was EC, DEC EMC 1:1:1, 5% FEC, 1M LiPF6And Celgard 2400 is a diaphragm, and a CR2025 battery shell, a 0.5mm gasket and a 1.0mm elastic sheet are assembled into the button cell.
And (3) using a LAND battery test system to perform cycle performance test on the assembled button cell at a current density of 100mA/g, wherein the voltage window is 0.01V-2.5V. After the electrode is circulated for 50 circles under the current density of 100mA/g, the discharge specific capacity is 262mAh/g, and the capacity retention rate is 80%. The charge and discharge curve is shown in figure 2 a.
For comparison, using 9.3g of aniline and 2.325g of triphenylamine as comonomers, corresponding polyaniline and electrode sheet were prepared in the same manner as in example 1 except for the process conditions. And then, after 50 cycles of circulation are carried out under the same test condition of 100mA/g current density, the specific capacity of the graphite is 225mAh/g, and the capacity retention rate is 68%. In this comparison, the structural formula of the obtained branched polyaniline is as follows:
for comparison, the specific capacity of the graphite pole piece of the conventional CB-CMC conductive agent-binder system is 185mAh/g after 50 cycles of circulation under the same test condition, and the capacity retention rate is 58%.
As can be seen from the comparison of example 1, in the polyaniline prepared in example 1, the aniline structural unit forms a large ring-shaped three-dimensional conjugated cross-linked molecular structure, and compared with the conventional linear or branched polyaniline, the three-dimensional conjugated molecular structure not only can promote the improvement of the conductivity, but also can greatly improve the adhesive strength of the polyaniline in the electrode sheet, thereby improving the capacity exertion and the cycling stability of the negative electrode graphite.
Example 2
A method for synthesizing and applying a three-dimensional conjugated conductive polyaniline binder for a silicon cathode.
A method for synthesizing three-dimensional conjugated conductive polyaniline used for a nano silicon cathode comprises the following steps:
adding 9.12g of lithium chloride solid, 4.65g of aniline monomer and 6.15g of 1,3, 5-triaminobenzene into 50ml of hydrochloric acid aqueous solution with the concentration of 1mol/L, stirring and dissolving together, and placing the mixture at the constant temperature of 4 ℃ for magnetic stirring for 1h to dissolve completely to obtain a component A; weighing 4.56g of ammonium persulfate, dissolving in 10ml of deionized water, and obtaining a component B after the ammonium persulfate is completely dissolved; slowly adding the component B into the solution dropwise, continuing stirring and polymerizing for 4 hours after the dropwise addition is finished, finally centrifugally separating the product, washing the product with ethanol and deionized water until the filtrate is neutral, and drying the product in vacuum at 120 ℃ for 12 hours to obtain Li+Proton double-doped three-dimensional conjugated conductive polyaniline powder. The powder is subjected to compression molding to obtain a polyaniline sheet, and the conductivity of the polyaniline sheet is 3.65 multiplied by 10 through a four-probe conductivity test-4S/cm. The structure of the prepared polyaniline was similar to that of example 1.
Preparing nano silicon/three-dimensional conjugated conductive polyaniline composite slurry:
adding 15g of nano silicon powder into 25ml of 1mol/L hydrochloric acid aqueous solution, and performing ultrasonic dispersion for 1 hour; then weighing 4.56g of lithium chloride solid, 2.32g of aniline monomer and 3.1g of 1,3, 5-triaminobenzene, stirring and dissolving in the nano silicon-hydrochloric acid aqueous solution, placing the solution at the constant temperature of 4 ℃ and stirring for 1 hour by magnetic force, and performing proper ultrasonic dispersion to obtain a component A; weighing 4.56g of ammonium persulfate, dissolving in 10ml of deionized water, and obtaining a component B after the ammonium persulfate is completely dissolved; and slowly adding the component B into the component A dropwise, and continuously stirring and polymerizing for 4 hours at the constant temperature of 4 ℃ after the dropwise addition is finished to obtain the nano silicon/three-dimensional conjugated conductive polyaniline composite slurry. And uniformly coating the prepared nano silicon/three-dimensional conjugated conductive polyaniline composite slurry on a copper foil, and performing vacuum drying in a vacuum drying oven at 120 ℃ for 12 hours. Cutting the pole piece into
The wafer is soaked and washed by ethanol, and then is put into a glove box filled with argon, the water content and the oxygen content of which are less than 0.1ppm, and the glove box is used as a working electrode and a metal lithium sheet as a counter electrode and a reference electrode to assemble a battery, wherein the electrolyte is EC, DEC, EMC 1:1:1, 5% FEC, 1M LiPF6 and Celgard 2400 are used as a diaphragm, and a CR2025 battery shell, a 0.5mm gasket and a 1.0mm elastic sheet are used to assemble a button battery.
And (3) using a LAND battery test system to perform cycle performance test on the assembled button cell at a current density of 100mA/g, wherein the voltage window is 0.01V-2.5V. After the electrode is cycled for 50 circles under the current density of 100mA/g, the discharge specific capacity is 1790.4mAh/g, and the capacity retention rate is as high as 70%.
For comparison, the conventional CB-CMC conductive agent-adhesive system nano silicon pole piece is used, the discharge specific capacity is 1500mAh/g under the same test condition, and the capacity retention rate is 60%.
Example 3
The synthesis method of the three-dimensional conjugated conductive polyaniline for the nano silicon cathode comprises the following steps:
respectively weighing 0.93g of aniline, 0.31g of o-phenylenediamine and 0.2g of 1,3, 5-triphenylanilino benzene monomer, dissolving in 10ml of 0.5mol/L hydrochloric acid aqueous solution, and magnetically stirring for 1h at the constant temperature of 4 ℃ to obtain a component A; 1g of ammonium persulfate was weighed and dissolved in 20ml of deionized water to obtain a B component. And (3) dropwise adding the component B into the component A at a low speed, continuously stirring and polymerizing for 4 hours at a constant temperature of 4 ℃ after dropwise adding, finally centrifugally separating a product, washing the product with ethanol and deionized water until the filtrate is neutral, and drying for 12 hours in vacuum at 120 ℃ to obtain the three-dimensional conjugated conductive polyaniline powder. The powder is subjected to compression molding to obtain a polyaniline sheet, and the conductivity of the polyaniline sheet is 7.96 multiplied by 10 through a four-probe conductivity test-5S/cm. The structure of the prepared polyaniline was similar to that of example 1.
Preparing nano silicon/three-dimensional conjugated conductive polyaniline composite slurry:
respectively weighing 0.93g of aniline, 0.31g of o-phenylenediamine, 0.2g of 1,3, 5-triphenylamine aminobenzene monomer and 5g of nano silicon powder, stirring and ultrasonically dispersing in 10ml of hydrochloric acid aqueous solution with the concentration of 0.5mol/L, and placing the mixture in a constant temperature of 4 ℃ for magnetic stirring for 1 hour to obtain a component A; 1g of ammonium persulfate was weighed and dissolved in 20ml of deionized water to obtain a B component. And slowly adding the component B into the component A dropwise, and continuously stirring and polymerizing for 4 hours at the constant temperature of 4 ℃ after the dropwise addition is finished to obtain the nano silicon/three-dimensional conjugated conductive polyaniline composite slurry.
And uniformly coating the prepared nano silicon/three-dimensional conjugated conductive polyaniline composite slurry on a copper foil, and performing vacuum drying in a vacuum drying oven at 120 ℃ for 12 hours. Cutting the pole piece into
After the wafer is soaked and washed by ethanol, the wafer is put into a glove box filled with argon, and the water content and the oxygen content of the wafer are less than 0.1ppm, and the wafer is taken as a working electrode, and a metal lithium sheet is taken as a counter electrode and a reference electrode to assemble a battery. The electrolyte used was EC: DEC: EMC 1:1:1, 5% FEC, 1M LiPF6, Celgard 2400 was a separator, and a button cell was assembled using a CR2025 cell case, 0.5mm gaskets, and 1.0mm spring plates.
And (3) using a LAND battery test system to perform cycle performance test on the assembled button cell under the current densities of 100mA/g and 500mA/g, wherein the voltage window is 0.01V-2.5V. After the electrode is circulated for 50 circles under the current density of 100mA/g, the discharge specific capacity is 2096mAh/g, and the capacity retention rate is up to 76%. When the current density of 500mA/g is adopted for 100 cycles, the discharge specific capacity of 1169mAh/g can still be achieved.
For comparison, after the nano silicon pole piece of the conventional CB-CMC conducting agent-binder system is circulated for 50 circles under the current density of 100mA/g, the specific discharge capacity is 1220mAh/g, and the capacity retention rate is 59%. When the current density of 500mA/g is adopted for 100 cycles, the discharge specific capacity is only 1020mAh/g, and the capacity retention rate is 50%.
Example 4
The synthesis method of the three-dimensional conjugated conductive polyaniline for the silicon-carbon composite cathode comprises the following steps:
0.93g aniline monomer and 1.23g 1,3, 5-triaminobenzene monomer are weighed and dissolved in 10ml aqueous solution with the concentration of 0.5mol/L hydrochloric acid and 0.5mol/L LiCl, and the solution is placed at the constant temperature of 4 DEG CMagnetically stirring for 1h to obtain a component A; weighing 1.2g of ammonium persulfate, and dissolving in 5ml of deionized water to obtain a component B; slowly adding the component B into the component A dropwise, continuing stirring and polymerizing for 4h at the constant temperature of 4 ℃ after dropwise addition is finished, finally centrifugally separating a product, washing the product with ethanol and deionized water until the filtrate is neutral, and performing vacuum drying for 12h at 120 ℃ to obtain three-dimensional conjugated conductive polyaniline powder, wherein an SEM picture is shown in an attached figure 3. The powder is subjected to compression molding to obtain a polyaniline sheet, and the conductivity of the polyaniline sheet is 6 multiplied by 10 through a four-probe conductivity test-3S/cm. The structure of the prepared polyaniline was similar to that of example 1.
Preparing silicon carbon/three-dimensional conjugated conductive polyaniline composite slurry:
respectively weighing 0.93g of aniline, 1.23g of 1,3, 5-triaminobenzene monomer and 20g of silicon-carbon composite negative electrode powder (fibrate-SiC-1000), stirring and ultrasonically dispersing in 10ml of aqueous solution of 0.5mol/L hydrochloric acid and 0.5mol/L LiCl, and magnetically stirring for 1h at the constant temperature of 4 ℃ to obtain a component A; 1.2g of ammonium persulfate was weighed and dissolved in 5ml of deionized water to obtain component B. And slowly adding the component B into the component A dropwise, and continuously stirring and polymerizing for 4 hours at the constant temperature of 4 ℃ after the dropwise addition is finished to obtain the silicon-carbon/three-dimensional conjugated conductive polyaniline composite slurry.
Uniformly coating the prepared silicon-carbon/three-dimensional conjugated conductive polyaniline composite slurry on a copper foil, carrying out vacuum drying for 12h in a vacuum drying oven at 120 ℃, and cutting a pole piece into pieces
After the wafer is soaked and washed by ethanol, the wafer is put into a glove box filled with argon, and the water content and the oxygen content of the wafer are less than 0.1ppm, and the wafer is taken as a working electrode, and a metal lithium sheet is taken as a counter electrode and a reference electrode to assemble a battery. The electrolyte used was EC, DEC EMC 1:1:1, 5% FEC, 1M LiPF6And Celgard 2400 is a diaphragm, and a CR2025 battery shell, a 0.5mm gasket and a 1.0mm elastic sheet are assembled into the button cell.
And (3) using a LAND battery test system to perform cycle performance test on the assembled button cell at a current density of 100mA/g, wherein the voltage window is 0.01V-2.5V. After the electrode is cycled for 50 circles under the current density of 100mA/g, the discharge specific capacity is 807mAh/g, and the capacity retention rate is up to 84%.
For comparison, 0.93g of aniline and 1.23g of triphenylamine monomer were dissolved in 10ml of aqueous solution with a concentration of 0.5mol/L hydrochloric acid +0.5mol/L LiCl and copolymerized, and other technical parameters were identical to those in example 4, and the corresponding electrodes were prepared. By adopting the same test method, after the obtained electrode is circulated for 50 circles under the current density of 100mA/g, the discharge specific capacity is 461mAh/g, and the capacity retention rate is 48%. In this comparison, the structural formula of the obtained polyaniline is as follows:
for comparison, the conventional graphite pole piece of the CB-CMC conducting agent-binder system has the specific discharge capacity of 450mAh/g and the capacity retention rate of 47 percent under the same test condition.
As can be seen from the comparison of example 4, in the polyaniline prepared in example 4, the structural unit of aniline forms a large-ring-shaped three-dimensional conjugated cross-linked molecular structure, and compared with polyaniline with a branched star-shaped structure obtained by polymerizing aniline and triphenylamine, the polyaniline prepared in example 4 has significantly improved conductivity, can exert higher adhesive strength and mechanical properties in an electrode plate, and improves the capacity exertion and cycling stability of a silicon-carbon negative electrode.
Example 5
The synthesis method of the three-dimensional conjugated conductive polyaniline of the nano silicon cathode comprises the following steps:
weighing 1.86g of aniline monomer and 2.45g of 1,3, 5-triaminobenzene monomer, dissolving in 10ml of 0.2mol/L hydrochloric acid aqueous solution, and magnetically stirring for 1h at the constant temperature of 4 ℃ to obtain a component A; weighing 2.28g of ammonium persulfate, and dissolving in 5ml of deionized water to obtain a component B; slowly adding the component B into the component A dropwise, continuing stirring and polymerizing for 4h at the constant temperature of 4 ℃ after dropwise addition is finished, finally centrifugally separating a product, washing the product with ethanol and deionized water until the filtrate is neutral, and performing vacuum drying for 12h at 120 ℃ to obtain three-dimensional conjugated conductive polyaniline powder, wherein an SEM picture is shown in an attached figure 3. The powder is subjected to compression molding to obtain polymerThe aniline sheet has conductivity of 3.8 × 10 by four-probe conductivity test-3S/cm. The structure of the prepared polyaniline was similar to that of example 1. The SEM of the three-dimensional conjugated conductive polyaniline powder is shown in the figure, and the three-dimensional conjugated polyaniline powder can be seen from the figure 3, has the appearance characteristic of loose and porous, can promote the swelling and liquid retention capacity of the three-dimensional conjugated conductive polyaniline powder in electrolyte, and becomes an ideal electrode adhesive.
Preparing nano silicon/three-dimensional conjugated conductive polyaniline composite slurry:
respectively weighing 1.86g of aniline, 2.45g of 1,3, 5-triaminobenzene monomer and 20g of nano silicon powder, stirring and ultrasonically dispersing in 10ml of 0.2mol/L hydrochloric acid aqueous solution, and magnetically stirring for 1h at the constant temperature of 4 ℃ to obtain a component A; 2.28g of ammonium persulfate was weighed and dissolved in 5ml of deionized water to obtain component B. And slowly adding the component B into the component A dropwise, and continuously stirring and polymerizing for 4 hours at the constant temperature of 4 ℃ after the dropwise addition is finished to obtain the nano silicon/three-dimensional conjugated conductive polyaniline composite slurry.
Uniformly coating the prepared nano-silicon/three-dimensional conjugated conductive polyaniline composite slurry on a copper foil, carrying out vacuum drying for 12h in a vacuum drying oven at 120 ℃, and cutting a pole piece into pieces
After the wafer is soaked and washed by ethanol, the wafer is put into a glove box filled with argon, and the water content and the oxygen content of the wafer are less than 0.1ppm, and the wafer is taken as a working electrode, and a metal lithium sheet is taken as a counter electrode and a reference electrode to assemble a battery. The electrolyte used was EC, DEC EMC 1:1:1, 5% FEC, 1M LiPF6And Celgard 2400 is a diaphragm, and a CR2025 battery shell, a 0.5mm gasket and a 1.0mm elastic sheet are assembled into the button cell.
And finally, using a LAND battery test system to test the cycle performance of the assembled button battery at a current density of 100mA/g, wherein the voltage window is 0.01V-2.5V. After the electrode is cycled for 50 circles under the current density of 100mA/g, the discharge specific capacity is 2400.7mAh/g, and the capacity retention rate is 74%. The charge-discharge curve of the nano-silicon/three-dimensional conjugated conductive polyaniline composite electrode is shown in figure 2b, and the cycle characteristic diagram is shown in figure 4 (Si + PANi).
For comparison, 1.86g of aniline and 0.46g of triphenylamine were used as comonomers, and the corresponding polyaniline and electrode sheet were prepared under the same process conditions. And then the capacity of the nano silicon pole piece is 1125mAh/g after the nano silicon pole piece is circulated for 50 circles under the same test condition of 100mA/g current density, and the capacity retention rate is 34%. In this comparison, the structural formula of the obtained polyaniline is as follows:
for comparison, the specific capacity of the conventional CB-CMC nano silicon pole piece adopting a conductive agent-binder system is 685mAh/g after 50 cycles of circulation under the same test condition, and the capacity retention rate is 17%.
When the nano-silicon/three-dimensional conjugated conductive polyaniline composite electrode sheet prepared in example 5 was further subjected to a tape adhesion-tearing test, it was found that it exhibited significantly better current collector adhesion strength than the conventional CMC-CB adhesion system, as shown in fig. 5.
It can be known from the comparison of example 5 that, in the polyaniline prepared in example 5, the structural unit of aniline forms a large ring-shaped three-dimensional conjugated cross-linked molecular structure, and compared with the branched star-shaped polyaniline molecular structure obtained by polymerizing aniline and triphenylamine, the polyaniline has significant advantages in the adhesive strength and mechanical properties of the electrode sheet, and the three-dimensional conjugated conductive molecular structure can improve the capacity exertion and the cycling stability of the nano-silicon/polyaniline composite electrode.
As can be seen from fig. 1 to 4, the three-dimensional conjugated conductive polyaniline binder prepared by the invention not only can effectively improve the bonding strength between the active material and the current collector, but also can be used as a high-performance electrode conductive agent, thereby avoiding the use of a conductive agent which is difficult to disperse, and simplifying the preparation steps of the lithium ion battery cathode slurry; meanwhile, the three-dimensional conjugated conductive polyaniline binder prepared by the invention has a relatively stable molecular structure, can effectively relieve huge volume expansion of an active material in the charging and discharging processes, and the electrode plate prepared by the binder material has the characteristics of high capacity and high cycle stability in a lithium ion battery.
Claims (10)
1. A method for synthesizing three-dimensional conjugated conductive polyaniline is characterized by comprising the following steps:
preparing protonic acid aqueous solution or mixed aqueous solution of a codopant and protonic acid, dissolving aniline and a comonomer in the protonic acid aqueous solution to form solution, marking as component A, wherein the molar ratio of aniline to comonomer is 1: (0.1-3), wherein the molar ratio of aniline to protonic acid is 1: (0.05-3), wherein the molar ratio of the aniline to the codoping agent is 1: (0.05-3); dissolving an initiator in deionized water, and marking as a component B; slowly dripping the component B into the component A at the temperature of 0-4 ℃ in an ice bath, and continuously stirring for polymerization for 4-8 h; and then washing with ethanol and deionized water until the filtrate is neutral, and drying the filter cake to obtain the three-dimensional conjugated conductive polyaniline.
2. The method of claim 1, wherein the comonomer is at least one of m-phenylenediamine, o-phenylenediamine, 1,3, 5-triphenylanilinobenzene, 1,3, 5-triaminobenzene, and p-diaminobiphenyl.
3. The method of claim 1, wherein the co-dopant is a chloride salt.
4. The method of claim 1, wherein the initiator is at least one of ammonium persulfate, sodium persulfate, and potassium persulfate; the molar ratio of aniline to initiator is 1: (0.05-1).
5. The method of claim 1, wherein the protonic acid is at least one of hydrochloric acid, sulfuric acid, and phosphoric acid.
6. The three-dimensional conjugated conducting polyaniline prepared by the method of any one of claims 1 to 5.
7. The use of the three-dimensional conjugated conducting polyaniline of claim 6 as a conducting agent and binder in a negative electrode of a lithium ion battery, comprising a graphite negative electrode, a hard carbon negative electrode, a soft carbon negative electrode, a silicon carbon negative electrode, and a silicon negative electrode.
8. An in-situ preparation method of a negative electrode material/three-dimensional conjugated conductive polyaniline composite slurry is characterized by comprising the following steps:
adding a negative electrode active material, aniline and a comonomer into a protonic acid aqueous solution or a mixed aqueous solution of a co-doping agent and protonic acid, and marking as a component A, wherein the using amount of the negative electrode active material is 50-90 wt% of the total solid content of the negative electrode active material and polyaniline, and the molar ratio of the aniline to the comonomer is 1: (0.1-3), wherein the molar ratio of aniline to protonic acid is 1: (0.05-3), wherein the molar ratio of the aniline to the codoping agent is 1: (0.05-3); dissolving an initiator in deionized water, and marking as a component B; slowly dripping the component B into the component A at the temperature of 0-4 ℃ in an ice bath, and continuously stirring for polymerization for 4-8 h; the viscosity of the slurry is regulated and controlled by controlling the concentration of the component A, so that the cathode active material/three-dimensional conjugated conductive polyaniline composite slurry is obtained.
9. The method of claim 8, wherein the comonomer is at least one of m-phenylenediamine, o-phenylenediamine, 1,3, 5-triphenylanilinobenzene, 1,3, 5-triaminobenzene, and p-diaminobiphenyl; the negative active material is at least one of graphite powder, hard carbon powder, soft carbon powder, silicon carbon powder and nano silicon powder; the codopant is a chloride salt; the initiator is at least one of ammonium persulfate, sodium persulfate and potassium persulfate; the protonic acid is at least one of hydrochloric acid, sulfuric acid and phosphoric acid.
10. A lithium ion battery cathode is characterized in that the cathode material/three-dimensional conjugated conductive polyaniline composite slurry prepared by the method of claim 8 or 9 is coated on a copper foil, dried in vacuum at 120 ℃ for 12-24 hours, and washed by ethanol and water to obtain the lithium ion battery cathode.
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| CN117050689A (en) * | 2023-07-28 | 2023-11-14 | 江苏理工学院 | Preparation method and application of conductive polymer adhesive |
| CN117050689B (en) * | 2023-07-28 | 2024-03-19 | 江苏理工学院 | Preparation method and application of conductive polymer adhesive |
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