CN110767469A - Polymer mixture for organic electrode material, preparation method and application thereof - Google Patents
Polymer mixture for organic electrode material, preparation method and application thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 42
- 229920002959 polymer blend Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims description 18
- -1 polycyclic aromatic compound Chemical class 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 13
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical group [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 3
- BFIWQSSAMKDRRZ-UHFFFAOYSA-N 2,4-bis(4-phenoxyphenyl)-2,4-bis(sulfanylidene)-1,3,2$l^{5},4$l^{5}-dithiadiphosphetane Chemical compound S1P(=S)(C=2C=CC(OC=3C=CC=CC=3)=CC=2)SP1(=S)C(C=C1)=CC=C1OC1=CC=CC=C1 BFIWQSSAMKDRRZ-UHFFFAOYSA-N 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 15
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 229920000547 conjugated polymer Polymers 0.000 abstract description 3
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 description 20
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 12
- 239000011888 foil Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 229910013872 LiPF Inorganic materials 0.000 description 6
- 101150058243 Lipf gene Proteins 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 208000031509 superficial epidermolytic ichthyosis Diseases 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- AFSDNFLWKVMVRB-UHFFFAOYSA-N Ellagic acid Chemical compound OC1=C(O)C(OC2=O)=C3C4=C2C=C(O)C(O)=C4OC(=O)C3=C1 AFSDNFLWKVMVRB-UHFFFAOYSA-N 0.000 description 1
- ATJXMQHAMYVHRX-CPCISQLKSA-N Ellagic acid Natural products OC1=C(O)[C@H]2OC(=O)c3cc(O)c(O)c4OC(=O)C(=C1)[C@H]2c34 ATJXMQHAMYVHRX-CPCISQLKSA-N 0.000 description 1
- 229920002079 Ellagic acid Polymers 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229960002852 ellagic acid Drugs 0.000 description 1
- 235000004132 ellagic acid Nutrition 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FAARLWTXUUQFSN-UHFFFAOYSA-N methylellagic acid Natural products O1C(=O)C2=CC(O)=C(O)C3=C2C2=C1C(OC)=C(O)C=C2C(=O)O3 FAARLWTXUUQFSN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- H01M10/24—Alkaline accumulators
-
- 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
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The application provides a polymer mixture of an organic electrode material, the polymer is a conjugated polymer polymerized by double bonds, compared with a polymer polymerized by single bonds, the polymer has narrower energy gap and higher conductivity, and the solubility can be effectively reduced by a conjugated system polymerized by double bonds, so that the polymer is insoluble in most organic solvents and can stably exist in electrolyte. In addition, the application also provides a preparation method and application of the polymer mixture.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a polymer mixture for an organic electrode material, a preparation method and application thereof.
Background
The battery is used as an energy source, can provide stable voltage and stable current and stably supply power for a long time, has simple structure, convenient carrying, simple and easy charging and discharging, is not influenced by external climate and temperature, has stable and reliable performance, and plays a great role in various aspects of modern social life. In order to meet the demand of the power tool, a battery system having a higher energy density, a discharge performance of a large current, a good cycle performance, and a long life is becoming a trend. The battery comprises electrolyte, diaphragm material, binder and anode and cathode materials, the performance of the materials can affect the performance of the battery, especially the performance of the anode and cathode materials has great influence on the performance of the battery, and the cost directly determines the cost of the battery.
Organic compound raw materials are widely used in various industries because of their wide variety, low price and easy availability. Among them, some organic compounds having conductive properties, especially small molecules or high molecular compounds containing sulfur, radicals, carbonyl groups, nitrogen, are increasingly used in alkali metal batteries and supercapacitors. Pyrimidines, imides, graphenes, and conductive polymers have all been demonstrated to be excellent positive or negative electrode materials.
However, the current application of organic compounds as electrode materials in chargeable and dischargeable batteries and capacitors has the following problems: (1) most of organic micromolecules have good solubility and can be slowly dissolved in electrolyte, so that the battery has poor cycle capacity; (2) most organic small molecules and macromolecules have low conductivity, and the conductivity needs to be improved by doping with other compounds to change the structure of the molecules, but the stability of the doped compounds is reduced, so that the service life of the battery is greatly reduced; (3) when organic molecules are used as electrodes, a large amount of conductive graphite or other conductors are required to be matched and combined with a binder, so that the organic molecules are used as electrodes in batteries with low efficiency.
Therefore, it is important to develop an organic compound which has high conductivity without doping, low solubility, and can be stably present in an electrolyte for a long time, and to produce an energy storage device having a long lifetime, a high cycle number, and a large capacity.
Disclosure of Invention
Based on this, there is a need to provide a polymer mixture for an organic electrode material having high conductivity, low solubility, insolubility in most organic solvents, and stability in an electrolyte.
A polymer mixture for an organic electrode material, the polymer comprising structural units according to formula (I):
wherein,represents a connecting bond to an adjacent structural unit;represents a residue of a conjugated polycyclic aromatic compound attached to the linkage; m is an integer of 2 or more.
In one embodiment, the polymer further comprises a terminal structural unit represented by formula (II):
wherein, Y is each independently O or S; m1+ m2 ═ m, and m1 and m2 are integers.
In one embodiment, the conjugated polycyclic aromatic compound residue is one of the following structures:
wherein R is1、R4、R5Each independently selected from alkyl, alkyl containing hetero atom or aryl with substituent;
R2、R3each independently selected from N, O, S or C, and R2And R3Connected to form a five-membered ring or a six-membered ring;
X1each independently N, P, B or CH;
X2each independently is N or CH.
In addition, the application also provides a preparation method of the polymer mixture for the organic electrode material, and the specific scheme is as follows:
a method for preparing a polymer mixture for an organic electrode material, comprising the steps of:
mixing a conjugated polycyclic aromatic compound containing more than two carbonyl groups with an oxygen-sulfur exchange reagent, heating and refluxing in a high-boiling point solvent for reaction, and separating and purifying after the reaction is finished to obtain a polymer mixture for the organic electrode material, wherein the polymer comprises a structural unit shown as a formula (I):
wherein,represents a connecting bond to an adjacent structural unit;represents a residue of a conjugated polycyclic aromatic compound attached to the linkage; m is an integer of 2 or more.
In one embodiment, the polymer further comprises a terminal structural unit represented by formula (II):
wherein, Y is each independently O or S; m1+ m2 ═ m, and m1 and m2 are integers.
In one embodiment, the conjugated polycyclic aromatic compound containing two or more carbonyl groups is selected from one of the following compounds:
wherein R is1、R4、R5Each independently selected from alkyl, alkyl containing hetero atom or aryl with substituent;
R2、R3each independently selected from N, O, S or C, and R2And R3Connected to form a five-membered ring or a six-membered ring;
X1each independently N, P, B or CH;
X2each independently is N or CH.
In one embodiment, the oxygen-sulfur exchange reagent is one or more of lawson's reagent, Davy's reagent, japan's reagent, Belleau's reagent, tetraphosphorus decasulfide, a mixture of hydrogen sulfide and hydrogen chloride, or other polysulfide-containing compounds.
In one embodiment, the high boiling point solvent is a solvent having a boiling point above 160 ℃.
In one embodiment, the high boiling point solvent is one or more of trichlorobenzene, trimethylbenzene, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, dimethylacetamide, N-dimethylpropyleneurea, 1, 3-dimethyl-2-imidazolidinone, quinoline, or diphenyl ether.
In addition, the application also provides an application of the polymer mixture for the organic electrode material in an alkali metal battery or a super capacitor, and the specific scheme is as follows:
use of the polymer mixture for organic electrode material described in any of the above or the polymer mixture for organic electrode material prepared by the preparation method described in any of the above in an alkali metal battery or a supercapacitor.
The polymer mixture for the organic electrode material is a conjugated polymer polymerized by double bonds, has a narrower energy gap and higher conductivity compared with a polymer polymerized by single bonds, can effectively reduce the solubility through a conjugated system polymerized by double bonds, is insoluble in most organic solvents, can stably exist in an electrolyte, is applied to an alkali metal battery or a super capacitor as the organic electrode material, and has excellent cyclic charge and discharge stability.
In addition, the polymer for the organic electrode material is mixed, and the conjugated polycyclic aromatic compound containing more than two carbonyl groups and the oxygen-sulfur exchange reagent are heated and reacted in a high-boiling-point solvent, so that the preparation method is simple and efficient, and has a relatively high application prospect in the field of electrode materials of super capacitors behind alkali metal batteries.
Drawings
FIG. 1 is an SEM image of polymer mixture nanoparticles prepared in example 1 at low magnification;
FIG. 2 is an SEM image of polymer mixture nanoparticles prepared in example 1 at high magnification;
FIG. 3 shows the scanning rate of 0.1mV for the lithium-ion button cell prepared in application example 1-1Cyclic voltammogram;
FIG. 4 shows the current density of 1000mAg for the lithium-ion button cell prepared in application example 1-1Long cycle performance in time;
FIG. 5 shows the scan rate of 0.1mV for the button cell prepared in application example 2-1Cyclic voltammogram;
FIG. 6 shows the current density of 500mAg for the button cell prepared in application example 2-1Long cycle performance in time;
fig. 7 is a first three-cycle discharge voltage curve of the positive electrode of the lithium-sulfur battery prepared in application example 3 at 0.1C;
fig. 8 is a cycle performance curve of the lithium sulfur battery prepared in application example 3.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In this application, "+" denotes a connection site.
An embodiment of a polymer mixture for an organic electrode material includes a structural unit represented by formula (I):
wherein,represents a connecting bond to an adjacent structural unit;represents a residue of a conjugated polycyclic aromatic compound linked to a linking bond; m is an integer of 2 or more.
Further, the polymer also comprises a terminal structural unit shown as a formula (II):
wherein, Y is each independently O or S; m1+ m2 ═ m, and m1, m2 are integers;andthe definition of (A) is as above.
Further, the conjugated polycyclic aromatic compound residue is one of the following structures:
wherein R is1、R4、R5Each independently selected from alkyl (linear or branched), alkyl containing hetero atom group (such as carbonyl, sulfhydryl, amino, amido, imido, siloxy, halogen, oxy, etc.), or substituted aromatic group (such as benzene, naphthalene, thiophene, furan, pyrrole, pyridine, etc.);
R2、R3each independently selected from N, O, S or C, and R2And R3Connected to form a five-membered ring or a six-membered ring;
X1each independently N, P, B or CH;
X2each independently is N or CH.
Further, the polymer comprises one of the following structural units:
The polymer mixture for the organic electrode material is a conjugated polymer polymerized by double bonds, has a narrower energy gap and higher conductivity compared with a polymer polymerized by single bonds, can effectively reduce the solubility through a conjugated system polymerized by double bonds, is insoluble in most organic solvents, can stably exist in an electrolyte, is applied to an alkali metal battery or a super capacitor as the organic electrode material, and has excellent cyclic charge and discharge stability and higher specific capacity.
The method for preparing the polymer mixture for an organic electrode material according to an embodiment includes the steps of:
mixing a conjugated polycyclic aromatic compound containing more than two carbonyl groups with an oxygen-sulfur exchange reagent, heating and refluxing in a high-boiling point solvent for reaction, and separating and purifying after the reaction is finished to obtain the polymer mixture for the organic electrode material.
Among them, the conjugated polycyclic aromatic compound containing two or more carbonyl groups can be represented as follows:
Further, the conjugated polycyclic aromatic compound containing two or more carbonyl groups is selected from one of the following compounds:
R1、R4、R5、R2、R3、X1and X2The definition of (A) is as above.
Further, the oxygen sulfur exchange reagent is selected from one or more of lawson's reagent, Davy's reagent, japan's reagent, Belleau's reagent, tetraphosphorus decasulfide, a mixture of hydrogen sulfide and hydrogen chloride, and other polysulfide-containing compounds.
Further, the high boiling point solvent is a solvent having a boiling point of 160 ℃ or higher. Further, the high boiling point solvent is selected from one or more of trichlorobenzene, trimethylbenzene, dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), Dimethylacetamide (DMAC), N-Dimethylpropyleneurea (DMPU), 1, 3-dimethyl-2-imidazolidinone (DMI), quinoline, and diphenyl ether.
Further, the separation and purification method comprises the following steps: cooling, filtering, washing and drying.
The preparation method of the polymer mixture for the organic electrode material is obtained by heating and reacting the conjugated polycyclic aromatic compound containing more than two carbonyl groups and the oxygen-sulfur exchange reagent in a high-boiling-point solvent, is simple and efficient, has low cost, and has a relatively high application prospect in the field of electrode materials of super capacitors after alkali metal batteries.
The following are specific examples.
The polymer mixtures for organic electrode materials of all examples were prepared according to the following method, in particular:
as shown in table 1, a conjugated polycyclic aromatic compound containing two or more carbonyl groups, an oxygen-sulfur exchange reagent, and a high boiling point solvent were mixed, heated, refluxed, and stirred until the reaction solution turned black, and cooled, filtered, washed, and dried to obtain a polymer mixture nanoparticle electrode material.
TABLE 1
Application example 1
Pasting 70 wt.% of the polymer mixture nanoparticles prepared in example 1 (SEM images of the polymer mixture nanoparticles are shown in fig. 1 and 2), 20 wt.% of super P and 10 wt.% of PVDF as a battery negative electrode on a Cu foil; using lithium foil as the counter electrode and 1M LiPF as the electrolyte6Ethylene Carbonate (EC)/diethyl carbonate (DEC) (1/1, w/w).
The lithium ion button cell prepared in example 1 was tested, and the results show that: at 100mAg-1The discharge and charge capacities of the lithium-ion button cell prepared in application example 1 are 503mAhg respectively at low current density-1And 494mAhg-1It is shown that the electrode material prepared in example 1 has a high specific capacity, which is higher than that of a commercial graphite anode (372 mAhg)-1) Higher than 50%, even higher than previously reported organic anodes (e.g. ellagic acid 450 mAhg)-1The poly-p-phenylene group is 400mAhg-1)。
In FIG. 3, at 2.23/1.50V and 1.06/0.70V vs. Li/Li+There are two pairs of reversible redox peaks in between. Further, the intensity of the redox peak obtained at 1.06V/0.70V was about four times the intensity of the peak obtained at 2.23V/1.50V. The cycling performance of the nanoparticle negative electrode is shown in fig. 4. Capacity of about 370mAhg after 600 long cycles-1The capacity fade is negligible. Due to early SEI formation and irreversible capacity loss, charge-discharge coulombic efficiency increased from 65% to over 99% over the initial 20 cycles, and then remained fairly stable over subsequent cycles. Unlike other small organic molecules that are easily dissolved in the electrolyte during charge/discharge, the nanoparticles swell only in the non-aqueous electrolyte during charge/discharge and remain adhered to the negative electrode sheet after a long cycle life, so that excellent cycle performance is facilitated.
Application example 2
The polymer mixture nanoparticles prepared in example 1 were used as a negative electrode material for assembling 2032 cells. The 2032 cell was assembled using sodium foil as the counter electrode and 1M NaPF6/EC-DMC as the electrolyte. After 500 cycles of long life, the capacity is from the initial 250mAhg-1Slightly decaying to a final 200mAh g-1The capacity retention rate is 80% or more. In the first 20 cycles, the coulombic efficiency was approaching 100%. These results confirm that the above-mentioned negative electrode also has a better cycle stability performance for sodium ion storage.
The CV curve of the nanoparticles is shown in fig. 5. In the CV curveAt 1.87/1.75V and 0.69/0.31V (vs. Na/Na)+) There are two pairs of reversible redox peaks. Much like the lithium ion/delithiation results in fig. 3, these two pairs of reversible redox reactions are due to the sodium association/dissociation process that occurs at the carbonyl oxygen on the end group and the unsaturated nitrogen of the aromatic ring, respectively. The potential at these peak positions is lower than-0.30V in FIG. 3 because of Na/Na+Potential ratio of Li/Li+0.30V higher. FIG. 6 shows the cycling performance of sodium ion storage at a current density of 500mAg-1 (1.6C). After 500 cycles of long life, the capacity was slightly attenuated from the initial 250mAhg-1 to the final 200 mAhg g-1, with capacity retention above 80%. The first coulombic efficiency was 43%, and the lithium ion/delithiation rate was 65%. This finding indicates a higher initial capacity loss due to SEI formation and side reactions of the sodium metal foil. In the first 20 cycles, the coulombic efficiency was approaching 100%. These results confirm that the negative electrode also has better cycling stability for sodium ion storage.
Application example 3
The polymer mixture nanoparticles prepared in example 1 were used as a positive electrode material for assembling a lithium sulfur battery.
Wherein, fig. 7 is a first three-turn charge-discharge voltage curve of the battery at room temperature and 0.1C. The specific discharge capacity of the battery under different multiplying powers is respectively 910mAh/g, 580mAh/g, 450mAh/g, 400mAh/g and 380mAh/g, and the coulombic efficiency is about 90%.
As can be seen in FIG. 8, the specific discharge capacity of the battery at 0.5C in the first cycle is 800mAh/g, and the capacity is maintained at about 420mAh/g after 80 cycles of cycling. Meanwhile, the coulombic efficiency of the battery is maintained to be about 92%. Multiplying power graphs of the lithium-sulfur batteries at 0.1C, 0.5C, 1C, 2C and 5C respectively.
Application example 4
Pasting 70 wt.% of the polymer mixture nanoparticles prepared in example 4, 20 wt.% of conductive carbon black and 10 wt.% of PVDF as a battery negative electrode on a Cu foil; using lithium foil as the counter electrode and 1M LiPF as the electrolyte6Ethylene Carbonate (EC)/diethyl carbonate (DEC) (1/1, w/w).
Corresponding to the lithium ion button cell prepared in example 4And (3) performing a test, and displaying the result: at 100mAg-1The discharge capacity and the charge capacity of the lithium-ion button cell prepared in application example 4 are 663mAhg respectively under low current density-1And 634mAhg-1It is shown that the electrode material prepared in example 4 has a high specific capacity, which is higher than that of a commercial graphite anode (372 mAhg)-1) Higher by 70%. The cycle performance test of the nano-particle cathode shows excellent cycle performance.
Application example 5
Pasting 80 wt.% of the polymer mixture nanoparticles prepared in example 6, 10 wt.% of conductive carbon black and 10 wt.% of PVDF as a battery negative electrode on a Cu foil; using lithium foil as the counter electrode and 1M LiPF as the electrolyte6Ethylene Carbonate (EC)/diethyl carbonate (DEC) (1/1, w/w).
The lithium ion button cell prepared in the example 5 was tested, and the results show that: at 100mAg-1The discharge and charge capacities of the lithium-ion button cell prepared in application example 5 are 522mAhg respectively at low current density-1And 522mAhg-1It is shown that the electrode material prepared in example 6 has a high specific capacity. The cycle performance test of the nano-particle cathode shows excellent cycle performance.
Application example 6
Pasting 70 wt.% of the polymer mixture nanoparticles prepared in example 2, 20 wt.% of conductive carbon black and 10 wt.% of PVDF as a battery negative electrode on a Cu foil; using lithium foil as the counter electrode and 1M LiPF as the electrolyte6Ethylene Carbonate (EC)/diethyl carbonate (DEC) (1/1, w/w).
The lithium ion button cell prepared in example 6 was tested, and the results show that the electrode material prepared in example 2 has high specific capacity. The cycle performance test of the nano-particle cathode shows excellent cycle performance.
Application example 7
Pasting 80 wt.% of the polymer mixture nanoparticles prepared in example 3, 10 wt.% of conductive carbon black and 10 wt.% of PVDF as a battery negative electrode on a Cu foil; using lithium foil as the counter electrode and 1M LiPF as the electrolyte6Ethylene Carbonate (EC)/diethyl carbonate (DEC) (1/1, w/w).
The lithium ion button cell prepared in example 7 was tested, and the results show that the electrode material prepared in example 3 has high specific capacity. The cycle performance test of the nano-particle cathode shows excellent cycle performance.
Application example 8
Pasting 70 wt.% of the polymer mixture nanoparticles prepared in example 5, 20 wt.% of conductive carbon black and 10 wt.% of PVDF as a battery negative electrode on a Cu foil; using lithium foil as the counter electrode and 1M LiPF as the electrolyte6Ethylene Carbonate (EC)/diethyl carbonate (DEC) (1/1, w/w).
The lithium ion button cell prepared in example 8 was tested, and the results show that the electrode material prepared in example 5 has high specific capacity. The cycle performance test of the nano-particle cathode shows excellent cycle performance.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A polymer mixture for an organic electrode material, wherein the polymer comprises structural units according to formula (I):
3. The polymer mixture for organic electrode material according to claim 1 or 2, wherein the conjugated polycyclic aromatic compound residue is one of the following structures:
wherein R is1、R4、R5Each independently selected from alkyl, alkyl containing hetero atom or aryl with substituent;
R2、R3each independently selected from N, O, S or C, and R2And R3Connected to form a five-membered ring or a six-membered ring;
X1each independently N, P, B or CH;
X2each independently is N or CH.
4. A method for preparing a polymer mixture for an organic electrode material, comprising the steps of:
mixing a conjugated polycyclic aromatic compound containing more than two carbonyl groups with an oxygen-sulfur exchange reagent, heating and refluxing in a high-boiling point solvent for reaction, and separating and purifying after the reaction is finished to obtain a polymer mixture for the organic electrode material, wherein the polymer comprises a structural unit shown as a formula (I):
6. The method for preparing a polymer mixture for an organic electrode material according to claim 4, wherein the conjugated polycyclic aromatic compound having two or more carbonyl groups is selected from one of the following compounds:
wherein R is1、R4、R5Each independently selected from alkyl, alkyl containing hetero atom or aryl with substituent;
R2、R3each independently selected from N, O, S or C, and R2And R3Connected to form a five-membered ring or a six-membered ring;
X1each independently N, P, B or CH;
X2each independently is N or CH.
7. The method of claim 4, wherein the oxygen-sulfur exchange reagent is selected from one or more of Lawson's reagent, Davy reagent, Japan reagent, Belleau's reagent, tetraphosphorus decasulfide, a mixture of hydrogen sulfide and hydrogen chloride, and other polysulfide-containing compounds.
8. The method for preparing a polymer mixture for an organic electrode material according to claim 4, wherein the high-boiling solvent is a solvent having a boiling point of 160 ℃ or higher.
9. The method of claim 8, wherein the high boiling point solvent is selected from one or more of trichlorobenzene, trimethylbenzene, dimethylsulfoxide, N-methylpyrrolidone, N-dimethylformamide, dimethylacetamide, N-dimethylpropylurea, 1, 3-dimethyl-2-imidazolidinone, quinoline, and diphenyl ether.
10. Use of the polymer mixture for organic electrode material according to any one of claims 1 to 3 or the polymer mixture for organic electrode material prepared by the preparation method according to any one of claims 4 to 9 in an alkali metal battery or a supercapacitor.
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