CN114409894A - Squaric acid-containing zwitterionic polymer electrode material, and preparation method and application thereof - Google Patents
Squaric acid-containing zwitterionic polymer electrode material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114409894A CN114409894A CN202111417160.2A CN202111417160A CN114409894A CN 114409894 A CN114409894 A CN 114409894A CN 202111417160 A CN202111417160 A CN 202111417160A CN 114409894 A CN114409894 A CN 114409894A
- Authority
- CN
- China
- Prior art keywords
- electrode material
- zwitterionic polymer
- lithium ion
- squaric acid
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 43
- 239000007772 electrode material Substances 0.000 title claims abstract description 40
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 239000012046 mixed solvent Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000000967 suction filtration Methods 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 32
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 12
- 239000011149 active material Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- WQOWBWVMZPPPGX-UHFFFAOYSA-N 2,6-diaminoanthracene-9,10-dione Chemical group NC1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 WQOWBWVMZPPPGX-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229940078552 o-xylene Drugs 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- JSFUMBWFPQSADC-UHFFFAOYSA-N Disperse Blue 1 Chemical compound O=C1C2=C(N)C=CC(N)=C2C(=O)C2=C1C(N)=CC=C2N JSFUMBWFPQSADC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- FBMQNRKSAWNXBT-UHFFFAOYSA-N 1,4-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=CC=C2N FBMQNRKSAWNXBT-UHFFFAOYSA-N 0.000 claims description 2
- VWBVCOPVKXNMMZ-UHFFFAOYSA-N 1,5-diaminoanthracene-9,10-dione Chemical compound O=C1C2=C(N)C=CC=C2C(=O)C2=C1C=CC=C2N VWBVCOPVKXNMMZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004156 Azodicarbonamide Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 2
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 claims 1
- 239000007773 negative electrode material Substances 0.000 abstract description 11
- 239000007774 positive electrode material Substances 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BSSNZUFKXJJCBG-UPHRSURJSA-N (z)-but-2-enediamide Chemical compound NC(=O)\C=C/C(N)=O BSSNZUFKXJJCBG-UPHRSURJSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001746 electroactive polymer Polymers 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- 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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
- H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A squaric acid-containing amphoteric ion polymer electrode material, a preparation method and application thereof belong to the technical field of organic lithium ion battery electrode materials. Under the inert condition, respectively adding a squaric acid monomer and an amino-containing monomer into a mixed solvent, and reacting under the condition of stirring and refluxing; and carrying out suction filtration on the obtained mixed solution, cleaning the obtained filter residue with an organic solvent until the filter residue is colorless and transparent, and drying the obtained solid in vacuum to obtain the target product. The invention realizes the reduction of the solubility of the material and the improvement of the cycle performance through an extended pi conjugated system, and avoids the introduction of inactive connecting groups to ensure higher capacity, thereby realizing excellent electrochemical performance. The electrode material can be used as a positive electrode active material and a negative electrode active material, has strong mobility, and can obtain excellent electrochemical performance when being used as a positive electrode active material, a negative electrode active material and an all-organic battery respectively, so that the electrode material has a very wide application prospect.
Description
Technical Field
The invention belongs to the technical field of organic lithium ion battery electrode materials, and particularly relates to a squaric acid-containing amphoteric ion polymer electrode material, a preparation method and application thereof.
Background
Over the past two decades, lithium ion batteries have enjoyed great success in the field of mobile electronic devices. However, with the rise and development of electric vehicles and large-scale energy storage devices, it is difficult for current commercial lithium ion batteries to meet the requirements of high energy density and high power density. In recent years, organic electrode materials are expected to replace traditional commercial inorganic electrode materials and gradually become research hotspots in the field of lithium ion battery electrode materials due to the advantages of high structure designability, environmental friendliness, low cost and the like. The existing organic electrode material generally has the defects of easy dissolution in organic electrolyte, low self conductivity and the like. In order to overcome the above disadvantages, development of an electrode material having excellent cycle performance, rate capability and high capacity has been a development trend in the field of organic electrode materials.
The invention constructs the electroactive polymer by utilizing an extended pi conjugated system through molecular design, thereby realizing excellent comprehensive electrochemical performance.
Disclosure of Invention
The invention aims to provide a squaric acid-containing zwitterionic polymer electrode material, a preparation method and application thereof. The invention aims to reduce the solubility of materials, improve the cycle performance and avoid introducing inactive connecting groups to ensure higher capacity through an extended pi conjugated system, thereby realizing excellent electrochemical performance. Research shows that the squaric acid-containing organic electrode material can be used as a positive electrode active material and a negative electrode active material, and can obtain excellent electrochemical properties when being used as a positive electrode active material, a negative electrode active material and an all-organic battery respectively, so that the squaric acid-containing organic electrode material has a very wide application prospect.
The structural formula of the amphoteric ion polymer electrode material containing squaric acid is shown as follows:
wherein n is a positive integer of 0<x<1；R1、R2Is one of the following structures, except that R1And R2Are not identical.
The preparation method of the squaric acid-containing zwitterionic polymer electrode material comprises the following chemical synthesis reaction:
the method comprises the following steps:
step 1: under the inert condition, respectively adding a squaric acid monomer and an amino-containing monomer into a mixed solvent containing n-hexane, and reacting for a certain time under the condition of stirring and refluxing;
step 2: and (3) cooling to room temperature after the reaction in the step (1) is finished, carrying out suction filtration on the obtained mixed solution, washing the obtained filter residue with other organic solvents until the filter residue is colorless and transparent, and drying the obtained solid in vacuum to obtain the amphoteric ion polymer electrode material containing the squaric acid.
In the step 1, the amino-containing monomer is 2, 6-diaminoanthraquinone (2,6-DAQ), 1, 4-diaminoanthraquinone (1,4-DAQ), 1, 5-diaminoanthraquinone (2,5-DAQ), DISPERSE BLUE 1(dispersE BLUE 1), Tetraaminobenzoquinone (TABQ), terephthalamide, azodicarbonamide, maleamide and the like.
In the step 1, the molar use ratio of the squaric acid monomer to the amino-containing monomer is 0.25-4: 1;
the mixed solvent containing n-hexane in the step 1 is one of mixed solvents of n-hexane and o-dichlorobenzene, n-hexane and toluene, and n-hexane and o-xylene; the volume usage ratio of n-hexane to o-dichlorobenzene, toluene or o-xylene is 0.5-5: 1;
in the mixed solvent containing n-hexane in the step 1, the concentration of the squaric acid monomer is 0.05-0.5 mol/L;
the reflux reaction time in the step 1 is 10-30 hours;
and 2, the other organic solvent is more than one of acetone, tetrahydrofuran and N, N-dimethylformamide.
The amphoteric ion polymer electrode material containing the squaric acid can be applied to lithium ion batteries as a positive electrode material or a negative electrode material and all-organic batteries (the positive electrode active material and the negative electrode active material are both composed of amphoteric ion polymers containing the squaric acid). The preparation method of the battery comprises the following steps: the method comprises the following steps of taking the amphoteric ion polymer electrode material containing the squaric acid as an active material (a positive electrode or a negative electrode), taking an Al foil or a Cu foil as a positive electrode current collector or a negative electrode current collector respectively, taking acetylene black as a conductive agent, uniformly mixing the active material, the conductive agent and a binder, coating the mixture on the current collector, and drying the mixture in a vacuum environment at the temperature of 80-120 ℃ for 8-12 hours; and cutting the obtained electrode slice into small round slices, using the small round slices as the anode or the cathode of the lithium ion battery, and assembling the lithium slice as the cathode or the anode of the lithium ion battery in a glove box to form the button battery.
The binder is one of PVDF, SBR/CMC, sodium alginate, LA132 or polyacrylic acid.
The electrolyte used by the button cell is LiPF6 in EC/DEC (volume ratio of 1: 1), LiTFSI in DOL/DME (volume ratio of 1: 1), LiPF6 in EC/DMC (volume ratio of 1: 1) or LiPF6 in EC/DEC/DMC (volume ratio of 1: 1).
The active material, the conductive agent and the binder account for 100% by mass, wherein the active material accounts for 40-80%, the conductive agent accounts for 10-50%, and the balance is the binder.
Compared with the prior art, the invention has the advantages that:
the preparation method of the squaric acid-containing zwitterionic polymer electrode material is simple, experimental raw materials are cheap and easy to obtain, the polymerization reaction yield is high, the electrode material can be used as an organic positive electrode material or a negative electrode material, an organic full battery can be assembled (the positive electrode material and the negative electrode material are the polymer electrode materials of the invention), and the electrode material has excellent electrochemical properties such as high capacity, long service life and the like, and is beneficial to large-scale application.
Drawings
FIG. 1 is an electron micrograph of a polymer according to example 1 of the present invention;
FIG. 2 is an infrared test chart of the polymer of example 1 of the present invention;
FIG. 3 is a graph of rate capability of the polymer of example 1 of the present invention;
FIG. 4 is a graph of the cycle performance at 2A/g for the polymer of example 1 of the present invention;
FIG. 5 is a cyclic voltammogram at a sweep rate of 0.2mV/S for the polymer of example 2 of the present invention;
FIG. 6 is a graph of the cycle performance at 0.1A/g for the polymer of example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings, but the scope of the present invention is not limited to the following examples.
Example 1:
under an inert condition, the squaric acid monomer and 2, 6-diaminoanthraquinone monomer (the molar weight is 3mmol) are respectively added into a mixed solvent of n-hexane and o-dichlorobenzene (the volumes are 40mL and 8mL respectively), and the reaction is carried out for 12 hours under the condition of stirring (500 revolutions per second) and refluxing.
After the reaction is finished, directly filtering the obtained mixed solution, respectively cleaning filter residues by using acetone, tetrahydrofuran and N, N-dimethylformamide to be colorless and transparent, drying the obtained solid in vacuum to obtain the target polymer, wherein the yield is 88%, the structural formula of the target product is shown in the following figure, and infrared tests prove that the polymer is successfully synthesized, and the formula is shown in the following formula.
As can be seen from FIG. 1, of PSQ1The microscopic morphology was a solid with uniform size (0.5-2 microns), and the target polymer PSQ was also demonstrated by the infrared test of FIG. 21Successful synthesis (appearance of carbonyl peaks ascribed to anthraquinone and squaric acid and appearance of N-H characteristic peaks, respectively)
Taking the polymer as a positive electrode active material, an Al foil as a positive electrode current collector, acetylene black as a conductive agent, and mixing the active material, the conductive agent and a binder (PVDF) in a ratio of 5: 4: 1, coating the mixture on a current collector, and drying the mixture in a vacuum environment at the temperature of 120 ℃ for 12 hours. The obtained electrode plate is cut into small round pieces and then is used as the anode of the lithium ion battery, the lithium piece is used as the cathode of the lithium ion battery, the electrolyte is LiTFSI in DOL/DME (volume ratio is 1: 1), and the CR2032 button battery assembled in a glove box is used for testing the performance of the half-cell.
The test shows that (figure 3), the initial capacity of the half cell corresponding to the polymer as the anode can reach 135.6mAh/g, and the polymer shows excellent rate performance after rate test, and can finally reach up to 215mAh/g reversible capacity after being continuously activated after returning to 0.05A/g. Furthermore, at a high current density of 2A/g (FIG. 4), 6000 cycles of ultra-long cycle performance can be realized, and the capacity retention rate is ultrahigh (95.1%). The above tests show the excellent performance of the polymer as a positive electrode material.
Example 2:
under an inert condition, the squaric acid monomer and 2, 6-diaminoanthraquinone monomer (the molar weight is 5mmol) are respectively added into a mixed solvent of n-hexane and o-dichlorobenzene (the volumes are 50mL and 10mL respectively), and the reaction is carried out for 12 hours under the condition of stirring (500 revolutions per second) and refluxing.
And after the reaction is finished, directly filtering the obtained mixed solution, washing filter residues by using acetone, tetrahydrofuran and N, N-dimethylformamide until the filter residues are colorless and transparent, and drying the obtained solid in vacuum to obtain the target polymer.
The polymer is used as a negative electrode active material, the Cu foil is used as a negative electrode current collector, the acetylene black is used as a conductive agent, and the active material, the conductive agent and the sodium alginate are mixed in a ratio of 5: 4: 1, and coating the mixture on a current collector, and drying the current collector in a vacuum environment at the temperature of 80 ℃ for 10 hours. And cutting the electrode slice into small round slices, and assembling the small round slices into the button cell in a glove box by taking a lithium slice as a negative electrode. The electrolyte composition is LiPF6 in EC/DEC (volume ratio 1: 1). the assembled CR2032 button cell is used for half-cell performance test.
The polymer, namely the negative electrode material, is also tested to have highly reversible electrochemical activity, and the cyclic voltammogram of the polymer has reversible redox peaks at about 1.5V and below 0.5V (figure 5). The reversible capacity of the polymer can reach 1104mAh/g under 0.1A/g, and the reversible capacity of 601.5mAh/g (shown in figure 6) can be still maintained after the polymer is stabilized through a charge-discharge test of 300 circles, so that the polymer serving as a negative electrode material has excellent electrochemical performance and a very high application prospect.
Claims (10)
1. A zwitterionic polymer electrode material containing squaric acid has a structural formula shown as follows:
wherein n is a positive integer of 0<x<1；R1、R2Is one of the following structures, except that R1And R2Is different from the prior art in that,
2. the method for preparing the squarylium acid-containing zwitterionic polymer electrode material of claim 1, comprising the steps of:
step 1: under the inert condition, respectively adding a squaric acid monomer and an amino-containing monomer into a mixed solvent containing n-hexane, and reacting for a certain time under the condition of stirring and refluxing;
step 2: and (3) cooling to room temperature after the reaction in the step (1) is finished, carrying out suction filtration on the obtained mixed solution, cleaning the obtained filter residue with other organic solvents to be colorless and transparent, and drying the obtained solid in vacuum to obtain the squaric acid-containing zwitterionic polymer electrode material.
3. The method of claim 2, wherein the method comprises the steps of: in the step 1, the amino-containing monomer is 2, 6-diaminoanthraquinone, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, disperse blue 1, tetraaminobenzoquinone, p-phenylenediamine, azodicarbonamide or maleic amide; the mixed solvent containing n-hexane is one of mixed solvents of n-hexane and o-dichlorobenzene, n-hexane and toluene, and n-hexane and o-xylene.
4. A method of preparing a squarylium acid-containing zwitterionic polymer electrode material of claim 3, wherein: the volume usage ratio of n-hexane to o-dichlorobenzene, toluene or o-xylene is 0.5-5: 1.
5. the method of claim 2, wherein the method comprises the steps of: in the step 1, the molar use ratio of the squaric acid monomer to the amino-containing monomer is 0.25-4: 1, in a mixed solvent containing n-hexane, the concentration of a squaric acid monomer is 0.05-0.5 mol/L; the reflux reaction time in the step 1 is 10-30 hours.
6. The method for preparing the squarylium-containing zwitterionic polymer electrode material as defined in claim 2, wherein: and 2, the other organic solvent is more than one of acetone, tetrahydrofuran and N, N-dimethylformamide.
7. Use of the squarylium acid-containing zwitterionic polymer electrode material of claim 1 in a lithium ion battery electrode material.
8. The use of the squarylium acid-containing zwitterionic polymer electrode material of claim 7 in a lithium ion battery electrode material, wherein: the method comprises the steps of taking a zwitterionic polymer electrode material containing squaric acid as an active material, taking an Al foil or a Cu foil as a positive electrode current collector or a negative electrode current collector respectively, taking acetylene black as a conductive agent, uniformly mixing the active material, the conductive agent and a binder, coating the mixture on the current collector, and drying the mixture in a vacuum environment at the temperature of 80-120 ℃ for 8-12 hours; cutting the obtained electrode slice into small round slices, using the electrode slices as the anode or the cathode of the lithium ion battery, using the lithium slices as the cathode or the anode of the lithium ion battery, and assembling the electrode slices into a button battery in a glove box; or cutting the obtained electrode slice into small wafers which are used as the anode and the cathode of the lithium ion battery, and assembling the lithium ion battery into the button battery in a glove box.
9. The use of the squarylium acid-containing zwitterionic polymer electrode material of claim 8 in a lithium ion battery electrode material, wherein: the binder is one of PVDF, SBR/CMC, sodium alginate, LA132 or polyacrylic acid; the electrolyte of the button cell is LiPF6 in EC/DEC, LiTFSI in DOL/DME, LiPF6 in EC/DMC or LiPF6 in EC/DEC/DMC, and the volume ratio is 1: 1.
10. the use of the squarylium acid-containing zwitterionic polymer electrode material of claim 8 in a lithium ion battery electrode material, wherein: the active material, the conductive agent and the binder account for 100% by mass, wherein the active material accounts for 40-80%, the conductive agent accounts for 10-50%, and the balance is the binder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111417160.2A CN114409894A (en) | 2021-11-26 | 2021-11-26 | Squaric acid-containing zwitterionic polymer electrode material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111417160.2A CN114409894A (en) | 2021-11-26 | 2021-11-26 | Squaric acid-containing zwitterionic polymer electrode material, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114409894A true CN114409894A (en) | 2022-04-29 |
Family
ID=81266430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111417160.2A Pending CN114409894A (en) | 2021-11-26 | 2021-11-26 | Squaric acid-containing zwitterionic polymer electrode material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114409894A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI826235B (en) * | 2023-01-13 | 2023-12-11 | 創芯科技有限公司 | Negative active material modified with double ion polymer, its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110702747A (en) * | 2019-10-28 | 2020-01-17 | 苏州大学 | Diaminoanthraquinone squaramide polymer, humidity-sensitive sensor based on squaramide polymer and preparation method of humidity-sensitive sensor |
| CN111007116A (en) * | 2020-01-06 | 2020-04-14 | 苏州大学 | Condensed ring squaramide polymer nitrogen dioxide sensor and preparation method and application thereof |
-
2021
- 2021-11-26 CN CN202111417160.2A patent/CN114409894A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110702747A (en) * | 2019-10-28 | 2020-01-17 | 苏州大学 | Diaminoanthraquinone squaramide polymer, humidity-sensitive sensor based on squaramide polymer and preparation method of humidity-sensitive sensor |
| CN111007116A (en) * | 2020-01-06 | 2020-04-14 | 苏州大学 | Condensed ring squaramide polymer nitrogen dioxide sensor and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI826235B (en) * | 2023-01-13 | 2023-12-11 | 創芯科技有限公司 | Negative active material modified with double ion polymer, its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107170965B (en) | Silicon-carbon composite material and preparation method and application thereof | |
| CN114883559B (en) | Naphthoquinone-quinoxaline organic electrode material and application thereof in water-based zinc ion battery | |
| CN110190284B (en) | Water-based binder for lithium-sulfur battery positive electrode and preparation method and application thereof | |
| CN111063884B (en) | Water-based ion battery negative electrode material, water-based ion battery negative electrode and preparation method thereof, and water-based ion battery | |
| CN104157875A (en) | Method for preparing nanometer silicon conductive polymer composite material for lithium ion batteries | |
| CN103779568A (en) | Column quinone positive pole material for lithium ion battery and application thereof | |
| CN110729456A (en) | Electrode pole piece, and preparation method and application thereof | |
| CN108461752B (en) | Triphenylamine polymer with side chain having conjugated carbonyl compound, preparation and application thereof | |
| CN111261872A (en) | Organic electrode material and preparation method and application thereof | |
| CN108623787B (en) | Novel conjugated microporous organic polymer and synthesis and application thereof | |
| CN114106327B (en) | Organic electrode material of multi-carbonyl polyimide, preparation method and application thereof | |
| CN115043970A (en) | Cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing maleimide structure, preparation method and application thereof | |
| CN109935813A (en) | A kind of preparation method and application of novel cathode material for lithium ion battery | |
| CN114409894A (en) | Squaric acid-containing zwitterionic polymer electrode material, and preparation method and application thereof | |
| CN109021231B (en) | Modified polydopamine material and application thereof | |
| CN116731635A (en) | Conductive adhesive and preparation method and application thereof | |
| CN114276357B (en) | 2,8, 14-trinitro substituted hexaazanaphthalene monomer and azo-based polymer thereof, preparation method and application | |
| CN111211327B (en) | Compound for lithium ion battery anode material and preparation method and application thereof | |
| CN109671978B (en) | High-voltage-resistant solid polymer electrolyte, preparation method and application thereof | |
| CN113248672A (en) | Schiff base polymer electrode material with increased capacity in circulation process and preparation method thereof | |
| CN107644996B (en) | Preparation method of pure organic polymer lithium ion battery electrode material | |
| CN111916690A (en) | Preparation method of silicon-carbon cathode of lithium ion battery | |
| CN112072062A (en) | Multi-carbonyl aza-condensed ring material for proton battery and preparation method of electrode thereof | |
| CN116987087B (en) | High-conjugated pyrazine fused ring compound and application thereof in lithium ion battery | |
| CN104681281A (en) | Composite electrode material having excellent rate performance and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20220429 |
|
| WD01 | Invention patent application deemed withdrawn after publication |