CN115043970A - Cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing maleimide structure, preparation method and application thereof - Google Patents
Cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing maleimide structure, preparation method and application thereof Download PDFInfo
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- 239000012876 carrier material Substances 0.000 title claims abstract description 57
- 229920000642 polymer Polymers 0.000 title claims abstract description 56
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 26
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 229910013553 LiNO Inorganic materials 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 4
- 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 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 claims description 2
- WHSQATVVMVBGNS-UHFFFAOYSA-N 4-[4,6-bis(4-aminophenyl)-1,3,5-triazin-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=N1 WHSQATVVMVBGNS-UHFFFAOYSA-N 0.000 claims description 2
- SNLFYGIUTYKKOE-UHFFFAOYSA-N 4-n,4-n-bis(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 SNLFYGIUTYKKOE-UHFFFAOYSA-N 0.000 claims description 2
- -1 LA132 Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 13
- 239000005077 polysulfide Substances 0.000 abstract description 9
- 229920001021 polysulfide Polymers 0.000 abstract description 9
- 150000008117 polysulfides Polymers 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 12
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920003192 poly(bis maleimide) Polymers 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000013310 covalent-organic framework Substances 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001291 vacuum drying 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/36—Amides or imides
- C08F122/40—Imides, e.g. cyclic imides
-
- 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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
A cross-linking type porous polymer lithium-sulfur battery anode carrier material containing a maleimide structure, a preparation method and application thereof belong to the technical field of organic lithium-sulfur battery electrode materials. According to the invention, a multifunctional maleimide monomer is used for carrying out high-temperature crosslinking free radical polymerization reaction in a high-capacity reactor to prepare the porous anode carrier material so as to improve the yield, and the diphenyl sulfone serving as a reaction solvent can be recycled so as to reduce the production cost; the prepared porous positive electrode carrier material realizes the limitation of polysulfide diffusion through a large amount of nitrogen and oxygen heteroatoms contained in the porous positive electrode carrier material, and the pore passages of micropores and mesopores, thereby inhibiting the shuttle effect and realizing excellent electrochemical performance. The cross-linked porous polymer containing the maleimide structure can be applied as a positive electrode carrier material in a lithium-sulfur battery, and can remarkably improve the cycling stability of the battery, so that the battery can still maintain higher capacity and coulombic efficiency after long cycling.
Description
Technical Field
The invention belongs to the technical field of electrode materials of organic lithium-sulfur batteries, and particularly relates to a cross-linked porous polymer positive electrode carrier material containing a maleimide structure for lithium-sulfur batteries, and 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. The lithium-sulfur battery has theoretical energy density seven times higher than that of the current commercial lithium-ion battery, and the active substance sulfur has the advantages of high storage capacity, low price, no toxicity, environmental friendliness and the like, so that the lithium-sulfur battery is expected to replace the traditional commercial inorganic electrode material and gradually becomes a research hotspot in the field of lithium-ion battery electrode materials. However, the lithium sulfur battery generates polysulfide intermediate which is easily dissolved in the electrolyte during the charge and discharge processes to cause shuttle effect, and the low conductivity of the final product (sulfur and lithium sulfide) of the charge and discharge of the battery itself is a major challenge limiting the commercial use of the lithium sulfur battery. At present, researchers mainly adopt a strategy of developing a porous positive electrode carrier material containing heteroatoms such as N, O and the like to adsorb polysulfide and prevent the polysulfide from diffusing to a negative electrode so as to inhibit a shuttle effect, so that the cycling stability of the battery is improved. Based on such design concept, researchers have developed various porous positive electrode support electrode materials such as Covalent Organic Frameworks (COFs), Metal Organic Frameworks (MOFs), porous organic polymers, and the like. Due to the defects of complex preparation conditions, low yield, poor stability and the like of COF and MOF materials, the COF and MOF materials are difficult to be produced and applied on a large scale. In order to overcome the defects, the development of the positive porous material which has low cost and high yield and can obviously inhibit the shuttle effect becomes a development trend in the field of organic lithium-sulfur battery electrode materials.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing a maleimide structure, a preparation method and application thereof. The invention aims to prepare the porous anode carrier material by carrying out high-temperature crosslinking free radical polymerization reaction on a multifunctional maleimide monomer in a high-capacity reactor so as to improve the yield, and the diphenyl sulfone serving as a reaction solvent can be recycled so as to reduce the production cost; the prepared porous positive electrode carrier material realizes the limitation of polysulfide diffusion through a large amount of nitrogen and oxygen heteroatoms contained in the porous positive electrode carrier material, and the pore passages of micropores and mesopores, thereby inhibiting the shuttle effect and realizing excellent electrochemical performance.
The invention relates to a cross-linked porous polymer lithium-sulfur battery anode carrier material containing a maleimide structure, which has the structural formula shown as follows:
wherein R is 1 、R 2 Respectively has the following structures:
R 1 :
R 2: 
the invention relates to a preparation method of a cross-linked porous polymer lithium-sulfur battery anode carrier material containing a maleimide structure, which comprises the following chemical synthesis reaction:
the method comprises the following specific steps:
step 1: under the inert condition, dropwise adding an acetone solution dissolved with maleic anhydride into an acetone solution dissolved with an amino monomer, reacting for a certain time under the condition of stirring and heating, and reacting for a certain time under the condition of stirring and refluxing;
step 2: after the reaction in the step 1 is finished, pouring the obtained mixed solution into ice water while the mixed solution is hot, then carrying out suction filtration, washing the obtained filter residue with an alkaline aqueous solution until the washing liquid is neutral, then washing with an organic solvent until the washing liquid is colorless and transparent, and drying the obtained solid in vacuum to obtain a maleimide monomer;
and step 3: under the inert condition, adding the maleimide monomer obtained in the step (2) into a high-boiling-point organic solvent, and reacting for a certain time under the condition of stirring and refluxing;
and 4, step 4: and (3) after the reaction in the step (3) is finished, cooling the obtained mixed solution to 130-140 ℃, pouring the mixed solution into an organic solvent for suction filtration, washing filter residues with the organic solvent until the filter residues are colorless and transparent, and drying the obtained solid in vacuum to obtain the maleimide structure-containing cross-linked porous polymer lithium sulfur battery anode carrier material.
The amino monomer in the step 1 is one of p-phenylenediamine, 2- (4-aminophenyl) -5-aminobenzimidazole, 4' -diaminodiphenylmethane, tri (4-aminophenyl) amine, 1,3, 5-tri (4-aminophenyl) benzene and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine.
In the step 1, the molar use ratio of the maleic anhydride monomer to the amino monomer is 2.2-3.3: 1;
in the acetone solvent in the step 1, the concentration of the maleic anhydride monomer is 0.05-5 mol/L;
in the step 1, the reaction is carried out for 2 to 4 hours under the condition of stirring at 40 to 60 ℃, and then the reaction time is 3 to 6 hours under the condition of stirring and refluxing;
2, the alkaline aqueous solution is a sodium bicarbonate aqueous solution or a sodium carbonate aqueous solution;
in the step 2, the mass fraction of the alkaline aqueous solution is 5-10%;
in the step 2, the organic solvent is one of acetone, tetrahydrofuran and ethanol;
in the step 3, the high-boiling-point organic solvent is one of diphenyl sulfone and sulfolane, and the mass usage ratio of the maleimide monomer to the high-boiling-point solvent is 0.2-0.002: 1;
the reflux reaction time in the step 3 is 12-36 hours;
the organic solvent in the step 4 is one of acetone, tetrahydrofuran and ethanol.
The cross-linked porous polymer containing the maleimide structure can be applied as a positive electrode carrier material in a lithium-sulfur battery. The lithium sulfur battery is prepared as follows: taking the cross-linked porous polymer containing the maleimide structure as a positive electrode carrier material, fully grinding and mixing the positive electrode carrier material with sulfur, and heating the mixture under an inert condition at the temperature of 150-160 ℃ for 8-12 hours to prepare a positive electrode composite material; taking Al foil as a positive current collector and acetylene black as a conductive agent, uniformly mixing and coating a positive composite material, the conductive agent and a binder on the current collector, and drying for 12-24 hours under the conditions of vacuum and 60-80 ℃; and cutting the obtained electrode slice into small round slices to be used as the anode of the lithium ion battery, and assembling the small round slices into the button battery by using the lithium slice as the cathode of the lithium ion battery in the glove box.
The binder is one of PVDF, SBR/CMC, sodium alginate, LA132, carboxymethyl cellulose or polyacrylic acid.
The electrolyte used by the button cell is LiPF 6 in EC/DEC (volume ratio 1:1), LiTFSI in DOL/DME (volume ratio 1:1), LiPF 6 in EC/DMC (volume ratio 1:1) or LiPF 6 in one of EC/DEC/DMC (volume ratio 1:1), 2 wt% LiNO was added 3 And (3) an additive.
The cathode carrier material and the sulfur account for 100% of the sum of the mass, wherein the cathode carrier material accounts for 30-50%.
The positive electrode composite material, the conductive agent and the binder account for 100% of the total mass, wherein the positive electrode composite 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 cross-linked porous polymer lithium-sulfur battery anode carrier material containing the maleimide structure is simple, the experimental raw materials are cheap and easy to obtain, the polymerization reaction yield is high, and the cross-linked porous polymer lithium-sulfur battery anode carrier material has excellent electrochemical properties such as high capacity, long service life and the like, and is favorable for realizing large-scale application. Compared with the prior art, the invention obviously improves the cycling stability of the battery, so that the battery can still keep higher capacity and coulombic efficiency after long cycling.
Drawings
FIG. 1 is an infrared test chart of bismaleimide monomer of a cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing a maleimide structure according to example 1 of the present invention, where the abscissa is wave number and the ordinate is transmittance;
FIG. 2 is an infrared test chart of the cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing a maleimide structure according to example 1 of the present invention, wherein the abscissa is wave number and the ordinate is transmittance;
FIG. 3 shows N of the support material for the positive electrode of the cross-linked porous polymer lithium-sulfur battery containing a maleimide structure according to example 1 of the present invention 2 Adsorption/desorption isotherms with relative pressure on the abscissa and N for unit mass of polymer on the ordinate 2 The amount of adsorption;
FIG. 4 is a distribution diagram of the pore diameter of the support material of the positive electrode of the cross-linked porous polymer lithium-sulfur battery containing a maleimide structure according to example 1, wherein the abscissa represents the width of the pore diameter and the ordinate represents the pore volume of the pores with the corresponding pore diameter;
FIG. 5 is a graph of the cycle performance of the positive electrode carrier material of the cross-linked porous polymer lithium-sulfur battery containing a maleimide structure according to example 1 at 0.2C, wherein the abscissa is the number of cycles of the battery, and the ordinate is the capacity of an active material per unit mass and the coulombic efficiency;
FIG. 6 is an infrared test chart of bismaleimide monomer of the cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing a maleimide structure according to example 2 of the present invention, where the abscissa is wave number and the ordinate is transmittance;
FIG. 7 is an infrared test chart of the cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing a maleimide structure according to example 2 of the present invention, wherein the abscissa is the wave number and the ordinate is the transmittance;
FIG. 8 shows N of the support material for the positive electrode of the cross-linked porous polymer lithium-sulfur battery containing a maleimide structure according to example 2 of the present invention 2 Adsorption/desorption isotherms with relative pressure on the abscissa and N of the polymer in unit mass on the ordinate 2 The amount of adsorption;
FIG. 9 is a distribution diagram of the pore diameter of the support material of the positive electrode of the cross-linked porous polymer lithium-sulfur battery containing a maleimide structure according to example 2 of the present invention, wherein the abscissa represents the width of the pore diameter and the ordinate represents the pore volume of the pores having the corresponding pore diameter;
fig. 10 is a capacity-voltage curve of the cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing a maleimide structure in example 2 of the present invention at 0.2C, with the abscissa representing the capacity of the active material per unit mass and the ordinate representing the charging and discharging voltage of the battery.
Detailed Description
Example 1:
under inert conditions, maleic anhydride (with a molar weight of 220mmol) and p-phenylenediamine (with a molar weight of 100mmol) are respectively added into acetone (with a volume of 200mL and 400mL respectively) solvent, and an acetone solution of the maleic anhydride is dropwise added into an acetone solution of the p-phenylenediamine under the condition of stirring (500 revolutions per second) at room temperature, and then the mixture is reacted for 3 hours under the condition of stirring at 50 ℃, and finally the mixture is reacted for 3 hours under the condition of stirring and refluxing.
After the reaction is finished, pouring the obtained mixed solution into ice water while the mixed solution is hot, then carrying out suction filtration, washing the obtained filter residue with a sodium bicarbonate aqueous solution with the mass fraction of 10% until a washing liquid is neutral, then washing with acetone until the washing liquid is colorless and transparent, and vacuum-drying the obtained solid to obtain the bismaleimide monomer with the yield of 85%, wherein the structural formula is shown in the specification, and an infrared test chart 1 shows that the successful synthesis of the polymer is carried out at 1364cm shown in the chart 1 -1 The absorption peak of C-N-C appeared at and 1780cm -1 The formation of the imide structure is evidenced by the absorption peak at which C ═ O appears.
Bismaleimide monomer (30 mmol in molar amount) was added to diphenyl sulfone (35g) under inert conditions, and reacted for 36 hours under stirring (500 rpm) under reflux.
After the reaction is finished, cooling the obtained mixed solution to 135 ℃, pouring the mixed solution into acetone, then carrying out suction filtration, washing the obtained filter residue with 65 ℃ hot ethanol until the washing solution is colorless and transparent to remove diphenyl sulfone, and drying the obtained solid in vacuum to obtain the cross-linked porous polymer lithium sulfur battery anode carrier material containing the maleimide structure, wherein the yield is 95%, the structural formula is shown as follows, an infrared test chart 2 proves the successful synthesis of the polymer, and as shown in the chart 2, the bismaleimide monomer is cross-linked at 1636cm -1 Absorption peak of (C) ═ C and 3057cm -1 The disappearance of the absorption peak at C — H indicates that the double bond undergoes radical polymerization at high temperature to form a crosslinked polymer.
As can be seen from fig. 3, the target polymer has a high specific surface area, which is advantageous for the adsorption of polysulfides by the material and for the nucleation and growth of lithium sulfide upon battery discharge. As can be seen from fig. 4, the target polymer has a large number of micropores and mesopores, which is advantageous in limiting the diffusion of polysulfides.
Taking the polymer as a positive electrode carrier material, fully grinding and mixing the polymer with sulfur, heating the mixture under an inert condition at the temperature of 155 ℃ for 10 hours to prepare a positive electrode composite material, taking Al foil as a positive electrode current collector, taking acetylene black as a conductive agent, and mixing the positive electrode composite material, the conductive agent and a binder (PVDF) in a ratio of 6: 3: 1, coating the mixture on a current collector, and baking the current collector for 24 hours under the conditions of vacuum and 60 ℃. Cutting the obtained electrode plate into small round pieces to be used as the anode of a lithium sulfur battery, taking the lithium piece as the cathode of the lithium ion battery, adding 2 wt% LiNO into electrolyte which is LiTFSI in DOL/DME (volume ratio is 1:1) 3 Additive, CR2032 assembled in a glove boxThe button cell is used for testing the performance of the half cell.
Tests show that (figure 5) the initial capacity of the half-cell prepared by the method can reach 811mAh g at the charge-discharge rate of 0.2C -1 And the capacity attenuation rate of each circle is 0.32%, which shows that the prepared cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing a maleimide structure can fully inhibit the shuttle effect and has excellent capacity retention performance.
Example 2:
under inert conditions, maleic anhydride (110 mmol in molar weight) and p-phenylenediamine (50 mmol in molar weight) are respectively added into acetone (100 mL and 200mL in volume) solvent, an acetone solution of the maleic anhydride is dropwise added into an acetone solution of the p-phenylenediamine under the condition of stirring (500 revolutions per second) at room temperature, and then the mixture is reacted for 3 hours under the condition of stirring at 50 ℃, and finally the mixture is reacted for 3 hours under the condition of stirring and refluxing.
After the reaction is finished, pouring the obtained mixed solution into ice water while the mixed solution is hot, then carrying out suction filtration, washing the obtained filter residue by using a sodium bicarbonate aqueous solution with the mass fraction of 10% until the washing liquid is neutral, and drying the obtained solid in vacuum to obtain the bismaleimide monomer with the yield of 87%, wherein the structural formula is shown in the specification, and an infrared test chart 6 shows that the successful synthesis of the polymer is carried out at 1364cm shown in the chart 6 -1 The absorption peak of C-N-C appeared in (g) and 1780cm -1 The formation of the imide structure is evidenced by the absorption peak at C ═ O.
Bismaleimide monomer (0.75 mmol in molar amount) was added to diphenyl sulfone (25g) under inert conditions, and reacted for 36 hours under stirring (500 rpm) under reflux.
After the reaction is finished, cooling the obtained mixed solution to 135 ℃, pouring the mixed solution into acetone, then carrying out suction filtration, washing the obtained filter residue with 65 ℃ hot ethanol until the washing solution is colorless and transparent to remove diphenyl sulfone, and drying the obtained solid in vacuum to obtain the cross-linked porous polymer lithium sulfur containing the maleimide structureThe yield of the cell anode carrier material is 95%, the structural formula is shown as follows, an infrared test chart 7 proves the successful synthesis of the polymer, and as shown in the chart 7, the bismaleimide monomer is crosslinked at 1636cm -1 Absorption peak of (C) and 3057cm -1 The disappearance of the absorption peak of (C-H) indicates that the double bond undergoes radical polymerization at high temperature to form a crosslinked polymer.
Watch (A)
As can be seen from fig. 8, the target polymer has a higher specific area, which is advantageous for the adsorption of polysulfides by the material and for the nucleation and growth of lithium sulfide upon battery discharge. As can be seen from fig. 9, the target polymer has a large number of micropores and mesopores, which is advantageous in limiting the diffusion of polysulfides.
Taking the polymer as a positive electrode carrier material, fully grinding and mixing the polymer and sulfur, heating the mixture under an inert condition at the temperature of 155 ℃ for 10 hours to obtain a positive electrode composite material, taking Al foil as a positive electrode current collector, taking acetylene black as a conductive agent, and mixing the positive electrode composite material, the conductive agent and a binder (PVDF) in a ratio of 6: 3: 1, coating the mixture on a current collector, and baking the current collector for 24 hours under the conditions of vacuum and 60 ℃. Cutting the obtained electrode plate into small round pieces to be used as the anode of a lithium sulfur battery, taking the lithium piece as the cathode of the lithium ion battery, adding 2 wt% LiNO into electrolyte which is LiTFSI in DOL/DME (volume ratio is 1:1) 3 Additives, CR2032 coin cells assembled in a glove box were used for half-cell performance testing.
Tests show that (figure 10), the initial capacity of a half cell corresponding to a positive electrode prepared from the composite material prepared by using the polymer as a positive electrode carrier material can reach 938mAh g at a charge-discharge rate of 0.2C -1 The prepared cross-linked porous polymer positive electrode carrier material containing the maleimide structure has excellent electrochemical performance.
Claims (9)
1. A cross-linking type porous polymer lithium-sulfur battery positive electrode carrier material containing a maleimide structure has a structural formula shown as follows:
wherein R is 1 、R 2 Each having one of the following structures:
R 1 :
R 2: 
2. the preparation method of the cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing the maleimide structure as claimed in claim 1, comprises the following steps:
step 1: under the inert condition, dropwise adding an acetone solution dissolved with maleic anhydride into an acetone solution dissolved with an amino monomer, reacting for a certain time under the condition of stirring and heating, and reacting for a certain time under the condition of stirring and refluxing;
step 2: after the reaction in the step 1 is finished, pouring the obtained mixed solution into ice water while the mixed solution is hot, then carrying out suction filtration, washing the obtained filter residue with an alkaline aqueous solution until the washing liquid is neutral, then washing with an organic solvent until the washing liquid is colorless and transparent, and drying the obtained solid in vacuum to obtain a maleimide monomer;
and step 3: under the inert condition, adding the maleimide monomer obtained in the step 2 into a high-boiling-point organic solvent, and reacting for a certain time under the condition of stirring and refluxing;
and 4, step 4: and (3) after the reaction in the step (3) is finished, cooling the obtained mixed solution to 130-140 ℃, pouring the mixed solution into an organic solvent for suction filtration, washing filter residues with the organic solvent until the filter residues are colorless and transparent, and drying the obtained solid in vacuum to obtain the maleimide structure-containing cross-linked porous polymer lithium sulfur battery anode carrier material.
3. The method for preparing the cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing the maleimide structure according to claim 1, wherein the cross-linked porous polymer lithium-sulfur battery positive electrode carrier material comprises the following steps: the amino monomer in the step 1 is one of p-phenylenediamine, 2- (4-aminophenyl) -5-aminobenzimidazole, 4' -diaminodiphenylmethane, tri (4-aminophenyl) amine, 1,3, 5-tri (4-aminophenyl) benzene and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine; the molar use ratio of the maleic anhydride monomer to the amino monomer is 2.2-3.3: 1; in an acetone solvent, the concentration of a maleic anhydride monomer is 0.05-5 mol/L; the reaction is carried out for 2-4 hours under the condition of stirring at 40-60 ℃, and then the reaction time is 3-6 hours under the condition of stirring and refluxing.
4. The method for preparing the carrier material of the positive electrode of the cross-linked porous polymer lithium-sulfur battery containing the maleimide structure according to claim 1, wherein the carrier material comprises the following components in percentage by weight: 2, the alkaline aqueous solution is a sodium bicarbonate aqueous solution or a sodium carbonate aqueous solution, and the mass fraction of the alkaline aqueous solution is 5-10%; the organic solvent is one of acetone, tetrahydrofuran and ethanol.
5. The method for preparing the cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing the maleimide structure according to claim 1, wherein the cross-linked porous polymer lithium-sulfur battery positive electrode carrier material comprises the following steps: in the step 3, the high-boiling-point organic solvent is one of diphenyl sulfone and sulfolane, and the mass usage ratio of the maleimide monomer to the high-boiling-point solvent is 0.2-0.002: 1; the reflux reaction time is 12-36 hours.
6. The method for preparing the cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing the maleimide structure according to claim 1, wherein the cross-linked porous polymer lithium-sulfur battery positive electrode carrier material comprises the following steps: the organic solvent in the step 4 is one of acetone, tetrahydrofuran and ethanol.
7. The use of the cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing a maleimide structure according to claim 1 as a positive electrode carrier material in a lithium-sulfur battery.
8. The use of the maleimide structure-containing cross-linked porous polymer lithium-sulfur battery positive electrode carrier material as claimed in claim 7, as a positive electrode carrier material in a lithium-sulfur battery, wherein: taking the cross-linked porous polymer containing the maleimide structure as a positive electrode carrier material, fully grinding and mixing the positive electrode carrier material with sulfur, and heating the mixture under an inert condition at the temperature of 150-160 ℃ for 8-12 hours to prepare a positive electrode composite material; taking Al foil as a positive current collector and acetylene black as a conductive agent, uniformly mixing and coating a positive composite material, the conductive agent and a binder on the current collector, and drying for 12-24 hours under the conditions of vacuum and 60-80 ℃; and cutting the obtained electrode slice into small round slices to be used as the anode of the lithium ion battery, and assembling the small round slices into the button battery by using the lithium slice as the cathode of the lithium ion battery in the glove box.
9. The use of the maleimide structure-containing cross-linked porous polymer lithium-sulfur battery positive electrode carrier material as claimed in claim 8, as a positive electrode carrier material in a lithium-sulfur battery, wherein: the binder is one of PVDF, SBR/CMC, sodium alginate, LA132, carboxymethyl cellulose or polyacrylic acid; the electrolyte used by the button cell is LiPF 6 in EC/DEC (volume ratio 1:1), LiTFSI in DOL/DME (volume ratio 1:1), LiPF 6 in EC/DMC (volume ratio 1:1) or LiPF 6 in one of EC/DEC/DMC (volume ratio 1:1), 2 wt% LiNO was added 3 An additive; the positive electrode carrier material and sulfur account for 100% by mass, wherein the positive electrode carrier material accounts for 30-50%; the positive electrode composite material, the conductive agent and the binder account for 100% of the total mass, wherein the positive electrode composite material accounts for 40-80%, the conductive agent accounts for 10-50%, and the balance is the binder.
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| TW200909427A (en) * | 2007-08-22 | 2009-03-01 | Ind Tech Res Inst | Triphenylamine-containing bismaleimide compound and preparation thereof |
| CN104269513A (en) * | 2014-08-26 | 2015-01-07 | 江苏华东锂电技术研究院有限公司 | Cathode composite material, lithium ion battery and preparation method thereof |
| CN106785041A (en) * | 2016-12-28 | 2017-05-31 | 国联汽车动力电池研究院有限责任公司 | A kind of additive for lithium ion battery, electrolyte and anode sizing agent |
| CN113410444A (en) * | 2021-06-18 | 2021-09-17 | 吉林大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
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| TW200909427A (en) * | 2007-08-22 | 2009-03-01 | Ind Tech Res Inst | Triphenylamine-containing bismaleimide compound and preparation thereof |
| CN104269513A (en) * | 2014-08-26 | 2015-01-07 | 江苏华东锂电技术研究院有限公司 | Cathode composite material, lithium ion battery and preparation method thereof |
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