CN114773555A - Pre-lithiation modified Schiff base polymer electrode material and preparation method thereof - Google Patents
Pre-lithiation modified Schiff base polymer electrode material and preparation method thereof Download PDFInfo
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- 239000002262 Schiff base Substances 0.000 title claims abstract description 72
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 72
- 229920005601 base polymer Polymers 0.000 title claims abstract description 72
- 239000007772 electrode material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006138 lithiation reaction Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 14
- FEHLIYXNTWAEBQ-UHFFFAOYSA-N 4-(4-formylphenyl)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=C(C=O)C=C1 FEHLIYXNTWAEBQ-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 3
- 125000000129 anionic group Chemical group 0.000 abstract description 2
- 150000004678 hydrides Chemical class 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000002715 modification method Methods 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
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- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
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- 238000002329 infrared spectrum Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910014276 N-Li Inorganic materials 0.000 description 1
- 229910014326 N—Li Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
-
- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
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- Polymers & Plastics (AREA)
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Abstract
The invention discloses a prelithiation modified Schiff base polymer electrode material and a preparation method thereof, wherein the Schiff base polymer is modified by a chemical prelithiation method, reducing hydride LiH is used for treating active-NH-bonds in the Schiff base polymer to deprotonate-NH-sites, a neutral framework is changed into an anionic framework, and stable-N is used for preparing the Schiff base polymer electrode material‑Li+Sites to modify the product, which can be used as anode material in lithium ion batteries. The modification method provided by the invention is simple in process, environment-friendly, low in cost and easy for large-scale production, and the cycle performance of the organic electrode material is improved.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a modification method of an organic electrode material and application thereof.
Background
The organic electrode material has the potential of sustainable production and low carbon, most of which widely exist in the nature, or can be produced from natural products by using a more environment-friendly process, thereby reducing the influence on the environment. But its greatest drawback is the dissolution problem, i.e. different degrees of dissolution occur in the aprotic electrolyte, which seriously affects the cycle performance.
Furthermore, initial irreversible capacity loss is inevitable due to the formation of the Solid Electrolyte Interface (SEI), which typically results in excessive consumption of lithium ions, and a method to overcome this problem is prelithiation. Generally, in the lithium ion intercalation process, when the potential of the negative electrode is less than about 1V, the organic electrolyte undergoes a side reaction at the surface of the anode to be reduced to form SEI. Although SEI plays a key role in preventing ion intercalation into the bulk of the electrode in the electrolyte, a small fraction of lithium ions can be irreversibly fixed in the electrode, resulting in additional consumption of lithium ions and drastic changes in the electrolyte concentration. Prelithiation, which is considered to be an effective way to solve the above problems, has a positive impact on the cycle life of lithium ion batteries by building, regulating and optimizing SEI. By pre-lithiation, the problem of high-capacity irreversible lithium ion batteries can be effectively solved, and the cycle stability is improved.
There are three main techniques for prelithiation of current anode materials: the negative electrode is directly prelithiated by adding a prelithiation agent, such as a stabilized lithium metal powder and a lithium alloy compound, to the negative electrode; an electrochemical prelithiation process, based on the electrochemical reaction of an anode with lithium metal in the presence of an electrolyte, similar to the process of lithiation of an anode in a battery; the invention adopts a chemical prelithiation method, utilizes a lithiation reagent with strong reducing power to transfer active lithium to the negative electrode material through oxidation-reduction reaction, has simple and practical preparation process and better prelithiation effect.
Disclosure of Invention
Based on the problems existing in the prior art, the invention provides a prelithiation modified Schiff base polymer electrode material and a preparation method thereof, aiming at obtaining a lithium ion battery cathode material with excellent cycle performance.
In order to solve the technical problem, the invention adopts the following technical scheme:
a method for preparing a prelithiation modified Schiff base polymer electrode material is characterized by comprising the following steps: the preparation method comprises the steps of taking melamine and 4, 4' -biphenyldicarboxaldehyde as raw materials and dimethyl sulfoxide as a solvent, carrying out reflux reaction to obtain a Schiff base polymer, and carrying out heating and stirring reaction on the Schiff base polymer and lithium hydride to obtain the prelithiation modified Schiff base polymer electrode material. The method specifically comprises the following steps:
step 2, adding the mixed solution into a reflux device for reflux reaction, and performing suction filtration on the obtained reaction product to obtain a Schiff base polymer;
and 3, heating and stirring the Schiff base polymer and lithium hydride for reaction to obtain the pre-lithiation modified Schiff base polymer electrode material.
Further, the molar ratio of the melamine to the 4, 4' -biphenyldicarboxaldehyde is 1: 0.75-1.5.
Further, the reflux reaction and the heating stirring reaction are both carried out under the protection of nitrogen. .
Further, the temperature of the reflux reaction is 160-180 ℃, and the time is 12-24 hours.
Further, the washing reagents used in the suction filtration are ethanol and dichloromethane which are washed sequentially.
Further, the molar ratio of the Schiff base polymer to the lithium hydride is 1: 2-5.
Further, the heating and stirring reaction is carried out at the temperature of 80-100 ℃ for 8-12 h.
The prelithiation modified Schiff base polymer electrode material prepared by the preparation method can be used as a lithium ion battery cathode material. The invention relates to a preparation method of a pre-lithiation modified Schiff base polymer, which modifies the Schiff base polymer by a chemical pre-lithiation method and uses a reducing hydride LiH positionDeprotonating the-NH-site by activating the-NH-bond in the Schiff base polymer to convert the neutral framework to an anionic framework using the stabilized-N-Li+Sites to modify the product, which can be used as anode material in lithium ion batteries.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method provided by the invention is simple in process, environment-friendly, low in cost and suitable for large-scale production, and the modified Schiff base polymer prepared by the preparation method is excellent in electrochemical performance, so that the cycle performance of the organic electrode material when being used as a lithium ion battery cathode material is greatly improved.
2. The results of the electrochemical tests show that: the cycle performance test is carried out under the same current density, the cycle performance of the prelithiation modified Schiff base polymer is greatly improved, and the original Schiff base polymer begins to decay rapidly after being cycled for hundreds of cycles. After the pre-lithiation, the electrode supplements additional lithium ions for the solid electrolyte interface in the first cycle process, so that the consumption of lithium salt in the electrolyte is reduced, the influence of part of irreversible capacity is eliminated, and in long-term cycle, the pre-lithiation material and the electrolyte have larger polarity difference, so that the self-dissolution is favorably inhibited.
Drawings
FIG. 1 is a diagram showing the synthesis steps of a Schiff base polymer and a modified Schiff base polymer according to the present invention;
FIG. 2 is a comparison of IR spectra before and after modification of the Schiff base polymer in example 1 of the present invention;
FIG. 3 is a chemical formula of a structural unit of the modified Schiff base polymer obtained by the invention;
FIG. 4 is a scanning electron micrograph of a modified Schiff base polymer according to example 1 of the present invention;
FIG. 5 is a graph of rate capability of a modified Schiff base polymer in example 1 of the invention;
FIG. 6 is a graph showing the comparison of the cycle performance at a current density of 1A/g before and after modification of the Schiff base polymer in example 1 of the present invention;
FIG. 7 is a cyclic voltammogram of the modified Schiff base polymer of example 2 of the present invention at a scan rate of 2 mV/s;
FIG. 8 is a graph of rate capability of modified Schiff base polymers in example 2 of the invention;
FIG. 9 is a graph showing the comparison of the cycle performance at a current density of 0.5A/g before and after modification of the Schiff base polymer in example 2 of the present invention.
Detailed Description
The technical solution of the present invention is described in detail by the following specific examples, which are carried out on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following examples.
Example 1
Weighing melamine and 4,4 '-biphenyldicarboxaldehyde according to the molar ratio of 1:0.75, adding the melamine and the 4, 4' -biphenyldicarboxaldehyde into a beaker filled with dimethyl sulfoxide, carrying out ultrasonic treatment for 1 hour to form a transparent solution, transferring the solution into a three-neck flask of a reflux device, introducing nitrogen for protection, and then heating and refluxing for 12 hours at 160 ℃ to obtain a reaction product. And after the reaction product is cooled to room temperature, alternately washing the reaction product by using excessive ethanol and dichloromethane until the filtrate is clear and colorless, and drying the filter cake in a forced air drying oven to obtain the Schiff base polymer.
Weighing the Schiff base polymer and lithium hydride according to the molar ratio of 1:2, heating and stirring at 80 ℃ under the protection of nitrogen for reacting for 8 hours, after the reaction is finished, sequentially performing suction filtration on the product by using ethanol and dichloromethane, washing by using ethanol until the filtrate is neutral, and drying to obtain the modified Schiff base polymer.
FIG. 1 is a diagram showing the synthesis steps of a Schiff base polymer and a modified Schiff base polymer in example 1 of the present invention, and FIG. 2 is a comparison graph of infrared spectra before and after modification of the Schiff base polymer in this example, both of which are at 1600cm-1～1400cm-1And 810cm-1The nearby peaks are characteristic signals of triazine ring and benzene ring structures respectively, which proves that the Schiff base polymer is successfully prepared in the embodiment, the chemical structure of the Schiff base polymer is not damaged after modification, and the chemical formula of the structural unit is shown in FIG. 3.
Fig. 4 is a scanning electron micrograph of the schiff base polymer obtained in this example, which shows that the modified schiff base polymer is particles aggregated to form a block.
The schiff base polymer and the modified schiff base polymer prepared in the embodiment are respectively and uniformly mixed with conductive carbon black and polyvinylidene fluoride according to the mass ratio of 5:4:1, and a proper amount of N-methyl pyrrolidone is added to be prepared into slurry. And uniformly coating the slurry on a copper foil by using a 200-micron scraper, and performing vacuum drying at 80 ℃ for 12 hours to obtain the Schiff base polymer pole piece.
Punching the prepared Schiff base polymer pole piece into a circular sheet with the diameter of 12 mm; taking a metal lithium sheet with the diameter of 16mm as a positive electrode and taking Celgard2400 as a diaphragm; dissolving electrolyte lithium hexafluorophosphate in a mixed solution of dimethyl carbonate and ethylene carbonate in a volume ratio of 1:1 to prepare 1mol/L electrolyte; and assembling the button cell in a glove box filled with argon. And testing the button cell in a 0.01-3V charging and discharging voltage by adopting a NEWARE-CT-4008T cell testing system and a CHI660E electrochemical workstation.
Fig. 5 is a graph of rate performance of a button cell assembled by the modified schiff base polymer in this embodiment, and after cycling is performed at a plurality of different current densities of 0.1A/g, 0.3A/g, 0.5A/g, 1A/g, 3A/g, and 5A/g, the capacity of the button cell can still be recovered to 299.6mAh/g, which indicates that the material has excellent cycling stability and rate performance.
Fig. 6 is a comparison graph of the cycling performance of the button cell assembled with the schiff base polymer electrode material before and after modification at a current density of 1A/g in this example. After 1000 cycles of circulation, the Schiff base polymer only has 266mAh/g of specific capacity, and the modified Schiff base polymer has 588mAh/g, which successfully proves that the electrode material has greatly improved circulation performance after the pre-lithiation modification.
Example 2
Weighing melamine and 4,4 '-biphenyldicarboxaldehyde according to a molar ratio of 1:1.5, adding the melamine and the 4, 4' -biphenyldicarboxaldehyde into a beaker filled with dimethyl sulfoxide, carrying out ultrasonic treatment for 1 hour to form a transparent solution, transferring the solution into a three-neck flask of a reflux device, introducing nitrogen for protection, and heating and refluxing at 180 ℃ for 24 hours to obtain a reaction product. And after the reaction product is cooled to room temperature, alternately washing the reaction product by using excessive ethanol and dichloromethane until the filtrate is clear and colorless, and drying the filter cake in a forced air drying oven to obtain the Schiff base polymer.
Weighing the Schiff base polymer and lithium hydride according to a molar ratio of 1:5, heating and stirring at 100 ℃ under the protection of nitrogen for reaction for 12 hours, sequentially performing suction filtration on a product after the reaction is finished by using ethanol and dichloromethane, washing the product by using ethanol until a filtrate is neutral, and drying to obtain the modified Schiff base polymer.
The modified schiff base polymer prepared in the embodiment is uniformly mixed with conductive carbon black and polyvinylidene fluoride according to the mass ratio of 5:4:1, and a proper amount of N-methylpyrrolidone is added to be mixed into slurry. And uniformly coating the slurry on a copper foil by using a 200-micron scraper, and performing vacuum drying at 80 ℃ for 12 hours to obtain the Schiff base polymer pole piece.
Punching the prepared Schiff base polymer pole piece into a circular sheet with the diameter of 12 mm; taking a metal lithium sheet with the diameter of 16mm as a positive electrode and taking Celgard2400 as a diaphragm; dissolving electrolyte lithium hexafluorophosphate in a mixed solution of dimethyl carbonate and ethylene carbonate in a volume ratio of 1:1 to prepare 1mol/L electrolyte; and assembling the button cell in a glove box filled with argon. And testing the button cell in a 0.01-3V charging and discharging voltage by adopting a NEWARE-CT-4008T cell testing system and a CHI660E electrochemical workstation.
Fig. 7 is a cyclic voltammogram of a button cell assembled by the electrode material of the modified schiff base polymer in this example, it can be observed that CV curves almost overlap after the second cycle, which indicates that the redox reaction occurring on the schiff base polymer has high stability and reversibility.
Fig. 8 is a graph of rate performance of the button cell battery made of the modified schiff base polymer electrode material in this embodiment, and after cycling is performed at a plurality of different current densities of 0.1A/g, 0.3A/g, 0.5A/g, 1A/g, 3A/g, and 5A/g, the capacity of the button cell battery can still be recovered to 305.4mAh/g, which indicates that the material has excellent cycle stability and rate performance.
Fig. 9 is a graph of the cycling performance at 0.5A/g current density for a button cell assembled with the schiff base polymer electrode material before and after modification in this example. The capacity of the Schiff base polymer is increased to about 600mAh/g after 400 cycles of circulation, then the capacity is continuously decreased, and only 446mAh/g is left after 100 cycles of subsequent circulation. The specific capacity of the modified Schiff base polymer is up to 571mAh/g at 500 circles, and the improvement of the cycle performance by the pre-lithiation modification is strongly proved.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. A preparation method of a prelithiation modified Schiff base polymer electrode material is characterized by comprising the following steps: the preparation method comprises the steps of taking melamine and 4, 4' -biphenyldicarboxaldehyde as raw materials and dimethyl sulfoxide as a solvent, carrying out reflux reaction to obtain a Schiff base polymer, and carrying out heating and stirring reaction on the Schiff base polymer and lithium hydride to obtain the prelithiation modified Schiff base polymer electrode material.
2. The method of claim 1, comprising the steps of:
step 1, adding melamine and 4,4 '-biphenyldicarboxaldehyde into dimethyl sulfoxide, and performing ultrasonic treatment until the melamine and the 4, 4' -biphenyldicarboxaldehyde are dissolved to obtain a mixed solution;
step 2, adding the mixed solution into a reflux device for reflux reaction, and performing suction filtration on the obtained reaction product to obtain a Schiff base polymer;
and 3, heating and stirring the Schiff base polymer and lithium hydride for reaction to obtain the pre-lithiation modified Schiff base polymer electrode material.
3. The production method according to claim 1 or 2, characterized in that: the mol ratio of the melamine to the 4, 4' -biphenyldicarboxaldehyde is 1: 0.75-1.5.
4. The production method according to claim 1 or 2, characterized in that: the reflux reaction and the heating stirring reaction are carried out under the protection of nitrogen.
5. The production method according to claim 1 or 2, characterized in that: the temperature of the reflux reaction is 160-180 ℃, and the time is 12-24 h.
6. The method of claim 2, wherein: and the washing reagents used in the suction filtration are ethanol and dichloromethane.
7. The production method according to claim 1 or 2, characterized in that: the molar ratio of the Schiff base polymer to the lithium hydride is 1: 2-5.
8. The production method according to claim 1 or 2, characterized in that: the heating and stirring reaction is carried out at the temperature of 80-100 ℃ for 8-12 h.
9. The prelithiation modified schiff base polymer electrode material prepared by the preparation method of any one of claims 1 to 8.
10. Use of the prelithio modified schiff base polymer electrode material of claim 9 in a lithium ion battery negative electrode material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200019105A (en) * | 2018-08-13 | 2020-02-21 | 주식회사 엘지화학 | Modified conjugated diene polymer and preparation method thereof |
| CN112510186A (en) * | 2020-12-03 | 2021-03-16 | 珠海冠宇电池股份有限公司 | Pre-lithiated silicon negative electrode material, silicon negative electrode piece, preparation method of silicon negative electrode piece and lithium battery |
| CN112940156A (en) * | 2021-01-25 | 2021-06-11 | 珠海冠宇电池股份有限公司 | Pre-lithiation polymer and preparation method and application thereof |
| CN113248672A (en) * | 2021-06-25 | 2021-08-13 | 安徽大学 | Schiff base polymer electrode material with increased capacity in circulation process and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200019105A (en) * | 2018-08-13 | 2020-02-21 | 주식회사 엘지화학 | Modified conjugated diene polymer and preparation method thereof |
| CN112510186A (en) * | 2020-12-03 | 2021-03-16 | 珠海冠宇电池股份有限公司 | Pre-lithiated silicon negative electrode material, silicon negative electrode piece, preparation method of silicon negative electrode piece and lithium battery |
| CN112940156A (en) * | 2021-01-25 | 2021-06-11 | 珠海冠宇电池股份有限公司 | Pre-lithiation polymer and preparation method and application thereof |
| CN113248672A (en) * | 2021-06-25 | 2021-08-13 | 安徽大学 | Schiff base polymer electrode material with increased capacity in circulation process and preparation method thereof |
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