CN103825011B - The tin of lithium ion battery and the preparation method of conducting polymer composite negative pole material film - Google Patents
The tin of lithium ion battery and the preparation method of conducting polymer composite negative pole material film Download PDFInfo
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- CN103825011B CN103825011B CN201410070298.3A CN201410070298A CN103825011B CN 103825011 B CN103825011 B CN 103825011B CN 201410070298 A CN201410070298 A CN 201410070298A CN 103825011 B CN103825011 B CN 103825011B
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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
- H01M4/387—Tin or alloys based on tin
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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
- H01M4/624—Electric conductive 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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 discloses a kind of tin of lithium ion battery and the preparation method of conducting polymer composite negative pole material film, described tin and conducting polymer composite negative pole material film take graphite paper as substrate, the metallic tin of described graphite paper surface deposition is graininess, conductive macromolecular nano fiber is scattered between metallic tin particle and surface, specifically comprises the following steps: the pre-treatment of a, graphite paper; B, galvanostatic deposition metallic tin; C, conducting polymer electro-deposition prepare; D, potentiostatic method electrochemistry formated conducting polymer film; F, tin and conducting polymer composite negative pole material film are prepared.Conducting polymer of the present invention is scattered between tin nanoparticles and surface, tin plays the electrochemical action of storage lithium/de-lithium, conductive polymer sub-network play electric action same limit, cushioned the change in volume of tin nanoparticles in charge and discharge process, prevent particle agglomeration, ensure that the cyclical stability of material.
Description
Technical field
The present invention relates to the field of lithium battery material, particularly relate to a kind of tin of lithium ion battery and the preparation method of conducting polymer composite negative pole material film.
Background technology
Growing along with energy demand, extremely urgent to the research and development of novel energy material.Lithium ion battery has that output voltage is high, specific capacity is large, discharging voltage balance and the advantage such as fail safe is good, has become one of focus of novel secondary field of chemical power source research and development.The performance of lithium ion battery depends on the raising of anode and cathode active materials performance.Lithium ion battery negative material conventional is at present based on material with carbon element, and its theoretical specific capacity relatively low (372mAh/g), exists the shortcomings such as first charge-discharge efficiency is low, organic solvent embeds altogether simultaneously.Therefore the research and development of non-carbon negative material become the hot subject improving performance of lithium ion battery.
Metallic tin can carry out reversible alloying with lithium and removal alloying reacts, and have good embedding lithium/de-lithium performance, friendly to solvent selectivity, its theoretical specific capacity reaches 990mAh/g, because of but the very promising negative material of one.The preparation method of tin-based negative electrode materials for lithium-ion battery is more, mainly contains chemical reduction method, Physical and electrodeposition process etc.Chinese invention patent (Guo Hong etc.; a preparation method for high capacity tin antimony nickel alloy complex lithium ion battery cathode material, CN1786221A) adopt carbothermic method to prepare tin antimony nickel alloy dusty material, this method needs high temperature, argon shield; cost is higher, also higher to equipment requirement.Compared with dusty material, can complete under metal alloy class electrode material normal temperature and pressure conditions prepared by electrodeposition process, the coating of gained and the adhesion of matrix are better, simple to operate, cost is low.The people such as Wang Huijuan ([J] Wang Huijuan etc., the lithium ion battery storage lithium performance of metallic tin deposition layer, China YouSe Acta Metallurgica Sinica, 2010,20,1155) take Copper Foil as matrix, electrodeposition process is adopted to prepare tin deposition layer, and being made into lithium ion battery tin negative pole, its problem is, in electrochemistry cyclic process, tin particles reunion causes cycle performance significantly to reduce.
Because metallic tin is in removal lithium embedded process repeatedly, tin particles is easily assembled and is caused active reduction and cycle performance reduction, and there is bulk effect in tin base cathode material, cause tin base cathode material to have larger irreversible capacity, cycle performance not good in lithium alloyage/removal alloying process.The method of current employing has, and one is prepare tin nano material, and the specific area of nano particle is large, is conducive to more lithium generation electrochemical action, is conducive to the change in volume cushioning its charge and discharge process simultaneously; Secondly tin and other materials are formed composite construction, tin makes negative material, and other materials has cushioning effect, suppresses the bulk effect of tin.Chinese invention patent (Li Changdong etc., a kind of preparation method of lithium ion battery tin antimony nickel alloy negative material, Authorization Notice No. CN102332570B) for substrate, adopts electrodeposition process in substrate, generate tin antimony nickel alloy layer with mesh structural porous carbon cloth.But the method sedimentation time used long (30-120 minute), secondly not mentioned carbon cloth thickness and with tin mass ratio, 3rd the method carbon cloth tin supported used negative pole, directly cannot be used as cathode of lithium battery film, still need to mix with acetylene black, bonding agent to mix and starch, coat on Copper Foil and make cathode of lithium battery film.Chinese invention patent (Dan Zhongqiang etc., the tin-cobalt alloy negative electrode material of lithium ion battery and preparation method, Authorization Notice No. CN100565978C) first on Copper substrate, adhere to one deck tin, then obtain tin-cobalt alloy material by electro-deposition method, electrodeposition time is 0.5-2.5 hour.For improving the tack of Copper substrate surface tin coating; Chinese invention patent (Wang Jianming etc.; electro-deposition-hydro thermal method prepares the method for lithium ionic cell tin negative pole material; Authorization Notice No. CN101478038B) hydrothermal treatment consists is carried out to tin electrode; the method increase the cyclical stability of metal tin electrode, but process loaded down with trivial details, be difficult to large-scale production.
Summary of the invention
The technical problem that the present invention mainly solves is to provide a kind of tin of lithium ion battery and the preparation method of conducting polymer composite negative pole material film, adopt graphite paper as substrate, first in 2-10 minute, prepare tin nanoparticles by electrodeposition process and be deposited on graphite paper surface, electrochemical polymerization tin/conducting polymer composite negative pole material on this basis, conducting polymer is scattered between tin nanoparticles and surface, in tin and conducting polymer composite construction, tin plays the electrochemical action of storage lithium/de-lithium, conductive polymer sub-network plays the same limit of electric action, cushion the change in volume of tin nanoparticles in charge and discharge process, compared to Copper Foil matrix of the prior art, it is little that graphite paper has density, inexpensive, firmly advantage is combined with metallic tin, compared to the grinding needed for carbon cloth matrix, mix slurry, again masking, tin/conducting polymer/graphite paper composite membrane can be directly used in cathode of lithium battery film.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: provide a kind of tin of lithium ion battery and the preparation method of conducting polymer composite negative pole material film, described tin and conducting polymer composite negative pole material film take graphite paper as substrate, the metallic tin of described graphite paper surface deposition is graininess, conductive macromolecular nano fiber is scattered between metallic tin particle and surface, specifically comprises the following steps:
The pre-treatment of a, graphite paper: graphite paper is undertaken cleaning and surface treatment by cleaning fluid in rinse bath;
B, galvanostatic deposition metallic tin: connecting external power source by graphite paper by electrode brush contact is work electrode, and adopt graphite cake to be to electrode, be placed in tin galvanic deposition cell, the tin electrodeposit liquid temperature in tin galvanic deposition cell is 35-80 degree; Adopt galvanostatic deposition, control current density is 0.2-1.2mA/cm
2, sedimentation time is 2-20 minute, and stir bottom tin electrodeposit liquid in electrodeposition process, stir speed (S.S.) is 120-600rpm, obtains tin/graphite paper material;
C, conducting polymer electro-deposition prepare: be placed in high molecular monomer solution groove by the above-mentioned tin/graphite paper material that obtains, and stir bottom the monomer solution in monomer solution groove, stir speed (S.S.) is 120-600rpm;
D, potentiostatic method electrochemistry formated conducting polymer film: connecting external power source by tin/graphite paper material by electrode brush contact is work electrode, be Pt, Cu or graphite flake to electrode, be placed in conducting polymer electrodeposit liquid, regulation voltage is between 0.5-1.2V, sedimentation time is 5-22 minute, and solution temperature is 0-25 degree, stirs bottom conducting polymer electrodeposit liquid, stir speed (S.S.) is 120-600rpm, obtains conducting polymer film;
F, tin and conducting polymer composite negative pole material film are prepared: by conducting polymer film obtained above through rinse bath, the bottom of stirring and washing groove cleaning liquid inside, stir speed (S.S.) is 120-600rpm, remove high polymer monomer and the inorganic salts of conducting polymer film adsorption, finally obtaining conducting polymer is scattered between tin nanoparticles and the tin on surface and conducting polymer composite negative pole material film, by tin and conducting polymer composite negative pole material film through air dry oven, dry temperature is 60-90 degree.
In a preferred embodiment of the present invention, the size of described metallic tin is 0.5-2um; The diameter of described conductive macromolecular nano fiber is 0.1-0.8um.
In a preferred embodiment of the present invention, described graphite paper adopts high-carbon scale graphite through chemical treatment, high-temperature expansion rolled products, phosphorus content: 90-99.5%, thickness: 0.05-0.3mm.
In a preferred embodiment of the present invention, in described step a, the liquid of cleaning fluid is two kinds or whole in deionized water, ethanol, surfactant A, monoethanolamine.
In a preferred embodiment of the present invention, in described step b, the composition of raw materials of tin electrodeposit liquid is: the pink salt of 0.2-2mol/L, the K of 0.2-1.0mol/L
4p
2o
73H
2the ascorbic acid of the NaOH of O, 0.2-1.5mol/L, 0.1-0.5mol/L, wherein, the pH=8.5-10 of tin electrodeposit liquid.
In a preferred embodiment of the present invention, described pink salt adopts solubility pink salt, and described solubility pink salt is at least one in stannic chloride, STANNOUS SULPHATE CRYSTALLINE, sodium stannate.
In a preferred embodiment of the present invention, in described step c monomer solution be aniline, pyrroles, thiophene one or both, concentration is 0.2-2mol/L.
In a preferred embodiment of the present invention, in described steps d, conducting polymer electrodeposit liquid composition of raw materials is: the conductive high polymer monomer solution of 0.05-0.6mol/L, the acid solution of 0.1-1mol/L, the KCl solution of 0.5-1mol/L, the surfactant B solution of 0.1-0.5mol/L, wherein, the pH=2.5-5 of conducting polymer electrodeposit liquid.
In a preferred embodiment of the present invention, described acid solution is one or both in phosphoric acid, sulfuric acid, nitric acid, DBSA.
In a preferred embodiment of the present invention, in described step f, the component of tin and conducting polymer composite negative pole material film and mass percentage content are:
Tin: 80-92%,
Conducting polymer: 8-20%.
The invention has the beneficial effects as follows: the tin of lithium ion battery of the present invention and the preparation method of conducting polymer composite negative pole material film, adopt graphite paper as substrate, first in 2-10 minute, prepare tin nanoparticles by electrodeposition process and be deposited on graphite paper surface, electrochemical polymerization tin/conducting polymer composite negative pole material on this basis, conducting polymer is scattered between tin nanoparticles and surface, in tin and conducting polymer composite construction, tin plays the electrochemical action of storage lithium/de-lithium, conductive polymer sub-network plays the same limit of electric action, cushion the change in volume of tin nanoparticles in charge and discharge process, compared to Copper Foil matrix of the prior art, it is little that graphite paper has density, inexpensive, firmly advantage is combined with metallic tin, compared to the grinding needed for carbon cloth matrix, mix slurry, again masking, tin/conducting polymer/graphite paper composite membrane can be directly used in cathode of lithium battery film.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings, wherein:
Fig. 1 is the schematic flow diagram that the present invention prepares tin/conducting polymer/graphite paper composite membrane;
Fig. 2 is the XRD spectra (except mark graphite spectrum peak, all the other are metallic tin spectrum peak) of the present invention two step electro-deposition tin/conducting polymer/graphite paper composite membrane, and sample is prepared by embodiment 1;
The scanning electron microscope (SEM) photograph of Fig. 3 sample synthesized by the present invention, sample is prepared by embodiment 1;
Fig. 4 is sample chemical property figure synthesized by the present invention, and sample is prepared by embodiment 1.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only a part of embodiment of the present invention, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments all obtained under creative work prerequisite, belong to the scope of protection of the invention.
Refer to Fig. 1, the embodiment of the present invention comprises:
A kind of tin of lithium ion battery and the preparation method of conducting polymer composite negative pole material film, described tin and conducting polymer composite negative pole material film take graphite paper as substrate, the metallic tin of described graphite paper surface deposition is graininess, the size of metallic tin is 0.5-2um, conductive macromolecular nano fiber is scattered between metallic tin particle and surface, the diameter of conductive macromolecular nano fiber is 0.1-0.8um, specifically comprises the following steps:
The pre-treatment of a, graphite paper: graphite paper is undertaken cleaning and surface treatment by cleaning fluid in rinse bath;
B, galvanostatic deposition metallic tin: connecting external power source by graphite paper by electrode brush contact is work electrode, and adopt graphite cake to be to electrode, be placed in tin galvanic deposition cell, the tin electrodeposit liquid temperature in tin galvanic deposition cell is 35-80 degree; Adopt galvanostatic deposition, control current density is 0.2-1.2mA/cm
2, sedimentation time is 2-20 minute, and stir bottom tin electrodeposit liquid in electrodeposition process, stir speed (S.S.) is 120-600rpm, obtains tin/graphite paper material;
C, conducting polymer electro-deposition prepare: be placed in high molecular monomer solution groove by the above-mentioned tin/graphite paper material that obtains, and stir bottom the monomer solution in monomer solution groove, stir speed (S.S.) is 120-600rpm;
D, potentiostatic method electrochemistry formated conducting polymer film: connecting external power source by tin/graphite paper material by electrode brush contact is work electrode, be Pt, Cu or graphite flake to electrode, be placed in conducting polymer electrodeposit liquid, regulation voltage is between 0.5-1.2V, sedimentation time is 5-22 minute, and solution temperature is 0-25 degree, stirs bottom conducting polymer electrodeposit liquid, stir speed (S.S.) is 120-600rpm, obtains conducting polymer film;
F, tin and conducting polymer composite negative pole material film are prepared: by conducting polymer film obtained above through rinse bath, the bottom of stirring and washing groove cleaning liquid inside, stir speed (S.S.) is 120-600rpm, remove high polymer monomer and the inorganic salts of conducting polymer film adsorption, finally obtaining conducting polymer is scattered between tin nanoparticles and the tin on surface and conducting polymer composite negative pole material film, by tin and conducting polymer composite negative pole material film through air dry oven, dry temperature is 60-90 degree.
In above-mentioned, in described step a, the liquid of cleaning fluid is two kinds or whole in deionized water, ethanol, surfactant A, monoethanolamine; In described step b, the composition of raw materials of tin electrodeposit liquid is: the pink salt of 0.2-2mol/L, the K of 0.2-1.0mol/L
4p
2o
73H
2the ascorbic acid of the NaOH of O, 0.2-1.5mol/L, 0.1-0.5mol/L, wherein, the pH=8.5-10 of tin electrodeposit liquid.Wherein, described pink salt adopts solubility pink salt, and described solubility pink salt is at least one in stannic chloride, STANNOUS SULPHATE CRYSTALLINE, sodium stannate.
In described step c monomer solution be aniline, pyrroles, thiophene one or both, concentration is 0.2-2mol/L; The pH=2.5-5 of conducting polymer electrodeposit liquid in described steps d, conducting polymer electrodeposit liquid composition of raw materials is: the conductive high polymer monomer solution of 0.05-0.6mol/L, the acid solution of 0.1-1mol/L, the KCl solution of 0.5-1mol/L, the surfactant B solution of 0.1-0.5mol/L.Wherein, described acid solution is one or both in phosphoric acid, sulfuric acid, nitric acid, DBSA.
The present invention, described graphite paper adopts high-carbon scale graphite through chemical treatment, high-temperature expansion rolled products, phosphorus content: 90-99.5%, thickness: 0.05-0.3mm; Made tin and the component of conducting polymer composite negative pole material film and mass percentage content are:
Tin: 80-92%,
Conducting polymer: 8-20%.
The present invention adopts graphite paper (phosphorus content: 90-99.5%, thickness: 0.05-0.3mm) as substrate, in two steps obtained metallic tin/conductive polymer composite film.(1) adopt electrodeposition process, in 2-10 minute, plated metal tin nanoparticles is in graphite paper surface; (2) adopt chemical polymerization to prepare tin/conducting polymer composite negative pole material, conducting polymer is scattered between tin nanoparticles and surface.In tin and conducting polymer composite construction, metallic tin plays the electrochemical action of storage lithium/de-lithium, limits the reunion of tin nanoparticles, cushioned the change in volume of tin particles in charge and discharge process while conductive polymer sub-network plays electric action.
Embodiment 1:
Thickness be 0.08mm graphite paper through surface clean and process, enter the galvanic deposition cell of metallic tin.Graphite paper is work electrode (connecting external power source by electrode brush contact), and thickness is the graphite cake of 1cm is to electrode, and tin electrodeposit liquid configures: the sodium stannate of 0.6mol/L, the K of 0.2mol/L
4p
2o
73H
2the ascorbic acid of the NaOH of O, 0.2mol/L, 0.25mol/L, the H of 0.05mol/L
2o
2; Tank liquor pH=9; Tank liquor temperature is 60 degree; Electro-deposition current density is 0.6mA/cm
2, sedimentation time is 5 minutes, tank liquor stir speed (S.S.) 180rpm;
Be placed in by tin/graphite paper material in high molecular monomer solution groove, trench bottom stirs, stir speed (S.S.) 120rpm.Then enter conducting polymer dislodger, tin/graphite paper is work electrode (connecting external power source by electrode brush contact), is the Pt sheet that 0.5mm is thick to electrode.Conducting polymer electrodeposit liquid configures: the aniline solution of 0.05mol/L, the sulfuric acid solution of 1mol/L, the KCl solution of 0.5mol/L, the surfactant B solution of 0.1mol/L, tank liquor pH=2.5, regulation voltage is 0.6V, and sedimentation time is 15 minutes, tank liquor temperature is 25 degree, tank liquor stir speed (S.S.) 120rpm;
After two step depositions terminate, composite membrane, through rinse bath, removes high polymer monomer and the inorganic salts of absorption; Tin/polyaniline/graphite paper composite lithium ion battery negative electrode film is obtained through 90 degree of air dry ovens.The bright graphite paper surface of XRD test chart is metallic tin crystalline phase (see accompanying drawing 2), and the metallic tin granularity of deposition is that 0.5-1um(is shown in accompanying drawing 3), elemental composition analysis shows that metallic tin and polyaniline mass ratio are 89:11.This example gained sample film is directly as cathode of lithium battery film, and after 30 circulations, specific capacity remains on 650mAh/g.
Embodiment 2:
Thickness be 0.2mm graphite paper through surface clean, enter the galvanic deposition cell of metallic tin.Graphite paper is work electrode (connecting external power source by electrode brush contact), and thickness is the graphite cake of 1cm is to electrode.Tin electrodeposit liquid configures: the sodium stannate of 0.4mol/L, the K of 0.2mol/L
4p
2o
73H
2the ascorbic acid of the NaOH of O, 0.2mol/L, 0.25mol/L, the H of 0.05mol/L
2o
2; Tank liquor pH=9; Tank liquor temperature is 60 degree; Electro-deposition current density is 0.8mA/cm
2, sedimentation time is 10 minutes, tank liquor stir speed (S.S.) 180rpm;
Be placed in by tin/graphite paper material in high molecular monomer solution groove, bottom is stirred, stir speed (S.S.) 120rpm.Then enter conducting polymer dislodger, tin/graphite paper is work electrode (connecting external power source by electrode brush contact), is the Pt sheet that 0.5mm is thick to electrode.Conducting polymer electrodeposit liquid configures: the aniline solution of 0.05mol/L, the sulfuric acid solution of 1mol/L, the KCl solution of 0.5mol/L, the surfactant B solution of 0.1mol/L, tank liquor pH=2.5, regulation voltage is 0.6V, and sedimentation time is 10 minutes, tank liquor temperature is 25 degree, tank liquor stir speed (S.S.) 120rpm;
After two step depositions terminate, composite membrane, through rinse bath, removes high polymer monomer and the inorganic salts of adsorption; Tin/polyaniline/graphite paper composite lithium ion battery negative electrode film is obtained through 90 degree of air dry ovens.The metallic tin of deposition is nano particle distribution, and granularity 1-1.5um, elemental composition analysis shows that metallic tin and polyaniline mass ratio are 94:6.This example gained sample film is directly as cathode of lithium battery film, and after 30 circulations, capacity remains on 450mAh/g.
Embodiment 3:
Thickness be 0.08mm graphite paper through surface clean, enter the galvanic deposition cell of metallic tin.Graphite paper is work electrode (connecting external power source by electrode brush contact), and thickness is the graphite cake of 1cm is to electrode.Tin electrodeposit liquid configures: the STANNOUS SULPHATE CRYSTALLINE of 0.6mol/L, the K of 0.2mol/L
4p
2o
73H
2the ascorbic acid of the NaOH of O, 0.3mol/L, 0.25mol/L, the H of 0.05mol/L
2o
2; Tank liquor pH=10; Tank liquor temperature is 70 degree; Electro-deposition current density is 0.2mA/cm
2, sedimentation time is 10 minutes, tank liquor stir speed (S.S.) 180rpm;
Tin/graphite paper material is placed in high molecular monomer solution groove, bottom stir speed (S.S.) 120rpm.Then enter conducting polymer dislodger, tin/graphite paper is work electrode (connecting external power source by electrode brush contact), is the Pt sheet that 0.5mm is thick to electrode.Conducting polymer electrodeposit liquid configures: the aniline solution of 0.05mol/L, the sulfuric acid solution of 1mol/L, the KCl solution of 0.5mol/L, the surfactant B solution of 0.1mol/L, tank liquor pH=2.5, regulation voltage is 0.7V, and sedimentation time is 15 minutes, tank liquor temperature is 5 degree, tank liquor stir speed (S.S.) 120rpm;
After two step depositions terminate, composite membrane, through rinse bath, removes high polymer monomer and the inorganic salts of absorption; Tin/polyaniline/graphite paper composite lithium ion battery negative electrode film is obtained through 90 degree of air dry ovens.The metallic tin of deposition is nano particle distribution, and granularity 0.2-0.7um, elemental composition analysis shows that metallic tin and polyaniline mass ratio are 80:20.This example gained sample film is directly as cathode of lithium battery film, and after 30 circulations, capacity remains on 455mAh/g.
Embodiment 4:
Thickness be 0.05mm graphite paper through surface clean, enter the galvanic deposition cell of metallic tin.Graphite paper is work electrode (connecting external power source by electrode brush contact), and thickness is the graphite cake of 1cm is to electrode.Tin electrodeposit liquid configures: the STANNOUS SULPHATE CRYSTALLINE of 0.6mol/L, the K of 0.2mol/L
4p
2o
73H
2the ascorbic acid of the NaOH of O, 0.3mol/L, 0.25mol/L, the H of 0.1mol/L
2o
2; Tank liquor pH=10; Tank liquor temperature is 70 degree; Electro-deposition current density is 0.6mA/cm
2, sedimentation time is 10 minutes, tank liquor stir speed (S.S.) 180rpm;
Tin/graphite paper material is placed in high molecular monomer solution groove, bottom stir speed (S.S.) 120rpm.Then enter conducting polymer dislodger, tin/graphite paper is work electrode (connecting external power source by electrode brush contact), is the Cu sheet that 1mm is thick to electrode.Conducting polymer electrodeposit liquid configures: the aniline solution of 0.05mol/L, the sulfuric acid solution of 1mol/L, the KCl solution of 0.5mol/L, the surfactant B solution of 0.1mol/L, tank liquor pH=2.5, regulation voltage is 0.7V, and sedimentation time is 8 minutes, tank liquor temperature is 5 degree, tank liquor stir speed (S.S.) 120rpm;
After two step depositions terminate, composite membrane, through rinse bath, removes high polymer monomer and the inorganic salts of absorption; Tin/polyaniline/graphite paper composite lithium ion battery negative electrode film is obtained through 90 degree of air dry ovens.The metallic tin of deposition is nano particle distribution, and granularity 0.5-1.0um, elemental composition analysis shows that metallic tin and polyaniline mass ratio are 92:8.This example gained sample film is directly as cathode of lithium battery film, and after 30 circulations, capacity remains on 631mAh/g.
Embodiment 5:
Thickness be 0.2mm graphite paper through surface clean, enter the galvanic deposition cell of metallic tin.Graphite paper is work electrode (connecting external power source by electrode brush contact), and thickness is the graphite cake of 1cm is to electrode.Tin electrodeposit liquid configures: the stannic chloride of 0.6mol/L, the K of 0.2mol/L
4p
2o
73H
2the ascorbic acid of the NaOH of O, 0.3mol/L, 0.25mol/L, the H of 0.1mol/L
2o
2; Tank liquor pH=9; Tank liquor temperature is 25 degree; Electro-deposition current density is 1.2mA/cm
2, sedimentation time is 10 minutes, tank liquor stir speed (S.S.) 240rpm;
Tin/graphite paper material is placed in high molecular monomer solution groove, bottom stir speed (S.S.) 120rpm.Then enter conducting polymer dislodger, tin/graphite paper is work electrode (connecting external power source by electrode brush contact), is the Cu sheet that 1mm is thick to electrode.Conducting polymer electrodeposit liquid configures: the aniline solution of 0.1mol/L, the sulfuric acid solution of 1mol/L, the KCl solution of 0.5mol/L, the surfactant B solution of 0.1mol/L, tank liquor pH=1.5, regulation voltage is 0.8V, and sedimentation time is 10 minutes, tank liquor temperature is 5 degree, tank liquor stir speed (S.S.) 240rpm;
After two step depositions terminate, composite membrane, through rinse bath, removes high polymer monomer and the inorganic salts of absorption; Tin/polyaniline/graphite paper composite lithium ion battery negative electrode film is obtained through 90 degree of air dry ovens.The metallic tin of deposition is nano particle distribution, and granularity 1-2um, elemental composition analysis shows that metallic tin and polyaniline mass ratio are 90:10.This example gained sample film is directly as cathode of lithium battery film, and after 30 circulations, capacity remains on 431mAh/g.
The tin of lithium ion battery provided by the invention and the preparation method of conducting polymer composite negative pole material film, tool has the following advantages:
(1) prepare tin negative pole material with electrodeposition process, preparation condition is gentle, good film-forming property, and nanoscale tin particles has good chemical property;
(2), between tin nanoparticles and surface deposition one deck conducting polymer, in electrochemical process, play the bulk effect of the embedding lithium of buffering tin/de-lithium, prevent particle agglomeration, ensure that the cyclical stability of material;
(3) adopt graphite paper to be electro-deposition substrate, have that quality is light, corrosion-resistant, pliability, after surface deposition tin/conductive polymer composite, can directly be used as lithium ion battery negative film.
The tin of lithium ion battery that the present invention discloses and the preparation method of conducting polymer composite negative pole material film, adopt graphite paper as substrate, first in 2-10 minute, prepare tin nanoparticles by electrodeposition process and be deposited on graphite paper surface, electrochemical polymerization tin/conducting polymer composite negative pole material on this basis, conducting polymer is scattered between tin nanoparticles and surface, in tin and conducting polymer composite construction, tin plays the electrochemical action of storage lithium/de-lithium, conductive polymer sub-network plays the same limit of electric action, cushion the change in volume of tin nanoparticles in charge and discharge process, compared to Copper Foil matrix of the prior art, it is little that graphite paper has density, inexpensive, firmly advantage is combined with metallic tin, compared to the grinding needed for carbon cloth matrix, mix slurry, again masking, tin/conducting polymer/graphite paper composite membrane can be directly used in cathode of lithium battery film.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize description of the present invention to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical field, be all in like manner included in scope of patent protection of the present invention.
Claims (10)
1. the tin of a lithium ion battery and the preparation method of conducting polymer composite negative pole material film, it is characterized in that, described tin and conducting polymer composite negative pole material film are using graphite paper as substrate, the metallic tin of described graphite paper surface deposition is graininess, conductive macromolecular nano fiber is scattered between metallic tin particle and surface, specifically comprises the following steps:
The pre-treatment of a, graphite paper: graphite paper is undertaken cleaning and surface treatment by cleaning fluid in rinse bath;
B, galvanostatic deposition metallic tin: using graphite paper as work electrode, it connects external power source by electrode brush contact, and adopt graphite cake to be to electrode, be placed in tin galvanic deposition cell, the tin electrodeposit liquid temperature in tin galvanic deposition cell is 35-80 degree Celsius; Adopt galvanostatic deposition, control current density is 0.2-1.2mA/cm
2, sedimentation time is 2-10 minute, and stir bottom tin electrodeposit liquid in electrodeposition process, stir speed (S.S.) is 120-600rpm, obtains tin/graphite paper material;
C, conducting polymer electro-deposition prepare: be placed in by tin obtained above/graphite paper material in high molecular monomer solution groove, and stir bottom the monomer solution in monomer solution groove, stir speed (S.S.) is 120-600rpm;
D, potentiostatic method electrochemistry formated conducting polymer film: using graphite paper as work electrode, it connects external power source by electrode brush contact, be Pt, Cu or graphite flake to electrode, be placed in conducting polymer electrodeposit liquid, regulation voltage is between 0.5-1.2V, and sedimentation time is 5-22 minute, solution temperature is 0-25 degree Celsius, stir bottom conducting polymer electrodeposit liquid, stir speed (S.S.) is 120-600rpm, obtains conducting polymer film;
F, tin and conducting polymer composite negative pole material film are prepared: by conducting polymer film obtained above through rinse bath, the bottom of stirring and washing groove cleaning liquid inside, stir speed (S.S.) is 120-600rpm, remove high polymer monomer and the inorganic salts of conducting polymer film adsorption, finally obtaining conducting polymer is scattered between tin nanoparticles and the tin on surface and conducting polymer composite negative pole material film, by tin and conducting polymer composite negative pole material film through air dry oven, dry temperature is 60-90 degree Celsius.
2. the tin of lithium ion battery according to claim 1 and the preparation method of conducting polymer composite negative pole material film, is characterized in that, the size of described metallic tin is 0.5-2 μm; The diameter of described conductive macromolecular nano fiber is 0.1-0.8 μm.
3. the tin of lithium ion battery according to claim 1 and the preparation method of conducting polymer composite negative pole material film, it is characterized in that, described graphite paper adopts by the high-carbon scale graphite product that high-temperature expansion rolling obtains after chemical treatment, phosphorus content: 90-99.5%, thickness: 0.05-0.3mm.
4. the tin of lithium ion battery according to claim 1 and the preparation method of conducting polymer composite negative pole material film, it is characterized in that, in described step a, the liquid of cleaning fluid is two kinds or whole in deionized water, ethanol, surfactant A, monoethanolamine.
5. the tin of lithium ion battery according to claim 1 and the preparation method of conducting polymer composite negative pole material film, it is characterized in that, in described step b, the composition of raw materials of tin electrodeposit liquid is: the pink salt of 0.2-2mol/L, the K of 0.2-1.0mol/L
4p
2o
73H
2the ascorbic acid of the NaOH of O, 0.2-1.5mol/L, 0.1-0.5mol/L, wherein, the pH=8.5-10 of tin electrodeposit liquid.
6. the tin of lithium ion battery according to claim 5 and the preparation method of conducting polymer composite negative pole material film, it is characterized in that, described pink salt adopts solubility pink salt, and described solubility pink salt is at least one in stannic chloride, STANNOUS SULPHATE CRYSTALLINE, sodium stannate.
7. the tin of lithium ion battery according to claim 1 and the preparation method of conducting polymer composite negative pole material film, is characterized in that, in described step c monomer solution be aniline, pyrroles, thiophene one or both, concentration is 0.2-2mol/L.
8. the tin of lithium ion battery according to claim 1 and the preparation method of conducting polymer composite negative pole material film, it is characterized in that, in described steps d, conducting polymer electrodeposit liquid composition of raw materials is: the conductive high polymer monomer solution of 0.05-0.6mol/L, the acid solution of 0.1-1mol/L, the KCl solution of 0.5-1mol/L, the surfactant B solution of 0.1-0.5mol/L, wherein, the pH=2.5-5 of conducting polymer electrodeposit liquid.
9. the tin of lithium ion battery according to claim 8 and the preparation method of conducting polymer composite negative pole material film, is characterized in that, described acid solution is one or both in phosphoric acid, sulfuric acid, nitric acid, DBSA.
10. the tin of lithium ion battery according to claim 1 and the preparation method of conducting polymer composite negative pole material film, is characterized in that, in described step f, the component of tin and conducting polymer composite negative pole material film and mass percentage content are:
Tin: 80-92%,
Conducting polymer: 8-20%.
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| CN108878796A (en) * | 2017-05-16 | 2018-11-23 | 天津大学 | Graphene modified conductive polymer gel and its preparation method and application |
| CN108122688A (en) * | 2017-11-24 | 2018-06-05 | 西安工业大学 | A kind of preparation method of flexible electrochemical electrode available for all-solid-state power storage device |
| CN114976028A (en) * | 2022-01-10 | 2022-08-30 | 河南超力新能源有限公司 | Composite current collector for zinc secondary battery, preparation method of composite current collector, negative plate and zinc secondary battery |
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