CN118027848A - Double-conductive adhesive for silicon-carbon negative electrode of lithium ion battery, and preparation method and application thereof - Google Patents
Double-conductive adhesive for silicon-carbon negative electrode of lithium ion battery, and preparation method and application thereof Download PDFInfo
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- CN118027848A CN118027848A CN202410002574.6A CN202410002574A CN118027848A CN 118027848 A CN118027848 A CN 118027848A CN 202410002574 A CN202410002574 A CN 202410002574A CN 118027848 A CN118027848 A CN 118027848A
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- lithium ion
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- sodium alginate
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- 239000000853 adhesive Substances 0.000 title claims abstract description 36
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000021615 conjugation Effects 0.000 claims abstract description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 28
- 235000010413 sodium alginate Nutrition 0.000 claims description 28
- 239000000661 sodium alginate Substances 0.000 claims description 28
- 229940005550 sodium alginate Drugs 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 claims description 17
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 claims description 17
- 229960004502 levodopa Drugs 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000011267 electrode slurry Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000006258 conductive agent Substances 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 6
- 238000007112 amidation reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 7
- 239000011259 mixed solution Substances 0.000 claims 4
- 230000002862 amidating effect Effects 0.000 claims 1
- 238000010586 diagram Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 10
- 239000013543 active substance Substances 0.000 abstract description 9
- 238000012546 transfer Methods 0.000 abstract description 6
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000009396 hybridization Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000002003 electrode paste Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- -1 nitrogen-containing organic compound Chemical class 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000011530 conductive current collector Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229940002612 prodrug Drugs 0.000 description 1
- 239000000651 prodrug Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
- C09J105/04—Alginic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention relates to a double-guide adhesive for a silicon-carbon negative electrode of a lithium ion battery, and a preparation method and application thereof, and belongs to the technical field of lithium ion batteries; and uniformly dispersing the two-dimensional conductive graphene therein, wherein the graphene with SP 2 hybridization is in pi-pi conjugation with aromatic rings in an SA-DPA system side by side. The three-dimensional network structure of the system and rich polar ether bonds effectively promote the ion conduction of the binder; graphene with high electron conduction provides a 'surface-point' contact type electron fast transfer network for an active substance, so that the electron conduction of a binder is improved. Based on excellent double-conductivity and good mechanical properties of the SA-DPA-G binder, the Si/C negative electrode has good dynamic properties, meanwhile, the volume expansion of Si/C in the charge and discharge process is effectively relieved, and good long-cycle stability is shown.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a double-conductive adhesive for a silicon-carbon negative electrode (Si/C) of a lithium ion battery, and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high capacity, no memory effect, quick reversible charge and discharge, high coulomb effect and the like, and is widely applied to commercial products such as mobile phones, notebook computers, digital cameras, new energy automobiles and the like. Graphite is a common lithium ion battery cathode material, however, as the energy density of the lithium ion battery is continuously improved, the graphite cathode with the theoretical capacity of 372mAh g -1 cannot meet the existing requirements. Therefore, there is an urgent need to find high capacity anode materials that can replace graphite. Among the novel anode materials, the Si/C material has higher specific capacity than that of the graphite material, and the raw materials are convenient to obtain, so that the Si/C material has great application potential and market value. However, in the charge and discharge process of the Si/C material, repeated volume expansion causes continuous generation of a solid electrolyte phase interface (SEI) film, and the excessive SEI film seriously influences electron transfer and lithium ion transmission, so that electrochemical dynamic performance is reduced and capacity is reduced, and commercial application of the Si/C material is restricted.
The binder has the main functions of bridging active substances, conductive agents and current collectors in the electrode, and ensures the stability of the electrode structure. As the active material evolves, the function of the binder changes. The traditional binder of the negative electrode is CMC/SBR, however, the CMC/SBR has poor conductivity and weak charge transmission capability, and electrons and ions can only slowly transmit in a system by means of a conductive additive and an electrolyte and an active material contact point. The electrode lacks an efficient electron ion transfer path, so that the electrochemical dynamic performance of the electrode is reduced, and the multiplying power performance is poor. And lower electron and ion conductivities result in reduced active material utilization resulting in a concomitant reduction in electrode specific capacity. In order to improve the electrochemical performance of the electrode, an electronic ion transmission channel is urgently needed to be constructed in the electrode, and the binder is used as the connection among the active substance, the conductive agent and the current collector, so that a complicated network is provided, and therefore, the functional binder with the electronic ion rapid transfer network is designed, the charge transmission capacity of the system is effectively improved, the electrochemical dynamics of the electrode is enhanced, the utilization rate of the active substance is improved, the energy density is improved, and the functional binder becomes a great assistance for commercial application of Si/C materials.
Disclosure of Invention
The invention aims to provide a double-conductive adhesive for a Si/C negative electrode of a lithium ion battery, which can effectively improve the charge conduction of the Si/C negative electrode, relieve the volume expansion of the Si/C negative electrode and further enhance the electrochemical performance and the long-cycle stability of the Si/C negative electrode.
Another object of the present invention is to provide a method for preparing the above double-guide adhesive.
It is a further object of the present invention to provide the use of the above-described double-guide adhesive.
The aim of the invention is achieved by the following technical scheme:
A double-guide adhesive for Si/C negative electrode of lithium ion battery is prepared by adding levodopa into prepared sodium alginate water solution under nitrogen protection, adding catalyst for amidation reaction to obtain SA-DPA, purifying with pure water, adding conductive graphene, and forming stable adhesive system by pi-pi conjugation.
Sodium alginate is a byproduct of brown algae kelp or gulfweed after extracting iodine and mannitol, is a natural polysaccharide, is easily dissolved in water, and can obtain solutions with higher viscosity at different temperatures. Levodopa is an endogenous nitrogen-containing organic compound, has a chemical formula of C 9H11NO4, is a prodrug of dopamine, and contains amino, hydroxyl and carboxyl groups. The conductive graphene is a single-layer two-dimensional honeycomb lattice structure formed by closely stacking SP 2 hybridized carbon atoms, electrons can freely move in the honeycomb structure due to the unique structure, meanwhile, an electron transmission network can be constructed on a larger space by being in contact with the surface-point of an active material, so that long-distance conduction of the whole electrode is realized, and efficient transfer of charges is ensured. According to the invention, an SA-DPA ion conducting polymer is obtained through amidation reaction of sodium alginate and levodopa, conductive graphene is added after purification to construct an ion conducting rapid channel, SP2 hybridized graphene is in pi-pi conjugation with aromatic rings in the levodopa side by side, and the obtained double-conductive adhesive effectively improves electron and ion conduction of an electrode.
Preferably, the concentration of the levodopa solution is 0.002-0.005 mol L -1.
Preferably, the volume ratio of the sodium alginate mass to the deionized water is (25-28) mg/1 mL.
Preferably, the mass ratio of the conductive graphene to the SA-DPA is as follows: (1-3): (9-7)
The preparation method of the Si/C anode for the lithium ion battery comprises the following steps:
s1, adding sodium alginate into deionized water, and stirring until the sodium alginate is completely dissolved to obtain a solution;
s2, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide (EDC) into the sodium alginate solution, and stirring until the solution is completely dissolved.
S3, adding levodopa and N-hydroxysuccinimide (NHS) into the solution, and stirring under the protection of nitrogen until the mixture is uniformly mixed;
s4, placing the prepared solution into pure water for purification, and obtaining a polymer after the reaction is finished, wherein the polymer is abbreviated as SA-DPA;
S5, adding the conductive graphene into the purified SA-DPA solution for stirring uniformly, and then performing ultrasonic dispersion by using an ultrasonic dispersion instrument to obtain a double-conductive adhesive, which is abbreviated as SA-DPA-G;
s6, adding electrode active material Si/C (950K) and a conductive agent into the SA-DPA-G solution, mixing and stirring to obtain uniformly dispersed electrode slurry;
S7, coating the obtained electrode slurry on a current collector, and drying at the temperature of 80 ℃ in vacuum to obtain the Si/C negative electrode of the lithium ion battery.
Preferably, the conductive agent in step S7 is Super P.
Preferably, the Si/C in the step S6 is 80wt% of the total mass of the electrode paste, the conductive agent is 10wt% of the total mass of the electrode paste, and the SA-DPA-G is 10wt% of the total mass of the electrode paste.
Preferably, the time for the amidation reaction required in step S3 is 20 to 24 hours.
Preferably, the purification time required for step S4 is 20-24 hours.
Preferably, the drying time in the step S7 is 10-12 hours.
A Si/C negative electrode of a lithium ion battery is prepared by the method.
The adhesive is applied to lithium ion batteries.
The invention adopts sodium alginate to be added into deionized water to be completely dissolved to obtain a solution, the levodopa is added at normal temperature under the protection of nitrogen, EDC/NHS is utilized to activate amino and carboxyl, the amidation reaction is carried out on levodopa molecules and sodium alginate macromolecular chains, and the adhesive is prepared through purification. According to the adhesive, sodium alginate is used as a main chain, the side chain of sodium alginate molecules is prolonged through levodopa grafting, conductive graphene is added after purification, and the electron conduction of the adhesive can be effectively improved by utilizing a 'face-point' contact type electron fast transfer network of the graphene and an active substance, so that the double-conductive adhesive with a three-dimensional ion conductive net structure is formed. The three-dimensional network structure formed in the binder greatly improves the ion conductive performance of the binder; the Si/C negative electrode shows excellent cycling stability and electrochemical dynamic performance. Meanwhile, expensive and toxic NMP solvent is not needed in the preparation process of the Si/C electrode, so that the method has the advantages of green and environment-friendly performance and has good commercialization prospect.
Compared with the prior art, the invention has the following beneficial effects:
1. the SA-DPA-G negative electrode binder is prepared by carrying out amidation reaction on sodium alginate serving as a main chain and levodopa, and adding conductive graphene after purification. The double-conductive adhesive SA-DPA-G with high-conductivity ionic conductivity is obtained by using the abundant polar ether bond and graphene of the system as active substances to provide a 'surface-point' contact type electron fast transfer network.
2. The adhesive prepared by the invention is a water-based adhesive, and has the advantages of environmental friendliness and simple preparation. Wherein, sodium alginate is a natural polysaccharide, contains rich carboxylate radical and hydroxyl, has the characteristics of low price, good dispersibility, water solubility and the like, and is a binder with development prospect.
3. The double-guide adhesive has rich binding sites and higher mechanical property and adhesive strength. Based on good mechanical properties and adhesive strength, the Si/C negative electrode adopting the adhesive realizes stable long-cycle performance.
Drawings
Fig. 1 is a cycle performance chart of the button cell prepared in example 1.
Fig. 2 is a graph showing the cycle performance of the button cell prepared in example 1 and comparative examples 1 and 2.
Detailed Description
The present invention is further illustrated below in conjunction with specific examples, but should not be construed as limiting the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
1. Sodium alginate with the mass of 257-263 mg is dissolved in 10g of water to prepare sodium alginate solution, about 0.240g of EDC solid is added and stirred at room temperature to be completely dissolved, about 0.140g of NHS and 37-43 mg of levodopa are added and reacted for 20-24h under the protection of nitrogen, and SA-DPA is obtained. Wherein the mass ratio of the sodium alginate to the levodopa is (6-8): 1.
2. The solution after the reaction is poured into a MW3500 dialysis bag and placed into pure water for purification for 24 hours, wherein the water is replaced every 6 hours, and the purified solution is poured into a glass dish for drying and measuring the solid content.
3. Slowly adding 30-90 mg of conductive graphene into the purified SA-DPA solution in a fractional manner, rapidly stirring for 10-15 min, and performing ultrasonic treatment by using an ultrasonic dispersing instrument for 30-60 min to uniformly disperse to obtain the double-conductive adhesive SA-DPA-G.
4. Mixing active substances Si/C, a conductive agent Super P and a double-conductive adhesive according to a mass ratio of 8:1:1, adding a proper amount of deionized water, then placing into a defoaming stirrer for stirring to obtain uniformly dispersed electrode slurry, coating the electrode slurry on a copper foil, and cutting into round pole pieces with diameters of 14mm after vacuum drying at 80 ℃ for 12 hours.
5. The dried negative electrode sheet was transferred into a glove box filled with argon, lithium sheet was used as a counter electrode, 1.2mmol L -1 of LiPF 6 was used as a solute for the electrolyte, and Ethylene Carbonate (EC) and diethyl carbonate (DEC) were used as solvents in a volume ratio of 1:1, with 25wt% fluoroethylene carbonate (FEC) as an additive. Assembled using CR2032 button cell, the assembled button cell was left to stand for 10h. And carrying out constant current test on the electrochemical performance of the well-placed battery in a Xinwei test system. Fig. 1 is a cycle performance chart of the fabricated coin cell of example 1. As can be seen from fig. 1, the silicon electrode composed of the double conductive adhesive SA-DPA-G has a capacity of 808.94mAh G -1 after 100 cycles at a current density of 500 mAh -1, and as a result, shows excellent cycle stability.
Comparative example 1
1. Sodium alginate with the mass of 257-263 mg is dissolved in 10g of water to prepare sodium alginate solution, about 0.240g of EDC solid is added and stirred at room temperature to be completely dissolved, about 0.140g of NHS and 37-43 mg of levodopa are added and reacted for 20-24h under the protection of nitrogen, and SA-DPA is obtained. Wherein the mass ratio of the sodium alginate to the levodopa is (6-8): 1.
2. The solution after the reaction is poured into a MW3500 dialysis bag and placed into pure water for purification for 24 hours, wherein the water is replaced every 6 hours, and the purified solution is poured into a glass dish for drying and measuring the solid content.
3. Mixing active substances Si/C, a conductive agent Super P and an SA-DPA binder according to a mass ratio of 8:1:1, adding a proper amount of deionized water, then placing the mixture into a defoaming stirrer for stirring to obtain uniformly dispersed electrode slurry, coating the electrode slurry on a copper foil, and cutting the electrode slurry into round pole pieces with the diameter of 14mm after vacuum drying at 80 ℃ for 12 hours.
4. The dried negative electrode sheet was transferred into a glove box filled with argon, lithium sheet was used as a counter electrode, 1.2mmol L -1 of LiPF 6 was used as a solute for the electrolyte, and Ethylene Carbonate (EC) and diethyl carbonate (DEC) were used as solvents in a volume ratio of 1:1, with 25wt% fluoroethylene carbonate (FEC) as an additive. Assembled using CR2032 button cell, the assembled button cell was left to stand for 10h. And carrying out constant current test on the electrochemical performance of the well-placed battery in a Xinwei test system.
Comparative example 2
1. 300Mg of sodium alginate is added with a proper amount of deionized water to obtain the binder with the mass fraction of 3%.
2. Mixing active substances Si/C, a conductive agent Super P and a binder according to a mass ratio of 8:1:1, adding a proper amount of deionized water, defoaming and stirring to obtain uniformly dispersed electrode slurry, coating the electrode slurry on a copper foil, and vacuum-drying at 80 ℃ for 12 hours and then cutting into round pole pieces with the diameter of 14 mm.
3. And transferring the pole piece into a glove box filled with argon gas for battery assembly. Lithium sheets in the battery are used as a counter electrode, liPF 6 of 1.2mmol L -1 is used as a solute in the electrolyte, and the volume ratio is equal to 1:1 and DEC were solvents, with 25wt% fec as additive, assembled with CR2032 coin cell.
The assembled button cells of example 1, comparative examples 1 and 2 were allowed to stand at 28℃for 10 hours and then subjected to constant current test for electrochemical performance in a New Wei test system. The test conditions were: the current density is 500mAg -1. Fig. 2 is a graph showing the cycle performance of the button cells prepared in example 1 and comparative examples 1 and 2. The comparative examples 1 and 2 and the prepared coin cells were shown in fig. 2 to decay in capacity to 775.81mAh g -1 and 482.04mAh g -1 after 100 cycles at 500mA g -1 current density. The button cell prepared in example 1 still maintains the capacity of 808.94mAh g -1, and has higher discharge capacity and better cycle stability. As can be seen from fig. 2, the double conductive binder (SA-DPA-G) can cause the Si/C anode to exhibit good cycle stability.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The double-guide binder for the silicon-carbon negative electrode of the lithium ion battery is characterized in that: the double-conductive adhesive SA-DPA-G is prepared by amidating levodopa and sodium alginate through a catalyst under the protection of nitrogen to obtain SA-DPA, adding conductive graphene after purification, and forming a stable adhesive system through pi-pi conjugation; the structure schematic diagram of the double-guide adhesive is as follows:
2. the method for preparing the double-conductive adhesive for the silicon-carbon negative electrode of the lithium ion battery according to claim 1, which is characterized by comprising the following steps:
s1, adding sodium alginate into deionized water, and stirring until the sodium alginate is completely dissolved to obtain a sodium alginate solution;
s2, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide into the sodium alginate solution obtained in the step S1, and stirring until the sodium alginate solution is completely dissolved to obtain a mixed solution I;
s3, adding levodopa and N-hydroxysuccinimide into the mixed solution I obtained in the step S2, and stirring under the protection of nitrogen until the mixture is uniformly mixed to obtain a mixed solution II;
S4, placing the mixed solution II prepared in the step S3 into pure water for purification, and obtaining a polymer after the reaction is finished, wherein the polymer is abbreviated as SA-DPA;
S5, adding the conductive graphene into the SA-DPA solution purified in the S4 for stirring uniformly, and then performing ultrasonic dispersion by using an ultrasonic dispersion instrument to obtain a double-conductive adhesive, which is abbreviated as SA-DPA-G.
3. The preparation method according to claim 2, characterized in that: in the step S1, the ratio of the mass of the sodium alginate to the volume of the deionized water is (25-28) mg/1 mL.
4. The preparation method according to claim 2, characterized in that: in the step S3, the grafting time of the amidation reaction is 20-24h, and the mass ratio of sodium alginate to levodopa is (6-8): 1.
5. The preparation method according to claim 2, characterized in that: in the step S4, the purification time is 20-24 hours; the concentration of the SA-DPA solution is 0.02-0.04 mol L -1.
6. The preparation method according to claim 2, characterized in that: in the step S5, the mass ratio of the added conductive graphene to the SA-DPA is as follows: (1-3): (9-7), the concentration of the obtained SA-DPA-G solution is 0.01-0.05 mol L -1.
7. Use of the double conductive adhesive according to claim 1 or the double conductive adhesive prepared by the preparation method according to any one of claims 2 to 6 in lithium ion batteries.
8. The use according to claim 7, characterized in that: the application refers to the preparation of the Si/C anode of the lithium ion battery by using the double-conductive adhesive of claim 1 or the double-conductive adhesive prepared by the preparation method of any one of claims 2-6.
9. The use according to claim 8, characterized in that: the preparation method of the Si/C negative electrode of the lithium ion battery comprises the following steps:
Step one, adding electrode active material Si/C and a conductive agent into a double-conductive adhesive SA-DPA-G solution, mixing and stirring to obtain uniformly dispersed electrode slurry;
and secondly, coating the obtained electrode slurry on a current collector, and drying at the temperature of 80 ℃ in vacuum to obtain the Si/C anode of the lithium ion battery.
10. The use according to claim 9, characterized in that: in the first step, the conductive agent is Super P, the Si/C is 80wt% of the total mass of the electrode slurry, the conductive agent is 10wt% of the total mass of the electrode slurry, and the SA-DPA-G is 10wt% of the total mass of the electrode slurry; in the second step, the drying time is 10-12 h.
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