CN103825011A - Preparation method of tin of lithium ion battery and conductive polymer composite cathode material membrane - Google Patents
Preparation method of tin of lithium ion battery and conductive polymer composite cathode material membrane Download PDFInfo
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- CN103825011A CN103825011A CN201410070298.3A CN201410070298A CN103825011A CN 103825011 A CN103825011 A CN 103825011A CN 201410070298 A CN201410070298 A CN 201410070298A CN 103825011 A CN103825011 A CN 103825011A
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- 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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- 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 preparation method of tin of a lithium ion battery and a conductive polymer composite cathode material membrane. According to the invention, the tin of the lithium ion battery and the conducting polymer composite cathode material membrane take graphite paper as a substrate, metallic tin deposited on the surface of the graphite paper is in a granular state, and the conductive polymer nano fiber is dispersed between the metallic tin particles and on the surface of the metallic tin particles. The method comprises the following steps: a)pre-treating the graphite paper; b)depositing metallic tin by constant current; c)preparing conductive polymer electrodeposition; d)performing electrochemical synthesis on the conductive polymer membrane by a constant potential method; and f) preparing the tin of the lithium ion battery and the conductive polymer composite cathode material membrane. According to the invention, conductive polymer is dispersed between the metallic tin particles and on the surface of the metallic tin particles, tin plays a electrochemistry role for storing lithium/removing lithium, a conductive polymer network has the conductive effect, and is capable of simultaneously limiting and buffering the volume change of the tin nano particles during a charge and discharge process, the particle agglomeration is avoided, and the cycle stability of the material can be ensured.
Description
Technical field
The present invention relates to the field of lithium battery material, particularly relate to a kind of preparation method of tin and conducting polymer composite negative pole material film of lithium ion battery.
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 mainly depends on the raising of anode and cathode active materials performance.At present conventional lithium ion battery negative material is take material with carbon element as main, 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 pole material become the hot subject that improves performance of lithium ion battery.
Metallic tin can carry out reversible alloying with lithium and react with removal alloying, has good embedding lithium/de-lithium performance, and to solvent selectivity close friend, 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, CN 1786221 A) 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, under metal alloy class electrode material normal temperature and pressure conditions prepared by electrodeposition process, can complete, 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 storage lithium performance of metallic tin deposition layer for lithium ion battery, China YouSe Acta Metallurgica Sinica, 2010,20,1155) take Copper Foil as matrix, adopt electrodeposition process to prepare tin deposition layer, and be made into lithium ion battery tin negative pole, and its problem is, in electrochemistry cyclic process, tin particles is reunited and is caused cycle performance significantly to reduce.
Because metallic tin is in removal lithium embedded process repeatedly, tin particles is easily assembled and is caused activity decreased 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 adopting at present has, and the one, prepare tin nano material, the specific area of nano particle is large, is conducive to more lithium generation electrochemical action, is conducive to cushion the change in volume of its charge and discharge process simultaneously; Secondly tin and other materials are formed to composite construction, tin is made 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, Granted publication CN 102332570 B), take mesh structural porous carbon cloth as substrate, adopts electrodeposition process in substrate, to generate tin antimony nickel alloy layer.But the method sedimentation time used long (30-120 minute), secondly not mentioned carbon cloth thickness and with tin mass ratio, the 3rd the method carbon cloth tin supported used negative pole, cannot directly be used as cathode of lithium battery film, still need to mix with acetylene black, bonding agent and mix slurry, coat and on Copper Foil, 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, Granted publication CN 100565978 C) first on copper matrix, 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 matrix surface tin coating; Chinese invention patent (Wang Jianming etc.; electro-deposition-hydro thermal method is prepared the method for lithium ionic cell tin negative pole material; Granted publication CN 101478038 B) tin electrode is carried out to hydrothermal treatment consists; the method has improved 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 preparation method of tin and conducting polymer composite negative pole material film of lithium ion battery, adopt graphite paper as substrate, first in 2-10 minute, prepare sijna rice grain 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 sijna rice grain and surface, in tin and conducting polymer composite construction, tin plays the electrochemical action of storage lithium/de-lithium, restriction when conductive polymer sub-network plays electric action, cushion the change in volume of sijna rice grain in charge and discharge process, than Copper Foil matrix of the prior art, it is little that graphite paper has density, inexpensive, be combined firmly advantage with metallic tin, than the required grinding of carbon cloth matrix, mix slurry, masking again, 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: the preparation method that a kind of tin and conducting polymer composite negative pole material film of lithium ion battery are provided, described tin and conducting polymer composite negative pole material film are 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 cleaned and surface treatment by cleaning fluid in rinse bath;
B, galvanostatic deposition metallic tin: brushing contact connection external power source by electrode is work electrode by graphite paper, and adopting graphite cake is to electrode, is placed in tin galvanic deposition cell, and 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, stirs tin electrodeposit liquid bottom in electrodeposition process, stir speed (S.S.) is 120-600rpm, obtains tin/graphite paper material;
C, conducting polymer electro-deposition are prepared: above-mentioned tin/graphite paper material that obtains is placed in high molecular monomer solution groove, stirs the monomer solution bottom in monomer solution groove, stir speed (S.S.) is 120-600rpm;
D, potentiostatic method electrochemistry compositing conducting polymeric membrane: brushing contact connection external power source by electrode is work electrode by tin/graphite paper material, 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 conducting polymer electrodeposit liquid bottom, stir speed (S.S.) is 120-600rpm, obtains conducting polymer film;
F, prepared tin and conducting polymer composite negative pole material film: 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 sijna rice grain and tin and the conducting polymer composite negative pole material film on surface, by tin and conducting polymer composite negative pole material film process 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 0.1-0.8 um.
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 in deionized water, ethanol, surfactant A, monoethanolamine two kinds or all.
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 0.2-2 mol/L, the K of 0.2-1.0mol/L
4p
2o
73H
2o, the NaOH of 0.2-1.5mol/L, the ascorbic acid of 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 is one or both of aniline, pyrroles, thiophene, and concentration is 0.2-2 mol/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, component and the mass percentage content of tin and conducting polymer composite negative pole material film are:
Tin: 80-92%,
Conducting polymer: 8-20%.
The invention has the beneficial effects as follows: the preparation method of the tin of lithium ion battery of the present invention and conducting polymer composite negative pole material film, adopt graphite paper as substrate, first in 2-10 minute, prepare sijna rice grain 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 sijna rice grain and surface, in tin and conducting polymer composite construction, tin plays the electrochemical action of storage lithium/de-lithium, restriction when conductive polymer sub-network plays electric action, cushion the change in volume of sijna rice grain in charge and discharge process, than Copper Foil matrix of the prior art, it is little that graphite paper has density, inexpensive, be combined firmly advantage with metallic tin, than the required grinding of carbon cloth matrix, mix slurry, masking again, 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 of required use during embodiment is described is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing, 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's two step electro-deposition tin/conducting polymer/graphite paper composite membranes, and sample is prepared by embodiment 1;
Fig. 3 is the scanning electron microscope (SEM) photograph of synthesized sample of the present invention, and sample is prepared by embodiment 1;
Fig. 4 is synthesized sample chemical property figure of the present invention, and sample is prepared by embodiment 1.
Embodiment
To the technical scheme in the embodiment of the present invention be clearly and completely described below, obviously, described embodiment is only a part of embodiment of the present invention, rather than whole embodiment.Based on the embodiment in the present invention, those of ordinary skills, not making all other embodiment that obtain under creative work prerequisite, belong to the scope of protection of the invention.
Refer to Fig. 1, the embodiment of the present invention comprises:
The preparation method of a kind of tin of lithium ion battery and conducting polymer composite negative pole material film, described tin and conducting polymer composite negative pole material film are 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 0.1-0.8 um, specifically comprises the following steps:
The pre-treatment of a, graphite paper: graphite paper is cleaned and surface treatment by cleaning fluid in rinse bath;
B, galvanostatic deposition metallic tin: brushing contact connection external power source by electrode is work electrode by graphite paper, and adopting graphite cake is to electrode, is placed in tin galvanic deposition cell, and the tin electrodeposit liquid temperature in tin galvanic deposition cell is 35-80 degree; Adopt galvanostatic deposition, controlling current density is 0.2-1.2 mA/cm
2, sedimentation time is 2-20 minute, stirs tin electrodeposit liquid bottom in electrodeposition process, stir speed (S.S.) is 120-600rpm, obtains tin/graphite paper material;
C, conducting polymer electro-deposition are prepared: above-mentioned tin/graphite paper material that obtains is placed in high molecular monomer solution groove, stirs the monomer solution bottom in monomer solution groove, stir speed (S.S.) is 120-600rpm;
D, potentiostatic method electrochemistry compositing conducting polymeric membrane: brushing contact connection external power source by electrode is work electrode by tin/graphite paper material, 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 conducting polymer electrodeposit liquid bottom, stir speed (S.S.) is 120-600rpm, obtains conducting polymer film;
F, prepared tin and conducting polymer composite negative pole material film: 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 sijna rice grain and tin and the conducting polymer composite negative pole material film on surface, by tin and conducting polymer composite negative pole material film process air dry oven, dry temperature is 60-90 degree.
In above-mentioned, in described step a, the liquid of cleaning fluid is in deionized water, ethanol, surfactant A, monoethanolamine two kinds or all; In described step b, the composition of raw materials of tin electrodeposit liquid is: the pink salt of 0.2-2 mol/L, the K of 0.2-1.0mol/L
4p
2o
73H
2o, the NaOH of 0.2-1.5mol/L, the ascorbic acid of 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 is one or both of aniline, pyrroles, thiophene, and concentration is 0.2-2 mol/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; Component and the mass percentage content of made tin and conducting polymer composite negative pole material film 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, makes in two steps metallic tin/conductive polymer composite film.(1) adopt electrodeposition process, in 2-10 minute, plated metal sijna rice grain is in graphite paper surface; (2) adopt chemical polymerization to prepare tin/conducting polymer composite negative pole material, conducting polymer is scattered between sijna rice grain and surface.In tin and conducting polymer composite construction, metallic tin plays the electrochemical action of storage lithium/de-lithium, conductive polymer sub-network when playing electric action, limited sijna rice grain reunion, cushioned the change in volume of tin particles in charge and discharge process.
Embodiment 1:
Thickness is 0.08mm graphite paper process surface clean and processing, enters the galvanic deposition cell of metallic tin.Graphite paper is work electrode (brushes contact by electrode and connect external power source), and thickness is that the graphite cake of 1 cm is to electrode, tin electrodeposit liquid configuration: the sodium stannate of 0.6 mol/L, the K of 0.2 mol/L
4p
2o
73H
2o, the NaOH of 0.2 mol/L, the ascorbic acid of 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 0.6 mA/cm
2, sedimentation time is 5 minutes, tank liquor stir speed (S.S.) 180 rpm;
Tin/graphite paper material is placed in high molecular monomer solution groove, and trench bottom stirs, stir speed (S.S.) 120 rpm.Then enter conducting polymer dislodger, tin/graphite paper is work electrode (brushes contact by electrode and connect external power source), is the Pt sheet that 0.5mm is thick to electrode.Conducting polymer electrodeposit liquid configuration: the aniline solution of 0.05 mol/L, the sulfuric acid solution of 1mol/L, the KCl solution of 0.5mol/L, the surfactant B solution of 0.1 mol/L, tank liquor pH=2.5, regulation voltage is 0.6 V, sedimentation time is 15 minutes, tank liquor temperature is 25 degree, tank liquor stir speed (S.S.) 120 rpm;
After two step depositions finish, composite membrane, through rinse bath, is removed high polymer monomer and the inorganic salts of absorption; Make tin/polyaniline/graphite paper composite lithium ion battery negative electrode film through 90 degree air dry ovens.The bright graphite paper of XRD test chart surface is metallic tin crystalline phase (seeing accompanying drawing 2), and the metallic tin granularity of deposition is that 0.5-1 um(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 is 0.2mm graphite paper process surface clean, enters the galvanic deposition cell of metallic tin.Graphite paper is work electrode (brushes contact by electrode and connect external power source), and the graphite cake that thickness is 1cm is to electrode.Tin electrodeposit liquid configuration: the sodium stannate of 0.4mol/L, the K of 0.2mol/L
4p
2o
73H
2o, the NaOH of 0.2mol/L, the ascorbic acid of 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;
Tin/graphite paper material is placed in high molecular monomer solution groove, and stir bottom, stir speed (S.S.) 120rpm.Then enter conducting polymer dislodger, tin/graphite paper is work electrode (brushes contact by electrode and connect external power source), is the Pt sheet that 0.5mm is thick to electrode.Conducting polymer electrodeposit liquid configuration: 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 0.6 V, sedimentation time is 10 minutes, tank liquor temperature is 25 degree, tank liquor stir speed (S.S.) 120rpm;
After two step depositions finish, composite membrane, through rinse bath, is removed high polymer monomer and the inorganic salts of adsorption; Make tin/polyaniline/graphite paper composite lithium ion battery negative electrode film through 90 degree air dry ovens.The metallic tin of deposition is that nano particle distributes, granularity 1-1.5um, and 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, Capacitance reserve is at 450mAh/g.
Embodiment 3:
Thickness is 0.08mm graphite paper process surface clean, enters the galvanic deposition cell of metallic tin.Graphite paper is work electrode (brushes contact by electrode and connect external power source), and the graphite cake that thickness is 1cm is to electrode.Tin electrodeposit liquid configuration: the STANNOUS SULPHATE CRYSTALLINE of 0.6mol/L, the K of 0.2mol/L
4p
2o
73H
2o, the NaOH of 0.3mol/L, the ascorbic acid of 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 0.2 mA/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 to bottom stir speed (S.S.) 120rpm.Then enter conducting polymer dislodger, tin/graphite paper is work electrode (brushes contact by electrode and connect external power source), is the Pt sheet that 0.5mm is thick to electrode.Conducting polymer electrodeposit liquid configuration: 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, sedimentation time is 15 minutes, tank liquor temperature is 5 degree, tank liquor stir speed (S.S.) 120rpm;
After two step depositions finish, composite membrane, through rinse bath, is removed high polymer monomer and the inorganic salts of absorption; Make tin/polyaniline/graphite paper composite lithium ion battery negative electrode film through 90 degree air dry ovens.The metallic tin of deposition is that nano particle distributes, granularity 0.2-0.7um, and 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, Capacitance reserve is at 455mAh/g.
Embodiment 4:
Thickness is 0.05mm graphite paper process surface clean, enters the galvanic deposition cell of metallic tin.Graphite paper is work electrode (brushes contact by electrode and connect external power source), and the graphite cake that thickness is 1cm is to electrode.Tin electrodeposit liquid configuration: the STANNOUS SULPHATE CRYSTALLINE of 0.6mol/L, the K of 0.2mol/L
4p
2o
73H
2o, the NaOH of 0.3mol/L, the ascorbic acid of 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 to bottom stir speed (S.S.) 120rpm.Then enter conducting polymer dislodger, tin/graphite paper is work electrode (brushes contact by electrode and connect external power source), is the Cu sheet that 1mm is thick to electrode.Conducting polymer electrodeposit liquid configuration: the aniline solution of 0.05 mol/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, sedimentation time is 8 minutes, tank liquor temperature is 5 degree, tank liquor stir speed (S.S.) 120rpm;
After two step depositions finish, composite membrane, through rinse bath, is removed high polymer monomer and the inorganic salts of absorption; Make tin/polyaniline/graphite paper composite lithium ion battery negative electrode film through 90 degree air dry ovens.The metallic tin of deposition is that nano particle distributes, granularity 0.5-1.0um, and 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, Capacitance reserve is at 631mAh/g.
Embodiment 5:
Thickness is 0.2 mm graphite paper process surface clean, enters the galvanic deposition cell of metallic tin.Graphite paper is work electrode (brushes contact by electrode and connect external power source), and thickness is that the graphite cake of 1 cm is to electrode.Tin electrodeposit liquid configuration: the stannic chloride of 0.6mol/L, the K of 0.2mol/L
4p
2o
73H
2o, the NaOH of 0.3mol/L, the ascorbic acid of 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 to bottom stir speed (S.S.) 120rpm.Then enter conducting polymer dislodger, tin/graphite paper is work electrode (brushes contact by electrode and connect external power source), is the Cu sheet that 1mm is thick to electrode.Conducting polymer electrodeposit liquid configuration: the aniline solution of 0.1mol/L, the sulfuric acid solution of 1 mol/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, sedimentation time is 10 minutes, tank liquor temperature is 5 degree, tank liquor stir speed (S.S.) 240rpm;
After two step depositions finish, composite membrane, through rinse bath, is removed high polymer monomer and the inorganic salts of absorption; Make tin/polyaniline/graphite paper composite lithium ion battery negative electrode film through 90 degree air dry ovens.The metallic tin of deposition is that nano particle distributes, granularity 1-2um, and 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, Capacitance reserve is at 431mAh/g.
The preparation method of the tin of lithium ion battery provided by the invention and conducting polymer composite negative pole material film, tool has the following advantages:
(1) prepare tin negative pole material with electrodeposition process, preparation condition gentleness, good film-forming property, nanoscale tin particles has good chemical property;
(2) between sijna rice grain and surface deposition one deck conducting polymer, in electrochemical process, play buffering tin embedding lithium/de-lithium bulk effect, prevent particle agglomeration, guaranteed the cyclical stability of material;
(3) adopting graphite paper is electro-deposition substrate, has 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 and the preparation method of conducting polymer composite negative pole material film that the present invention discloses, adopt graphite paper as substrate, first in 2-10 minute, prepare sijna rice grain 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 sijna rice grain and surface, in tin and conducting polymer composite construction, tin plays the electrochemical action of storage lithium/de-lithium, restriction when conductive polymer sub-network plays electric action, cushion the change in volume of sijna rice grain in charge and discharge process, than Copper Foil matrix of the prior art, it is little that graphite paper has density, inexpensive, be combined firmly advantage with metallic tin, than the required grinding of carbon cloth matrix, mix slurry, masking again, 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 limit the scope of the claims of the present invention; every equivalent structure or conversion of equivalent flow process that utilizes description of the present invention to do; 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 preparation method of the tin of a lithium ion battery and conducting polymer composite negative pole material film, it is characterized in that, described tin and conducting polymer composite negative pole material film are 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 cleaned and surface treatment by cleaning fluid in rinse bath;
B, galvanostatic deposition metallic tin: brushing contact connection external power source by electrode is work electrode by graphite paper, and adopting graphite cake is to electrode, is placed in tin galvanic deposition cell, and 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, stirs tin electrodeposit liquid bottom in electrodeposition process, stir speed (S.S.) is 120-600rpm, obtains tin/graphite paper material;
C, conducting polymer electro-deposition are prepared: above-mentioned tin/graphite paper material that obtains is placed in high molecular monomer solution groove, stirs the monomer solution bottom in monomer solution groove, stir speed (S.S.) is 120-600rpm;
D, potentiostatic method electrochemistry compositing conducting polymeric membrane: brushing contact connection external power source by electrode is work electrode by tin/graphite paper material, 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 conducting polymer electrodeposit liquid bottom, stir speed (S.S.) is 120-600rpm, obtains conducting polymer film;
F, prepared tin and conducting polymer composite negative pole material film: 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 sijna rice grain and tin and the conducting polymer composite negative pole material film on surface, by tin and conducting polymer composite negative pole material film process air dry oven, dry temperature is 60-90 degree.
2. the preparation method of the tin of lithium ion battery according to claim 1 and conducting polymer composite negative pole material film, is characterized in that, the size of described metallic tin is 0.5-2um; The diameter of described conductive macromolecular nano fiber is 0.1-0.8 um.
3. the preparation method of the tin of lithium ion battery according to claim 1 and conducting polymer composite negative pole material film, it is characterized in that, 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.
4. the preparation method of the tin of lithium ion battery according to claim 1 and conducting polymer composite negative pole material film, it is characterized in that, in described step a, the liquid of cleaning fluid is in deionized water, ethanol, surfactant A, monoethanolamine two kinds or all.
5. the preparation method of the tin of lithium ion battery according to claim 1 and conducting polymer composite negative pole material film, is characterized in that, in described step b, the composition of raw materials of tin electrodeposit liquid is: the pink salt of 0.2-2 mol/L, the K of 0.2-1.0mol/L
4p
2o
73H
2o, the NaOH of 0.2-1.5mol/L, the ascorbic acid of 0.1-0.5mol/L, wherein, the pH=8.5-10 of tin electrodeposit liquid.
6. the preparation method of the tin of lithium ion battery according to claim 5 and 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 preparation method of the tin of lithium ion battery according to claim 1 and conducting polymer composite negative pole material film, is characterized in that, in described step c, monomer solution is one or both of aniline, pyrroles, thiophene, and concentration is 0.2-2 mol/L.
8. the preparation method of the tin of lithium ion battery according to claim 1 and 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 preparation method of the tin of lithium ion battery according to claim 8 and 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 preparation method of the tin of lithium ion battery according to claim 1 and conducting polymer composite negative pole material film, is characterized in that, in described step f, component and the mass percentage content of tin and conducting polymer composite negative pole material film are:
Tin: 80-92%,
Conducting polymer: 8-20%.
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