CN112500563B - Synthesis method of three-dimensional conjugated conductive polyaniline and application of three-dimensional conjugated conductive polyaniline as negative electrode binder of lithium ion battery - Google Patents
Synthesis method of three-dimensional conjugated conductive polyaniline and application of three-dimensional conjugated conductive polyaniline as negative electrode binder of lithium ion battery Download PDFInfo
- Publication number
- CN112500563B CN112500563B CN202011271619.8A CN202011271619A CN112500563B CN 112500563 B CN112500563 B CN 112500563B CN 202011271619 A CN202011271619 A CN 202011271619A CN 112500563 B CN112500563 B CN 112500563B
- Authority
- CN
- China
- Prior art keywords
- conjugated conductive
- negative electrode
- component
- dimensional conjugated
- conductive polyaniline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 101
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- 239000011883 electrode binding agent Substances 0.000 title abstract description 5
- 238000001308 synthesis method Methods 0.000 title description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 31
- 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 28
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000002002 slurry Substances 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 17
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000002019 doping agent Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000007773 negative electrode material Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 15
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 5
- 230000001276 controlling effect Effects 0.000 claims description 4
- 229910021385 hard carbon Inorganic materials 0.000 claims description 4
- 229910021384 soft carbon Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 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 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
- 239000011863 silicon-based powder Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 13
- 230000001070 adhesive effect Effects 0.000 abstract description 13
- 238000005406 washing Methods 0.000 abstract description 12
- 239000006258 conductive agent Substances 0.000 abstract description 10
- 239000000706 filtrate Substances 0.000 abstract description 8
- 230000007935 neutral effect Effects 0.000 abstract description 7
- 239000010406 cathode material Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000012065 filter cake Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 29
- 239000011230 binding agent Substances 0.000 description 22
- 238000001291 vacuum drying Methods 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 15
- 239000000178 monomer Substances 0.000 description 14
- 229910002804 graphite Inorganic materials 0.000 description 11
- 239000010439 graphite Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 229920002134 Carboxymethyl cellulose Polymers 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000011149 active material Substances 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
- 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
- 230000008569 process Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 238000002791 soaking Methods 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
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 230000021615 conjugation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 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
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 150000003841 chloride salts Chemical group 0.000 description 2
- 238000013329 compounding Methods 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
- 239000002153 silicon-carbon composite material Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 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 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 230000009286 beneficial effect 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
- 239000006257 cathode slurry Substances 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007789 gas Substances 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
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000006116 polymerization reaction 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
- 238000004513 sizing Methods 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 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
- 238000010998 test method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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 method for synthesizing three-dimensional conjugated conductive polyaniline and application of the three-dimensional conjugated conductive polyaniline as a negative electrode binder of a lithium ion battery. The synthesis of the three-dimensional conjugated conductive polyaniline comprises the following steps: preparing protonic acid aqueous solution or mixed aqueous solution of co-doping agent and protonic acid, dissolving aniline and comonomer in protonic acid solution to form solution, and marking as A component; dissolving an initiator in deionized water, and marking the solution as a component B; slowly dripping the component B into the component A at the temperature of 0-4 ℃ in ice bath, and continuing stirring and polymerizing for 4-8 hours; 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 invention has good adhesion capability and conductivity, can be used as a conductive agent and an adhesive at the same time, and can obviously improve the cycle stability of the 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
Along with the development of society, lithium ion batteries are widely applied to various fields such as mobile electronic equipment, electric automobiles, 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 demands on the performance of lithium ion batteries, and the current commercialized negative electrode materials have gradually changed from graphite, hard carbon and soft carbon to silicon-carbon composite negative electrode material systems, so as to further meet the battery performance demands of higher specific energy and longer cycle life. The above-mentioned negative electrode active material often needs to be matched with a conductive agent (typically one or more of carbon black, ketjen black, carbon nanotubes, graphene, etc.) and a binder (typically one or more of styrene-butadiene rubber latex SBR, carboxymethyl cellulose CMC, polyacrylic acid PAA, etc.) to be coated and molded in cooperation with an electrode paste, and to promote electron transport in a pole piece [ Journal of Power Sources,2014,257:421-443]. With the gradual increase of gram specific capacity of the cathode material, particularly the introduction of high gram capacity components such as silicon, a large volume expansion effect is caused during the cathode cycle [ Advanced Energy Materials,2018,8 (11): 1702314]. The development of the high-performance negative electrode adhesive improves the tolerance of the negative electrode plate to large-volume deformation, and has very important application value.
As an important part of the electrode, the nature of the binder has a crucial impact on the electrochemical performance of the electrode sheet. The traditional SBR-CMC bonding system is easy to cause rapid capacity decay and short cycle life when being applied in a silicon negative electrode 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, and the use of the conductive agent can reduce the energy density of the battery and increase the cost. Song Jie et al discloses a polymer composite binder that utilizes linear polymers and lamellar polymers to mutually complex, and establishes a three-dimensional network structure around a silicon negative electrode material through hydrogen bonds, thereby buffering volume changes [ CN108428869B ]; zhang Lijuan et al modify the traditional sodium alginate binder with graphene quantum dots to enable the binder to have higher mechanical property and elastic property, enhance the swelling property of the binder and effectively relieve the volume change of the cathode material; and the graphene quantum dots have conductivity, and simultaneously improve the conductivity of the adhesive [ CN108565406B ]. In general, the adhesion or conductivity can be effectively improved by using a novel polymer composite adhesive or modifying a conventional adhesive, however, these methods have disadvantages: (1) Most of polymer composite binders have better binding capacity, but have insulativity, and when the polymer composite binders are applied to lithium ion battery anode slurry, conductive agents are required to be additionally added; (2) Modification of the conventional adhesive is effective in improving the adhesive capacity and conductivity, but adds preparation steps, so that the application of the adhesive in industry is limited, and the production cost is increased.
Disclosure of Invention
The invention aims to provide a synthesis method of three-dimensional conjugated conductive polyaniline and application of the polyaniline as a negative electrode binder of a lithium ion battery, aiming at the defects of the prior art, wherein the polyaniline has good binding capacity and conductivity, and further the cycle stability of the lithium ion battery is obviously 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 co-doping agent and protonic acid, dissolving aniline and comonomer in protonic acid solution to form solution, and marking as A component; dissolving an initiator in deionized water, and marking the solution as a component B; slowly dripping the component B into the component A at the temperature of 0-4 ℃ in ice bath, and continuing stirring and polymerizing for 4-8 hours; 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, further, the comonomer is at least one of m-phenylenediamine, o-phenylenediamine, 1,3, 5-triphenylamine 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, further, the molar ratio of aniline to comonomer is 1: (0.1-3), the molar ratio of aniline to protonic acid is 1: (0.05-3), the molar ratio of aniline to co-dopant is 1: (0.05-3).
In the 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, further, the protonic acid is at least one of hydrochloric acid, sulfuric acid and phosphoric acid.
In the method, further, the filter cake is 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 binder has a three-dimensional macromolecular structure with intramolecular conjugation such as branching and crosslinking, and has good cohesiveness and conductivity up to 1×10 -6 ～1×10 -2 S/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 lithium ion battery negative electrode 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 application, further, is the use of both a conductive agent and an adhesive.
The invention provides an in-situ preparation method of a cathode 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 the mixture as a component A, wherein the dosage 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 the solution as a component B; slowly dripping the component B into the component A at the temperature of 0-4 ℃ in ice bath, and continuing stirring and polymerizing for 4-8 hours; the viscosity of the slurry is regulated and controlled by controlling the concentration of the component A, and the cathode active material/three-dimensional conjugated conductive polyaniline composite slurry is obtained.
In the above method, further, the comonomer is at least one of m-phenylenediamine, o-phenylenediamine, 1,3, 5-triphenylamine 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, further, the molar ratio of aniline to comonomer is 1: (0.1-3), the molar ratio of aniline to protonic acid is 1: (0.05-3), the molar ratio of aniline to co-dopant is 1: (0.05-3).
In the 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, further, the protonic acid is at least one of hydrochloric acid, sulfuric acid and phosphoric acid.
In the above method, the negative electrode 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 a copper foil with the cathode material/three-dimensional conjugated conductive polyaniline composite slurry prepared by the preparation method, vacuum drying at 120 ℃ for 12-24 hours to obtain a cathode active material/three-dimensional conjugated conductive polyaniline pole piece, and washing the pole piece with ethanol and water to remove residual acid and unreacted monomers to obtain an electrode piece.
The invention provides the lithium ion battery cathode prepared by the method.
The beneficial effects of the invention are as follows:
1. the invention adopts an in-situ chemical oxidation method as a main method to prepare the conductive polyaniline binder with a three-dimensional conjugated macromolecular structure with intramolecular conjugation. Compared with the traditional electrode bonding system, the conductive polyaniline bonding agent prepared by the invention has the following advantages when being used as the negative electrode bonding agent of the lithium ion battery: (1) The good bonding performance between the active material and the current collector is effectively improved, the conductivity of the anode material and the bonding force between the anode material and the current collector are improved, the three-dimensional conjugated structure improves the tolerance of the anode plate to volume expansion and strain, and the chalking of the anode plate and the falling of the active material are inhibited; shows the characteristics of high capacity, long service life and high cycle stability; (2) The electrode plate can give good electronic conductivity to the electrode plate without any conductive additive, simultaneously plays a dual role of a conductive agent and a binder, completely avoids the use of the conductive agent, simultaneously can form strong binding force between an active material and a current collector, improves the structural stability in the electrode circulation process, prolongs the battery circulation life and improves the capacity retention rate; (3) In-situ compounding with negative electrode active material to prepare slurry, so as to simplify the experimental steps and raise the circulation stability of negative electrode material.
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 processes of subsequent pole piece manufacturing, battery assembling and the like, 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 industrialized large-scale preparation.
Drawings
FIG. 1 is a general molecular structure diagram of a three-dimensional conjugated polyaniline;
FIG. 2 (a) is a charge-discharge curve of an electrode sheet formed in situ from graphite and three-dimensional conjugated conductive polyaniline in example 1; FIG. 2 (b) is a charge-discharge curve of an electrode sheet prepared from three-dimensional conjugated polyaniline and nano-silicon in example 5;
FIG. 3 is an SEM image of three-dimensional conjugated conductive polyaniline powder of example 5;
FIG. 4 is a graph showing cycle characteristics 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 before and after the test of the adhesive peel strength of the current collector of the three-dimensional conjugated polyaniline/nano-silicon electrode sheet (a) and the conventional CMC-CB nano-silicon electrode sheet (b) in example 5
Detailed Description
The invention will be further illustrated with reference to specific examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art without making any inventive effort, are intended to be within the 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:
9.3g of aniline, 2.7g of p-phenylenediamine and 6.15g of 1,3, 5-triaminobenzene monomer are weighed and dissolved in 40ml of hydrochloric acid aqueous solution with the concentration of 0.5mol/L, and the mixture is placed at the constant temperature of 4 ℃ for magnetic stirring for 1 hour and properly dispersed by ultrasound to obtain a component A; weighing 11.4g of ammonium persulfate, dissolving in 20ml of deionized water to obtain a component B, dropwise adding the component B into the component A slowly, continuing stirring and polymerizing for 4 hours after the dropwise adding is finished, finally centrifugally separating a product, washing the product with ethanol and deionized water until the filtrate is neutral, and vacuum drying at 120 ℃ for 12 hours to obtain the three-dimensional conjugated conductive polyaniline powder. The powder is molded to obtain polyaniline sheet, and the conductivity of the polyaniline sheet is measured to be 3.0X10 by four-probe conductivity test -3 S/cm. The structural formula of the prepared three-dimensional conjugated polyaniline is shown in figure 1, and the three-dimensional conjugated polyaniline 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 polyaniline adhesive with high conductivity is promoted, and the capacity exertion of pole pieces is improved.
Preparation of graphite/three-dimensional conjugated conductive polyaniline composite slurry:
9.3g of aniline, 2.7g of p-phenylenediamine and 6.15g of 1,3, 5-triaminobenzene monomer are weighed and dissolved in 40ml of hydrochloric acid aqueous solution with the concentration of 0.5mol/L, 100g of negative electrode graphite powder is added, and the mixture is placed at the constant temperature of 4 ℃ for magnetic stirring for 1 hour and proper ultrasonic dispersion is carried out, so that a component A is obtained; weighing 11.4g of ammonium persulfate, dissolving in 20ml of deionized water to obtain a component B, dropwise adding the component B into the component A slowly, continuing stirring and polymerizing for 4 hours after the dropwise adding, 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 copper foil, vacuum drying at 120 ℃ for 12 hours in a vacuum drying oven, and cutting the pole piece into the finished productAfter soaking and washing with ethanol, in a glove box filled with argon, the water content and the oxygen content of which are less than 0.1ppm, the wafer is used as a working electrode, and a metal lithium sheet is used as a counter electrode and a reference electrode to assemble the battery. The electrolyte used was EC DEC emc= 1:1:1,5%FEC,1M LiPF 6 Celgard 2400 was a separator and assembled into a button cell using CR2025 battery case, 0.5mm spacer, 1.0mm shrapnel.
The assembled button cell was tested for cycle performance at a current density of 100mA/g using a LAND cell test system with a voltage window of 0.01V-2.5V. After the electrode circulates for 50 circles under the current density of 100mA/g, the specific discharge capacity is 262mAh/g, and the capacity retention rate is 80%. The charge-discharge curve is shown in figure 2 a.
By way of comparison, using 9.3g of aniline and 2.325g of triphenylamine as comonomers, the corresponding polyanilines and electrode sheets were prepared in the same manner as in example 1. After 50 cycles of the same test conditions at a current density of 100mA/g, the specific capacity of graphite was 225mAh/g, and the capacity retention was 68%. In this comparison, the structural formula of the branched polyaniline obtained is as follows:
in contrast, the graphite pole piece of the conventional CB-CMC conductive agent-binder system is used, the specific capacity after 50 circles of circulation under the same test conditions is 185mAh/g, and the capacity retention rate is 58%.
As can be seen from example 1 and comparison, the polyaniline prepared in example 1 has an aniline structural unit formed into a large-ring three-dimensional conjugated cross-linked molecular structure, and compared with conventional linear or branched polyaniline, the three-dimensional conjugated molecular structure can not only promote conductivity improvement, but also greatly improve the bonding strength of polyaniline in electrode sheets, thereby improving capacity exertion and cycling stability of negative graphite.
Example 2
The synthesis and application method of three-dimensional conjugated conductive polyaniline binder for silicon cathode.
A method for synthesizing three-dimensional conjugated conductive polyaniline which can be used for nano silicon negative electrode 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 the mixture, and magnetically stirring the mixture for 1h at the constant temperature of 4 ℃ to completely dissolve the mixture 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 4h after the dropwise addition, centrifuging, separating the product, washing with ethanol and deionized water until the filtrate is neutral, and vacuum drying at 120deg.C for 12h to obtain Li + Proton double-doped three-dimensional conjugated conductive polyaniline powder. The powder is molded to obtain polyaniline sheet, and the conductivity of the polyaniline sheet is measured to be 3.65X10 by four-probe conductivity test -4 S/cm. The structure of the polyaniline prepared was similar to that of example 1.
Preparation of 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 1h; then weighing 4.56g of lithium chloride solid, 2.32g of aniline monomer and 3.1g of 1,3, 5-triaminobenzene, stirring and dissolving the mixture in the nano silicon-hydrochloric acid aqueous solution, magnetically stirring the mixture for 1h at the constant temperature of 4 ℃ 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; 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 to obtain the nano-silicon/three-dimensional conjugated conductive polyanilineAnd (3) compounding the sizing agent. Uniformly coating the prepared nano silicon/three-dimensional conjugated conductive polyaniline composite slurry on copper foil, and vacuum drying for 12 hours at 120 ℃ in a vacuum drying oven. Cutting the pole piece into piecesAfter soaking and washing with ethanol, in a glove box filled with argon gas, the water content and the oxygen content of which are less than 0.1ppm, the wafer is used as a working electrode, a metal lithium sheet is used as a counter electrode and a reference electrode to assemble a battery, an electrolyte used is EC, EMC= 1:1:1,5%FEC,1M LiPF6,Celgard 2400 is used as a diaphragm, and a CR2025 battery shell, a 0.5mm gasket and a 1.0mm elastic sheet are used to assemble the button cell.
The assembled button cell was tested for cycle performance at a current density of 100mA/g using a LAND cell test system with a voltage window of 0.01V-2.5V. After the electrode circulates for 50 circles under the current density of 100mA/g, the specific discharge capacity is 1790.4mAh/g, and the capacity retention rate is as high as 70%.
By contrast, the nano-silicon pole piece of the conventional CB-CMC conductive agent-binder system is used, the specific discharge capacity of the nano-silicon pole piece 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 negative electrode comprises the following steps:
respectively weighing 0.93g of aniline, 0.31g of o-phenylenediamine and 0.2g of 1,3, 5-triphenylamine-based benzene monomer, dissolving in 10ml of hydrochloric acid aqueous solution with the concentration of 0.5mol/L, 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 component B. And (3) slowly adding the component B into the component A dropwise, continuing stirring and polymerizing for 4 hours at the constant temperature of 4 ℃ after the dropwise addition, finally centrifugally separating a product, washing the product with ethanol and deionized water until the filtrate is neutral, and carrying out vacuum drying at 120 ℃ for 12 hours to obtain the three-dimensional conjugated conductive polyaniline powder. The powder is molded to obtain polyaniline sheet, and the conductivity of the polyaniline sheet is measured to be 7.96 multiplied by 10 by four-probe conductivity test -5 S/cm. The structure of the polyaniline prepared was similar to that of example 1.
Preparation of 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-based benzene 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 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 component B. And (3) dropwise adding the component B into the component A at a low speed, and continuing stirring and polymerizing for 4 hours at a constant temperature of 4 ℃ after the dropwise adding 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 copper foil, and vacuum drying for 12 hours at 120 ℃ in a vacuum drying oven. Cutting the pole piece into piecesAfter soaking and washing with ethanol, in a glove box filled with argon, the water content and the oxygen content of which are less than 0.1ppm, the wafer is used as a working electrode, and a metal lithium sheet is used as a counter electrode and a reference electrode to assemble the battery. The electrolyte used was EC DEC emc= 1:1:1,5%FEC,1M LiPF6,Celgard 2400 as separator, and a button cell was assembled using CR2025 battery case, 0.5mm gasket, 1.0mm spring.
The assembled button cell was tested for cycling performance at current densities of 100mA/g and 500mA/g using a LAND cell test system with a voltage window of 0.01V-2.5V. After the electrode circulates for 50 circles under the current density of 100mA/g, the specific discharge capacity is 2096mAh/g, and the capacity retention rate is as high as 76%. After 100 circles of current density circulation of 500mA/g are adopted, the discharge specific capacity of 1169mAh/g can still be achieved.
By contrast, the specific discharge capacity was 1220mAh/g and the capacity retention was 59% after 50 cycles at a current density of 100mA/g using the nano-silicon pole piece of the conventional CB-CMC conductive agent-binder system. After 100 cycles of current density of 500mA/g, the specific discharge 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 negative electrode comprises the following steps:
weighing 0.93g of aniline monomer and 1.23g of 1,3, 5-triaminobenzene monomer, dissolving in 10ml of aqueous solution of hydrochloric acid with the concentration of 0.5mol/L and 0.5mol/L, and magnetically stirring for 1h at the constant temperature of 4 ℃ to obtain a component A; weighing 1.2g of ammonium persulfate, and dissolving in 5ml of deionized water to obtain a component B; and (3) slowly adding the component B into the component A dropwise, continuing stirring and polymerizing for 4 hours at the constant temperature of 4 ℃ after the dropwise addition, finally centrifugally separating a product, washing the product with ethanol and deionized water until the filtrate is neutral, and vacuum-drying the filtrate at 120 ℃ for 12 hours to obtain the three-dimensional conjugated conductive polyaniline powder, wherein an SEM image is shown in figure 3. The powder is molded to obtain polyaniline sheet, and the conductivity of the polyaniline sheet is measured to be 6 multiplied by 10 by four-probe conductivity test -3 S/cm. The structure of the polyaniline prepared was similar to that of example 1.
Preparation of 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 (Bei Terui SiC-1000), stirring and ultrasonically dispersing in 10ml of aqueous solution of hydrochloric acid with the concentration of 0.5mol/L and 0.5mol/L, 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 (3) dropwise adding the component B into the component A at a low speed, and continuing stirring and polymerizing for 4 hours at a constant temperature of 4 ℃ after the dropwise adding 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 copper foil, vacuum drying at 120 ℃ for 12 hours in a vacuum drying oven, and cutting the pole piece into the finished productAfter soaking and washing with ethanol, in a glove box filled with argon, the water content and the oxygen content of which are less than 0.1ppm, the wafer is used as a working electrode, and a metal lithium sheet is used as a counter electrode and a reference electrode to assemble the battery. The electrolyte used was EC DEC emc= 1:1:1,5%FEC,1M LiPF 6 Celgard 2400 was a separator and assembled into a button cell using CR2025 battery case, 0.5mm spacer, 1.0mm shrapnel.
The assembled button cell was tested for cycle performance at a current density of 100mA/g using a LAND cell test system with a voltage window of 0.01V-2.5V. After the electrode circulates for 50 circles under the current density of 100mA/g, the specific discharge capacity is 807mAh/g, and the capacity retention rate is as high as 84%.
For comparison, the corresponding electrode was prepared using 0.93g of aniline, 1.23g of triphenylamine monomer dissolved in 10ml of aqueous solution of hydrochloric acid at a concentration of 0.5 mol/L+0.5 mol/L LiCl, and the other technical parameters were kept consistent with those in this example 4. The electrode obtained after 50 cycles at a current density of 100mA/g had a specific discharge capacity of 461mAh/g and a capacity retention of 48% by the same test method. In this comparison, the structural formula of the polyaniline obtained is as follows:
in contrast, the graphite pole piece of the conventional CB-CMC conductive agent-binder system is used, and the specific discharge capacity is 450mAh/g and the capacity retention rate is 47% under the same test conditions.
As can be seen from the comparison between the example 4 and the example 4, the polyaniline prepared in the example 4 has a large-ring three-dimensional conjugated cross-linked molecular structure formed by the aniline structural unit, and compared with the polyaniline with a branched star structure obtained by polymerizing aniline and triphenylamine, the polyaniline has the advantages that the conductivity is remarkably improved, and meanwhile, the polyaniline can exert higher bonding strength and mechanical property in the electrode plate, and the capacity exertion and the cycling stability of the silicon-carbon negative electrode are improved.
Example 5
The synthesis method of the three-dimensional conjugated conductive polyaniline of the nano silicon negative electrode comprises the following steps:
1.86g of aniline monomer and 2.45g of 1,3, 5-triaminobenzene monomer are weighed and dissolved in 10ml of hydrochloric acid aqueous solution with the concentration of 0.2mol/L, and the mixture is placed at the constant temperature of 4 ℃ and magnetically stirred for 1 hour to obtain a component A; 2.28g of ammonium persulfate is weighed and dissolved in 5ml of deionized water to obtain a component B; slowly adding component B into component A dropwise, continuously stirring at 4deg.C for polymerization for 4 hr, centrifuging, separating product, adding ethanol, removing ethanol, and concentratingWashing with ionized water until the filtrate is neutral, and vacuum drying at 120deg.C for 12 hr to obtain three-dimensional conjugated conductive polyaniline powder, wherein SEM image is shown in figure 3. The powder is molded to obtain polyaniline sheet, and the conductivity of the polyaniline sheet is measured to be 3.8X10 by four-probe conductivity test -3 S/cm. The structure of the polyaniline prepared 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 has loose and porous morphology characteristics, can promote the swelling and the liquid retaining capacity of the three-dimensional conjugated conductive polyaniline powder in electrolyte, and becomes an ideal electrode adhesive.
Preparation of 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 hydrochloric acid aqueous solution with the concentration of 0.2mol/L, and magnetically stirring for 1h at the constant temperature of 4 ℃ to obtain a component A; 2.28g of ammonium persulfate was weighed out and dissolved in 5ml of deionized water to obtain component B. And (3) dropwise adding the component B into the component A at a low speed, and continuing stirring and polymerizing for 4 hours at a constant temperature of 4 ℃ after the dropwise adding 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 copper foil, vacuum drying at 120 ℃ for 12 hours in a vacuum drying oven, and cutting the pole piece into the finished productAfter soaking and washing with ethanol, in a glove box filled with argon, the water content and the oxygen content of which are less than 0.1ppm, the wafer is used as a working electrode, and a metal lithium sheet is used as a counter electrode and a reference electrode to assemble the battery. The electrolyte used was EC DEC emc= 1:1:1,5%FEC,1M LiPF 6 Celgard 2400 was a separator and assembled into a button cell using CR2025 battery case, 0.5mm spacer, 1.0mm shrapnel.
And finally, using a LAND battery test system to test the cycle performance of the assembled button cell at the 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 specific discharge 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).
By contrast, using 1.86g of aniline and 0.46g of triphenylamine as comonomers, the corresponding polyaniline and electrode sheets were prepared under otherwise identical process conditions. Then, after 50 circles of circulation under the same test condition of 100mA/g current density, the capacity of the nano-silicon pole piece is 1125mAh/g, and the capacity retention rate is 34%. In this comparison, the structural formula of the polyaniline obtained is as follows:
by contrast, the specific capacity of the nano-silicon pole piece of the conventional CB-CMC conductive agent-binder system after 50 circles of circulation under the same test conditions is 685mAh/g, 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 an adhesive tape adhesion-tear 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.
As can be seen from the comparison between the example 5 and the example 5, the polyaniline prepared in the example 5 has a large-ring three-dimensional conjugated cross-linked molecular structure formed by the aniline structural unit, and compared with the branched star-shaped polyaniline molecular structure obtained by polymerizing aniline and triphenylamine, the three-dimensional conjugated conductive molecular structure has remarkable advantages in the bonding strength and mechanical properties of pole pieces, and can improve the capacity exertion and the cycling stability of the nano silicon/polyaniline composite electrode.
As can be seen from fig. 1 to fig. 4, the three-dimensional conjugated conductive polyaniline binder prepared by the method can not only effectively improve the bonding strength between an active material and a current collector, but also serve as a high-performance electrode conductive agent, avoid the use of a conductive agent difficult to disperse, and simplify 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 generated in the charge and discharge process of an active material, 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 (2)
1. The in-situ preparation method of the negative electrode active material/three-dimensional conjugated conductive polyaniline composite slurry is characterized by comprising the following steps of:
adding a negative electrode active material, aniline and a comonomer into an aqueous solution of protonic acid or a mixed aqueous solution of a co-dopant and protonic acid, and marking as a component A, wherein the dosage 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), the molar ratio of aniline to protonic acid is 1: (0.05-3), the molar ratio of aniline to co-dopant is 1: (0.05-3); dissolving an initiator in deionized water, and marking the solution as a component B; slowly dripping the component B into the component A at the temperature of 0-4 ℃ in an ice bath, and continuing stirring and polymerizing for 4-8 h; regulating and controlling the viscosity of the slurry by controlling the concentration of the component A to obtain negative electrode active material/three-dimensional conjugated conductive polyaniline composite slurry;
the comonomer is at least one of m-phenylenediamine, o-phenylenediamine, 1,3, 5-triphenylamine benzene, 1,3, 5-triaminobenzene and p-diaminobiphenyl; the negative electrode active material is at least one of graphite powder, hard carbon powder, soft carbon powder, silicon carbon powder and nanometer silicon powder; the co-dopant is chloride; 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.
2. The negative electrode of the lithium ion battery is characterized in that the negative electrode active material/three-dimensional conjugated conductive polyaniline composite slurry prepared by the method of claim 1 is coated on copper foil, dried in vacuum at 120 ℃ for 12-24 h, and then washed by ethanol and water to obtain the negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011271619.8A CN112500563B (en) | 2020-11-13 | 2020-11-13 | Synthesis method of three-dimensional conjugated conductive polyaniline and application of three-dimensional conjugated conductive polyaniline as negative electrode binder of lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011271619.8A CN112500563B (en) | 2020-11-13 | 2020-11-13 | Synthesis method of three-dimensional conjugated conductive polyaniline and application of three-dimensional conjugated conductive polyaniline as negative electrode binder of lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112500563A CN112500563A (en) | 2021-03-16 |
| CN112500563B true CN112500563B (en) | 2023-10-31 |
Family
ID=74957679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011271619.8A Active CN112500563B (en) | 2020-11-13 | 2020-11-13 | Synthesis method of three-dimensional conjugated conductive polyaniline and application of three-dimensional conjugated conductive polyaniline as negative electrode binder of lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112500563B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114335558A (en) * | 2021-12-07 | 2022-04-12 | 西安交通大学 | Preparation method of conjugate microporous polyaniline modified battery current collector and application of conjugate microporous polyaniline modified battery current collector in lithium-sulfur battery |
| CN116154178B (en) * | 2023-04-23 | 2023-09-01 | 宁德时代新能源科技股份有限公司 | Positive electrode plate, battery cell, battery and electricity utilization device |
| CN117050689B (en) * | 2023-07-28 | 2024-03-19 | 江苏理工学院 | Preparation method and application of conductive polymer adhesive |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4740436A (en) * | 1985-07-05 | 1988-04-26 | Showa Denko Kabushiki Kaisha | Secondary battery |
| CN102432874A (en) * | 2011-07-14 | 2012-05-02 | 华东理工大学 | Preparation method of graphene loaded ordered polyaniline nanorod array electrode material |
| JP2012216450A (en) * | 2011-04-01 | 2012-11-08 | Konica Minolta Holdings Inc | Method for producing conductive composition, transparent conductive film formed using the conductive composition, and organic electroluminescent element |
| EP2631925A2 (en) * | 2012-02-27 | 2013-08-28 | Antony P Chacko | Solid electrolytic capacitor with interlayer crosslinking |
| CN105602387A (en) * | 2015-11-25 | 2016-05-25 | 扬州大学 | Preparation method and application of carbon nanotube-reinforced polyaniline electrochemically-anticorrosive composite material |
| CN108063216A (en) * | 2017-11-27 | 2018-05-22 | 浙江衡远新能源科技有限公司 | A kind of lithium battery cathode pole piece and preparation method thereof |
| CN108598442A (en) * | 2018-05-31 | 2018-09-28 | 中国科学院上海微***与信息技术研究所 | A kind of preparation method of silicon substrate lithium ion battery negative material and thus obtained silicon substrate lithium ion battery negative material |
| CN108963227A (en) * | 2018-07-19 | 2018-12-07 | 周鲁中 | Conducting polymer coated Si composite carbon nanometer tube negative electrode material and its preparation method and application |
| CN109786707A (en) * | 2019-01-18 | 2019-05-21 | 常州大学 | A kind of composite cathode material of lithium ion battery and preparation method thereof |
| JP2019140034A (en) * | 2018-02-14 | 2019-08-22 | Tdk株式会社 | Binder for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060201664A1 (en) * | 2003-04-11 | 2006-09-14 | Hayahide Yamasaki | Polyaniline compound-containing composition and process for producing the same |
| JP5583447B2 (en) * | 2010-03-26 | 2014-09-03 | 三洋電機株式会社 | Lithium secondary battery and manufacturing method thereof |
| JP6900401B2 (en) * | 2016-05-19 | 2021-07-07 | ケメット エレクトロニクス コーポレーション | Polyanionic copolymer for use with conductive polymers in solid electrolytic capacitors |
-
2020
- 2020-11-13 CN CN202011271619.8A patent/CN112500563B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4740436A (en) * | 1985-07-05 | 1988-04-26 | Showa Denko Kabushiki Kaisha | Secondary battery |
| JP2012216450A (en) * | 2011-04-01 | 2012-11-08 | Konica Minolta Holdings Inc | Method for producing conductive composition, transparent conductive film formed using the conductive composition, and organic electroluminescent element |
| CN102432874A (en) * | 2011-07-14 | 2012-05-02 | 华东理工大学 | Preparation method of graphene loaded ordered polyaniline nanorod array electrode material |
| EP2631925A2 (en) * | 2012-02-27 | 2013-08-28 | Antony P Chacko | Solid electrolytic capacitor with interlayer crosslinking |
| CN105602387A (en) * | 2015-11-25 | 2016-05-25 | 扬州大学 | Preparation method and application of carbon nanotube-reinforced polyaniline electrochemically-anticorrosive composite material |
| CN108063216A (en) * | 2017-11-27 | 2018-05-22 | 浙江衡远新能源科技有限公司 | A kind of lithium battery cathode pole piece and preparation method thereof |
| JP2019140034A (en) * | 2018-02-14 | 2019-08-22 | Tdk株式会社 | Binder for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN108598442A (en) * | 2018-05-31 | 2018-09-28 | 中国科学院上海微***与信息技术研究所 | A kind of preparation method of silicon substrate lithium ion battery negative material and thus obtained silicon substrate lithium ion battery negative material |
| CN108963227A (en) * | 2018-07-19 | 2018-12-07 | 周鲁中 | Conducting polymer coated Si composite carbon nanometer tube negative electrode material and its preparation method and application |
| CN109786707A (en) * | 2019-01-18 | 2019-05-21 | 常州大学 | A kind of composite cathode material of lithium ion battery and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| H2Ti12O25负极材料的高导电性聚合物原位包覆及其电性能研究;梁晶晶;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20190715(第7期);第B020-127页 * |
| Highly conductive copolymer sulfur composites with covalently grafted polyaniline for stable and durable lithium-sulfur batteries;Shujie Dai，等;《Electrochimica Acta》;20190812;第321卷;第134678页 * |
| Morphology of Paraphenylenediamine-Aniline Conducting Copolymers;C. MailhC-Randolph，等;《Berichte der Bunsengesellschaft für physikalische Chemie》;19890831;第93卷(第8期);第905-908页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112500563A (en) | 2021-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112500563B (en) | Synthesis method of three-dimensional conjugated conductive polyaniline and application of three-dimensional conjugated conductive polyaniline as negative electrode binder of lithium ion battery | |
| CN109103399B (en) | Functional diaphragm for lithium-sulfur battery, preparation method of functional diaphragm and application of functional diaphragm in lithium-sulfur battery | |
| CN109004220B (en) | Boric acid compound modified lithium ion battery silicon cathode and preparation method thereof | |
| CN109119592B (en) | Lithium titanate negative electrode piece, preparation method and lithium titanate battery | |
| CN112909234A (en) | Preparation method and application of lithium cathode or sodium cathode | |
| CN107026262B (en) | High-capacity spherical hard carbon negative electrode material coated with graphene on surface | |
| CN108394884A (en) | A kind of preparation method of chitosan-based high-specific surface area nitrogen/phosphor codoping carbon nanosheet | |
| JP6153124B2 (en) | Nonaqueous electrolyte secondary battery and manufacturing method thereof | |
| CN110061239B (en) | Lignin-based binder, preparation method thereof and lithium ion battery | |
| CN108899522B (en) | High-capacity silicon-carbon negative electrode material, preparation method and application | |
| CN110707288A (en) | Silicon-based negative electrode active material and preparation method and application thereof | |
| CN108400335B (en) | Binder, composition, electrode material and preparation method thereof | |
| CN114937813B (en) | Lithium ion battery and electronic equipment | |
| CN115295802A (en) | Adhesive, preparation method thereof and application thereof in lithium ion battery | |
| CN110190258B (en) | Silicon-carbon composite material water-based composite slurry, preparation method thereof and lithium ion battery | |
| CN112133916A (en) | Silicon-based negative electrode material binder of lithium ion battery and preparation method and application thereof | |
| CN109728303B (en) | Water-based conductive binder suitable for silicon-based negative electrode material of lithium ion battery and preparation method thereof | |
| CN112467086A (en) | Preparation method of silicon-based negative electrode material based on polyamide-acid-based electrode binder | |
| CN112687948A (en) | Solid-state battery with improved interface performance and preparation method thereof | |
| CN109721713B (en) | High-conductivity lithium ion battery positive electrode slurry and preparation method thereof | |
| CN114243022B (en) | Three-dimensional network water system binder for lithium ion battery, preparation and application thereof | |
| CN113629358A (en) | Composite diaphragm, preparation method thereof and lithium ion battery | |
| CN115224278B (en) | Conductive composite binder for silicon anode, preparation method and lithium ion battery | |
| CN114204125B (en) | Preparation method of integrated solid-state lithium iron phosphate battery | |
| CN116987466B (en) | Modified adhesive and preparation method thereof, negative plate, lithium ion battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| CB03 | Change of inventor or designer information |
Inventor after: Liu Wei Inventor after: He Xiaoying Inventor after: Chen Yungui Inventor after: Liu Yongxiong Inventor after: Luo Xiaofeng Inventor before: Liu Wei Inventor before: He Xiaoying Inventor before: Chen Yungui |
|
| CB03 | Change of inventor or designer information | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |