CN105633364A - Preparation method of tin particle-sodium alginate-reinforced polyaniline composite material - Google Patents
Preparation method of tin particle-sodium alginate-reinforced polyaniline composite material Download PDFInfo
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- CN105633364A CN105633364A CN201511018063.0A CN201511018063A CN105633364A CN 105633364 A CN105633364 A CN 105633364A CN 201511018063 A CN201511018063 A CN 201511018063A CN 105633364 A CN105633364 A CN 105633364A
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- 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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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of a tin particle-sodium alginate-reinforced polyaniline composite material. Tin particles are prepared by a reduction method; and a sodium alginate-reinforced polyaniline high-molecular polymer material coats the outer surfaces of tin particles by a chemical in-situ polymerization method. The particle size range of the prepared tin particles is 60-100nm; and the tin particles are evenly dispersed into a three-dimensional polyaniline sodium alginate fiber gel network. The sodium alginate contains a lot of hydroxyl and carboxyl; and the sodium alginate and amino in polyaniline form a hydrogen bond and a covalent bond, so that the strength of polyaniline gel can be significantly strengthened; and the problems of agglomeration and volume expansion of a tin-based material in a long-term cycle process are well improved. The tin particle-sodium alginate-reinforced polyaniline composite material has relatively high capacity as an anode material for a lithium-ion battery; the capacity is still kept at 616mAhg<-1> after 100 cycles; and the tin particle-sodium alginate-reinforced polyaniline composite material has a wide application prospect in the aspect of prolonging the cycle lifetime of the anode material for the lithium-ion battery.
Description
Technical field
The present invention provides the Synthesis and applications of a kind of organic-inorganic nanocomposite, i.e. the Synthesis and applications of metal nanoparticle-organic polymer composite material.
Background technology
The advantages such as lithium ion battery has operating voltage height, energy density is big, cost is low, nothing is remembered, security is good, extensively for digital products such as mobile phone, notebook computer, cameras, are also the ideal sources that following electric vehicle uses. Business-like lithium ion battery negative is generally Graphene, but the lower (372mAhg of specific storage-1), first charge-discharge efficiency is low, limits its application in high-energy-density chemical power source. In the last few years, tin base cathode material was because of quality, volume and capacity ratio height (993mAhg-1, 7237AhL-1), have no side effect, the advantage such as price is cheap, processing synthesis is easy and be subject to the extensive concern of investigator. Although having higher theoretical capacity, but can there is serious volumetric expansion in tin in removal lithium embedded process, the electrode efflorescence that just produces to cause due to volume change, the problem such as peels off after tens circulations, and chemical property sharply declines thereupon. In addition, discharge process first can generate on the interface of tin-based material and electrolytic solution SEI film, cause Li+Translational speed become slow, cause the generation of the irreversible capacity that discharges first.
Owing to little size active material can effectively shorten lithium ion diffusion length, therefore tin-based material nanometer is conducive to realizing the high rate charge-discharge of electrode materials to a certain extent. But easily reuniting between nanoparticle, thus lose the characteristic of nanoparticle gradually, long-term charge-discharge performance is also undesirable. In order to improve cycle performance further, nano particle can be made to be dispersed in conductive polymer sub-network, to alleviate reunion and the volumetric expansion problem of nano particle in charge and discharge process.
The interface stability and structural stability that improve nano material are had important effect by the functional materials with nucleocapsid structure, and major cause is that shell structure can play effect that is stable and protection core well. The matrix material of this kind of structure can effectively avoid the reunion between nanoparticle or nano wire and bonding, simultaneously shell material will prevent nanoparticle efflorescence and reunion in charge and discharge process, and therefore this kind of structure is expected to obtain as the material of electrode and has high reversible capacity and good cycle performance.
Conductive polymers is widely used for encapsulated nanoparticles prepares negative material due to its good electroconductibility, excellent processing characteristics and low cost. Conductive polymers has buffer reagent and the conductive agent effect of active material concurrently, can effectively avoid the capacity fade problem caused in traditional electrode due to the interpolation of the non-active material such as conductive agent, tackiness agent. Common conductive polymers, such as polyaniline (PANI), polypyrrole (PPy) and Polythiophene etc., has been widely used in the support structure system of coating layer or metal and metal oxide, has significantly improved the chemical property of electrode. Some researchers have reported that by the silicon/polyaniline compound nucleus shell material of nano silicon particles and electrically conductive polyaniline synthesis, can the electroconductibility of obvious modified electrode, it is to increase electrode specific storage and cyclical stability.
But, conductive polymers always suffers the puzzlements such as physical strength is low, easy ruptural deformation to constrain its commercial applications to a certain extent in charge and discharge process. Sodium alginate itself is containing great amount of hydroxy group and carboxyl, it is possible to forms hydrogen bond and covalent linkage with the amino in polyaniline, thus can significantly strengthen the intensity of polyaniline gel, better improves the reunion of tin-based material in long-term working cycle and volumetric expansion problem.
Summary of the invention
Conductive polymers, due to its good electroconductibility, excellent processing characteristics and low cost, is widely used for encapsulated nanoparticles and prepares negative material. Although these polymkeric substance improve electroconductibility and the cyclical stability of electrode, but in charge and discharge process, always suffer the puzzlements such as physical strength is low, easy ruptural deformation, constrain its commercial applications to a certain extent. Sodium alginate itself, containing great amount of hydroxy group and carboxyl, forms hydrogen bond and covalent linkage, thus can significantly strengthen the intensity of polyaniline gel with the amino in polyaniline. Therefore the present invention's sodium alginate strengthens the intensity of polyaniline gel, form three dimensional gel fibre network, better improve the reunion of tin-based material in long-term working cycle and volumetric expansion problem.
The present invention provides the preparation method that a kind of tin particles-sodium alginate strengthens polyaniline composite material. Method of reducing is utilized to prepare tin nanoparticles; And then adopting the method for chemistry polymerizing in situ, the coated sodium alginate of the outside surface at tin nanoparticles strengthens polyaniline macromolecule polymer material. Tin nanoparticles particle size range prepared by the present invention is 60-100nm.
The tin particles of the present invention-sodium alginate strengthens the step that the preparation method of polyaniline composite material comprises:
(1) reduce stannous sulfate in the basic conditions with sodium borohydride, add polyvinylpyrrolidone as dispersion agent, the tin particles of black after centrifugal drying, can be obtained;
(2) take sodium alginate to be dissolved in distilled water to obtain sodium alginate soln, then take tin particles, aniline monomer and tensio-active agent sodium laurylsulfonate and be added drop-wise to sodium alginate soln, stir when frozen water and obtain solution;
(3) according to aniline monomer: ammonium persulphate mol ratio 1:3 weighs ammonium sulfate and is dissolved in distilled water, then solution with step (2) mixes, wherein sodium alginate is (0.5��1.2) than the molar ratio range of aniline monomer: 1, and mechanical stirring is also reacted when frozen water;
(4) question response terminates, and is separated by solution centrifugal, cleans impurity with distilled water, finally put oven drying for subsequent use.
The quality of above-mentioned sodium borohydride and stannous sulfate is (1��2) than scope: (2��3).
Above-mentioned taking sodium borohydride, stannous sulfate and polyvinylpyrrolidone total mass as 100%, it is 12.5% that polyvinylpyrrolidone adds massfraction.
Step 2) in the mass fraction proportioning of material be: sodium alginate 20��40 parts, tin particles 115 parts, aniline monomer 35 parts, tensio-active agent sodium laurylsulfonate 1��2 part.
The tin particles of the present invention-sodium alginate strengthens polyaniline composite material and is used for lithium ion battery negative material, only need to be cut by the Copper Foil scribbling active electrode material that prepare as diameter is that some of the Copper Foil of 8mm is directly for subsequent use as electrode materials. Electro-chemical test adopts button cell system (CR2032), polyaniline composite material is strengthened as working electrode taking tin particles-sodium alginate, adopt metallic lithium as to electrode, barrier film adopts Colgard-2300 lithium ion battery separator, electrolyte is 1mol/LLiPF6/EC+DMC+EMC (volume ratio 1:1:1), with 50mAg-1Electric current carry out charge-discharge test. Testing first charge-discharge capacity under the same conditions, the coated tin particles coated with sodium alginate enhancing polyaniline gel of pure polyaniline gel can reach all at 1100mAhg as negative material first charge-discharge capacity-1, therefore it can be shown that sodium alginate add the volumetric properties not affecting active material. Under constant current charge-discharge, test tin particles-sodium alginate strengthen the cycle performance of polyaniline composite material as negative material, be 200mAhg at charging and discharging currents-1When, this electrode materials capacity after 100 circulations still remains on 616mAhg-1, far away higher than the 355mAhg after polyaniline gel pure when same test coated 100 times circulations-1. This illustrates that sodium alginate p-poly-phenyl amine gel has significant enhancement, can significantly improve the cycle performance of battery as negative material with tin particles-sodium alginate enhancing polyaniline composite material. The present invention strengthens the coated tin nanoparticles of polyaniline gel with sodium alginate, can significantly improve the cycle performance of electrode, for tin-based material provides a kind of research method newly as the volumetric expansion problem of lithium ion battery negative material.
Accompanying drawing explanation
In Fig. 1 embodiment 4, tin particles-sodium alginate strengthens polyaniline three-dimensional fiber gel network transmission electron microscope picture.
Tin particles-polyaniline composite material scanning electron microscope (SEM) photograph in Fig. 2 embodiment 1.
In Fig. 3 embodiment 1, tin particles-polyaniline composite material is as negative material 50 cyclic voltammetry curves.
In Fig. 4 embodiment 2, tin particles-sodium alginate strengthens polyaniline composite material as negative material 50 cyclic voltammetry curves.
In Fig. 5 embodiment 3, tin particles-sodium alginate strengthens polyaniline composite material as negative material 50 cyclic voltammetry curves.
In Fig. 6 embodiment 4, tin particles-sodium alginate strengthens polyaniline composite material as negative material 50 cyclic voltammetry curves.
Embodiment
Raw material used in the embodiment of the present invention is commercial products, and purity is analytical pure. The shape looks that tin particles prepared by the present invention-sodium alginate strengthens polyaniline composite material are characterized by scanning electronic microscope (SEM) and transmission electron microscope (TEM). The present invention determines optimum synthesis condition by the different ratios of adjustment tin particles, polyaniline and sodium alginate, to take into account volumetric properties and the cycle performance of electrode. Electro-chemical test adopts button cell system (CR2032), polyaniline composite material is strengthened as working electrode taking tin particles-sodium alginate, adopt metallic lithium as to electrode, barrier film adopts Colgard-2300 lithium ion battery separator, electrolyte is 1mol/LLiPF6/EC+DMC+EMC (volume ratio 1:1:1), with 50mAg-1Electric current carry out charge-discharge test.
Embodiment 1
First tin particles is prepared by chemical reduction method. Reduce 0.1g stannous sulfate in the basic conditions with 0.05g sodium borohydride, add 0.02g polyvinylpyrrolidone as dispersion agent, the tin particles of black after centrifugal drying, can be obtained. Taking 115mg tin particles, 35mg aniline monomer and tensio-active agent sodium laurylsulfonate 1mg are added drop-wise in 3mL deionized water, and when frozen water, mechanical stirring 2h obtains solution A; According to aniline monomer: ammonium persulphate mol ratio 1:3 gets ammonium persulphate and is dissolved in 2mL distilled water and forms solution, drops in solution A by this solution, mechanical stirring is also reacted when frozen water; Question response terminates, and is separated by solution centrifugal, cleans impurity with distilled water, finally put oven drying for subsequent use.
In this example, tin particles, polyaniline and sodium alginate mass ratio are 3:1:0. Utilize scanning electronic microscope that obtained product sample is carried out morphology observation, can find out that it is porous coralliform structure from Figure of description 2. This product is applied to lithium ion battery negative material, and assembled battery carries out electrochemical Characterization, and as shown in Figure 3, after battery has carried out 50 circulations, cell container is by 1089mAhg-1Decay to 409mAhg-1, capability retention is lower, and cyclical stability is poor.
Embodiment 2
First tin particles is prepared by chemical reduction method. Reduce 0.18g stannous sulfate in the basic conditions with 0.1g sodium borohydride, add 0.04g polyvinylpyrrolidone as dispersion agent, the tin particles of black after centrifugal drying, can be obtained. Being dissolved in 3mL deionized water by 20mg sodium alginate, take 115mg tin particles, 35mg aniline monomer and tensio-active agent sodium laurylsulfonate 1mg are added drop-wise in above-mentioned solution, and when frozen water, mechanical stirring 2h obtains solution A; According to aniline monomer: ammonium persulphate mol ratio 1:3 gets ammonium persulphate and is dissolved in 2mL distilled water and forms solution, drops in solution A by this solution, mechanical stirring is also reacted when frozen water; Question response terminates, and is separated by solution centrifugal, cleans impurity with distilled water, finally put oven drying for subsequent use.
In this example, tin particles, polyaniline and sodium alginate mass ratio are 23:7:6. This product is applied to lithium ion battery negative material, and assembled battery carries out electrochemical Characterization, and as seen from Figure 4, after battery has carried out 50 circulations, cell container is by 1023mAhg-1Decay to 501mAhg-1��
Embodiment 3
First tin particles is prepared by chemical reduction method. Reduce 0.25g stannous sulfate in the basic conditions with 0.15g sodium borohydride, add 0.06g polyvinylpyrrolidone as dispersion agent, the tin particles of black after centrifugal drying, can be obtained. Being dissolved in 3mL deionized water by 40mg sodium alginate, take 115mg tin particles, 35mg aniline monomer and tensio-active agent sodium laurylsulfonate 1mg and be added drop-wise in above-mentioned solution, when frozen water, mechanical stirring 2h obtains solution A; According to aniline monomer: ammonium persulphate mol ratio 1:3 gets ammonium persulphate and is dissolved in 2mL distilled water and forms solution, drops in solution A by this solution, mechanical stirring is also reacted when frozen water; Question response terminates, and is separated by solution centrifugal, cleans impurity with distilled water, finally put oven drying for subsequent use.
In this example, tin particles, polyaniline and sodium alginate mass ratio are 23:7:8. This product is applied to lithium ion battery negative material, and assembled battery carries out electrochemical Characterization, and as seen from Figure 5, after battery has carried out 50 circulations, cell container is by 1007mAhg-1Decay to 572mAhg-1��
Embodiment 4
First tin particles is prepared by chemical reduction method. Reduce 0.3g stannous sulfate in the basic conditions with 0.2g sodium borohydride, add 0.07g polyvinylpyrrolidone as dispersion agent, the tin particles of black after centrifugal drying, can be obtained. Being dissolved in 3mL deionized water by 30mg sodium alginate, take 115mg tin particles, 35mg aniline monomer and tensio-active agent sodium laurylsulfonate 1mg and be added drop-wise in above-mentioned solution, when frozen water, mechanical stirring 2h obtains solution A; According to aniline monomer: ammonium persulphate mol ratio 1:3 gets ammonium persulphate and is dissolved in 2mL distilled water and forms solution, drops in solution A by this solution, mechanical stirring is also reacted when frozen water; Question response terminates, and is separated by solution centrifugal, cleans impurity with distilled water, finally put oven drying for subsequent use.
In this example, tin particles, polyaniline and sodium alginate mass ratio are 23:7:6. Utilizing transmission electron microscope that obtained product sample is carried out morphology observation, can be observed it for three-dimensional polyaniline and sodium alginate nano fiber gel network by Fig. 1, tin particles is dispersed in wherein. This product is applied to lithium ion battery negative material, and assembled battery carries out electrochemical Characterization, and as seen from Figure 6, after battery has carried out 50 circulations, cell container decays to 667mAhg-1 by 1104mAhg-1.
By these four examples it may be seen that the cycle performance to strengthening system that adds of sodium alginate has vital role.
Above embodiment is only lift for the present invention is described, protection scope of the present invention is not limited to this. Technician does on basis of the present invention in the art equivalent replacement and conversion, all within protection scope of the present invention.
Claims (4)
1. the preparation method of tin particles-sodium alginate enhancing polyaniline composite material; It is characterized in that step is as follows:
(1) reduce stannous sulfate in the basic conditions with sodium borohydride, add polyvinylpyrrolidone as dispersion agent, the tin particles of black after centrifugal drying, can be obtained;
(2) take sodium alginate to be dissolved in distilled water to obtain sodium alginate soln, then take tin particles, aniline monomer and tensio-active agent sodium laurylsulfonate and be added drop-wise to sodium alginate soln, stir when frozen water and obtain solution;
(3) according to aniline monomer: ammonium persulphate mol ratio 1:3 weighs ammonium sulfate and is dissolved in distilled water, then solution with step (2) mixes, wherein sodium alginate is 0.5��1.2:1 than the molar ratio range of aniline monomer, and mechanical stirring is also reacted when frozen water;
(4) question response terminates, and is separated by solution centrifugal, cleans impurity with distilled water, finally put oven drying for subsequent use.
2. the method for claim 1, is characterized in that the quality of sodium borohydride and stannous sulfate is 1��2 than scope): (2��3).
3. the method for claim 1, is characterized in that, taking sodium borohydride, stannous sulfate and polyvinylpyrrolidone total mass as 100%, it is 12.5% that polyvinylpyrrolidone adds massfraction.
4. the method for claim 1, is characterized in that the mass fraction proportioning of material in solution A is: sodium alginate 20��40 parts, tin particles 115 parts, aniline monomer 35 parts, tensio-active agent sodium laurylsulfonate 1��2 part.
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Cited By (5)
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| CN106229514A (en) * | 2016-09-10 | 2016-12-14 | 天津大学 | Preparation method and application of graphene modified conductive polymer gel coated metal nanoparticles |
| CN106299289A (en) * | 2016-09-10 | 2017-01-04 | 天津大学 | The preparation method of a kind of cobalt acid zinc/guar gum/Pt/Polypyrrole composite material and application |
| CN108520829A (en) * | 2018-04-11 | 2018-09-11 | 北京理工大学 | A kind of nitrogen oxygen codope activated carbon gas gel electrode material, solid-state super capacitor and preparation method thereof |
| CN112271293A (en) * | 2020-08-14 | 2021-01-26 | 安徽德亚电池有限公司 | Preparation method of high-conductivity lithium iron phosphate cathode material |
| WO2021079231A1 (en) * | 2019-10-25 | 2021-04-29 | 株式会社半導体エネルギー研究所 | Electrode, secondary battery and electronic device |
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| CN106229514A (en) * | 2016-09-10 | 2016-12-14 | 天津大学 | Preparation method and application of graphene modified conductive polymer gel coated metal nanoparticles |
| CN106299289A (en) * | 2016-09-10 | 2017-01-04 | 天津大学 | The preparation method of a kind of cobalt acid zinc/guar gum/Pt/Polypyrrole composite material and application |
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| WO2021079231A1 (en) * | 2019-10-25 | 2021-04-29 | 株式会社半導体エネルギー研究所 | Electrode, secondary battery and electronic device |
| CN112271293A (en) * | 2020-08-14 | 2021-01-26 | 安徽德亚电池有限公司 | Preparation method of high-conductivity lithium iron phosphate cathode material |
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