Preparation method of tin of lithium ion battery and conductive polymer composite cathode material membrane

A conductive polymer and lithium-ion battery technology, applied in battery electrodes, lithium batteries, non-aqueous electrolyte batteries, etc., can solve the problems of cumbersome process and difficult large-scale production, and achieve the effect of firm combination and low density

Active Publication Date: 2014-05-28

威海区域创新中心有限责任公司

8 Cites 7 Cited by

AI-Extracted Technical Summary

Problems solved by technology

In order to improve the adhesion of the tin coating on the surface of the copper substrate, a Chinese invention patent (Wang Jianming et al., Electrodeposition-hydrothermal method for preparing tin anode materials for lith...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine

Method used

(1) tin negative electrode material is prepared by electrodeposition, the preparation condition is mild, the film-forming property is good, and the nanoscale tin particles have good electrochemical properties;

(2) between the tin nanoparticle and its surface deposit one layer of conductive macromolecules, play the volume effect of buffering tin intercalation l...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine

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.

Application Domain

Cell electrodesLi-accumulators

Technology Topic

Lithium electrodeGraphite +16

Image

Examples

Experimental program(6)

Example Embodiment

[0031] A method for preparing a tin and conductive polymer composite negative electrode material film for a lithium ion battery. The tin and conductive polymer composite negative electrode material film is based on graphite paper, and the metal tin deposited on the surface of the graphite paper is granular , The size of the metal tin is 0.5-2um, the conductive polymer nanofibers are dispersed between and on the surface of the metal tin particles, and the diameter of the conductive polymer nanofibers is 0.1-0.8um, which specifically includes the following steps:

[0032] a. The pre-treatment of graphite paper: the graphite paper is cleaned and surface treated in the cleaning tank with cleaning fluid;

[0033] b. Constant current deposition of metal tin: connect the external power supply through the electrode brush to contact the graphite paper as the working electrode, use the graphite plate as the counter electrode, and place it in the tin electrodeposition tank. The temperature of the tin electrodeposition solution in the tin electrodeposition tank is 35- 80 degrees; using constant current deposition, control current density is 0.2-1.2 mA/cm 2 , The deposition time is 2-20 minutes, and the bottom of the tin electrodeposition liquid is stirred during the electrodeposition process at a stirring rate of 120-600rpm to obtain tin/graphite paper material;

[0034] c. Preparation of conductive polymer electrodeposition: Place the tin/graphite paper material obtained above in the monomer solution tank of the polymer, and stir the bottom of the monomer solution in the monomer solution tank at a stirring rate of 120-600 rpm;

[0035] d. Electrochemical synthesis of conductive polymer film by potentiostat method: connect the external power supply through the electrode brush to make the tin/graphite paper material as the working electrode, and the counter electrode is Pt, Cu or graphite sheet, placed in the conductive polymer electrodeposition solution, Adjust the voltage to be between 0.5-1.2V, the deposition time is 5-22 minutes, the solution temperature is 0-25 degrees, stir the bottom of the conductive polymer electrodeposition solution, the stirring rate is 120-600rpm, to obtain a conductive polymer film;

[0036] f. Preparation of tin and conductive polymer composite negative electrode material film: Pass the conductive polymer film obtained above through a cleaning tank, and stir the bottom of the cleaning solution in the cleaning tank at a stirring rate of 120-600 rpm to remove the adsorption on the surface of the conductive polymer film. The polymer monomer and inorganic salt finally obtain the tin and conductive polymer composite anode material film with conductive polymer dispersed between the tin nanoparticles and on the surface, and the tin and conductive polymer composite anode material film is passed through a blast drying box, The drying temperature is 60-90 degrees.

[0037] In the above, the liquid of the cleaning solution in the step a is two or all of deionized water, ethanol, surfactant A, and ethanolamine; the raw material formula of the tin electrodeposition solution in the step b is: 0.2- 2 mol/L tin salt, 0.2-1.0 mol/L K 4 P 2 O 7 ·3H 2 O, 0.2-1.5mol/L NaOH, 0.1-0.5mol/L ascorbic acid, wherein the pH of the tin electrodeposition solution is 8.5-10. Wherein, the tin salt is a soluble tin salt, and the soluble tin salt is at least one of tin chloride, tin sulfate, and sodium stannate.

[0038] In the step c, the monomer solution is one or two of aniline, pyrrole and thiophene, and the concentration is 0.2-2 mol/L; the pH of the conductive polymer electrodeposition solution in the step d=2.5-5, The raw material formula of conductive polymer electrodeposition solution is: 0.05-0.6mol/L conductive polymer monomer solution, 0.1-1mol/L acid solution, 0.5-1mol/L KCl solution, 0.1-0.5mol/L surface Active agent B solution. Wherein, the acid solution is one or two of phosphoric acid, sulfuric acid, nitric acid, and dodecylbenzenesulfonic acid.

[0039] In the present invention, the graphite paper is made of high-carbon phosphorous flake graphite after chemical treatment, high temperature expansion and rolling product, carbon content: 90-99.5%, thickness: 0.05-0.3mm; the made tin and conductive polymer composite The composition and mass percentage content of the anode material film are:

[0040] Tin: 80-92%,

[0041] Conductive polymer: 8-20%.

[0042] The invention uses graphite paper (carbon content: 90-99.5%, thickness: 0.05-0.3 mm) as a substrate, and a metal tin/conductive polymer composite film is prepared in two steps. (1) Using electrodeposition method, deposit metal tin nanoparticles on the surface of graphite paper within 2-10 minutes; (2) Using chemical polymerization method to prepare tin/conductive polymer composite anode material, conductive polymer is dispersed in the tin nanoparticles Between and its surface. In the composite structure of tin and conductive polymer, the metal tin plays an electrochemical function of lithium storage/delithiation, and the conductive polymer network plays a conductive role while limiting the agglomeration of tin nanoparticles and buffering the tin particles during charge and discharge. The volume changes.

Example Embodiment

[0043] Example 1:

[0044] Graphite paper with a thickness of 0.08mm is cleaned and treated on the surface and enters the electrodeposition tank of metal tin. Graphite paper is the working electrode (connected to the external power supply through the electrode brush contact), the graphite plate with a thickness of 1 cm is the counter electrode, and the tin electrodeposition solution configuration: 0.6 mol/L sodium stannate, 0.2 mol/L K 4 P 2 O 7 ·3H 2 O, 0.2 mol/L NaOH, 0.25 mol/L ascorbic acid, 0.05 mol/L H 2 O 2; Bath pH=9; bath temperature is 60 degrees; electrodeposition current density is 0.6 mA/cm 2 , The deposition time is 5 minutes, and the bath stirring rate is 180 rpm;

[0045] Place the tin/graphite paper material in the polymer monomer solution tank, and stir at the bottom of the tank at 120 rpm. Then enter the conductive polymer deposition tank, tin/graphite paper is the working electrode (connected to the external power supply through the electrode brush contact), and the counter electrode is a 0.5mm thick Pt sheet. Conductive polymer electrodeposition solution configuration: 0.05 mol/L aniline solution, 1 mol/L sulfuric acid solution, 0.5 mol/L KCl solution, 0.1 mol/L surfactant B solution, bath pH=2.5, adjust voltage It is 0.6 V, the deposition time is 15 minutes, the bath temperature is 25 degrees, and the bath stirring rate is 120 rpm;

[0046] After the two-step deposition is completed, the composite film passes through a cleaning tank to remove adsorbed polymer monomers and inorganic salts; passes through a 90-degree blast drying oven to prepare a tin/polyaniline/graphite paper composite lithium battery negative electrode film. XRD test shows that the surface of graphite paper is metallic tin crystal phase (see attached figure 2 ), the deposited metal tin particle size is 0.5-1 um (see attached image 3 ), elemental composition analysis shows that the mass ratio of metallic tin to polyaniline is 89:11. The sample film obtained in this example was directly used as the negative electrode film of a lithium battery. After 30 cycles, the specific capacity was maintained at 650mAh/g.

Example Embodiment

[0047] Example 2:

[0048] Graphite paper with a thickness of 0.2mm is cleaned on the surface and enters the electrodeposition tank of metal tin. Graphite paper is the working electrode (connected to an external power supply through electrode brush contact), and a graphite plate with a thickness of 1 cm is the counter electrode. Tin electrodeposition solution configuration: 0.4mol/L sodium stannate, 0.2mol/L K 4 P 2 O 7 ·3H 2 O, 0.2mol/L NaOH, 0.25mol/L ascorbic acid, 0.05mol/L H 2 O 2; Bath pH=9; Bath temperature is 60 degrees; Electrodeposition current density is 0.8mA/cm 2 , The deposition time is 10 minutes, and the bath stirring rate is 180rpm;

[0049] Place the tin/graphite paper material in the polymer monomer solution tank, stir at the bottom, and stir at 120 rpm. Then enter the conductive polymer deposition tank, tin/graphite paper is the working electrode (connected to the external power supply through the electrode brush contact), and the counter electrode is a 0.5mm thick Pt sheet. Conductive polymer electrodeposition solution configuration: 0.05mol/L aniline solution, 1mol/L sulfuric acid solution, 0.5mol/L KCl solution, 0.1mol/L surfactant B solution, bath pH=2.5, adjust voltage It is 0.6 V, the deposition time is 10 minutes, the bath temperature is 25 degrees, and the bath stirring rate is 120 rpm;

[0050] After the two-step deposition, the composite film passes through a cleaning tank to remove the adsorbed polymer monomers and inorganic salts on the surface; passes through a 90-degree blast drying box to prepare a tin/polyaniline/graphite paper composite lithium battery negative electrode film. The deposited metallic tin is distributed in nano-particles with a particle size of 1-1.5um. The elemental composition analysis shows that the mass ratio of metallic tin to polyaniline is 94:6. The sample film obtained in this example was directly used as the negative electrode film of a lithium battery, and the capacity remained at 450 mAh/g after 30 cycles.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine

Login to view more

PUM

Property	Measurement	Unit
Diameter	0.1 ~ 0.8	µm
Thickness	0.05 ~ 0.3	mm
tensile		MPa
Particle size		Pa
strength	10

Description & Claims & Application Information

We can also present the details of the Description, Claims and Application information to help users get a comprehensive understanding of the technical details of the patent, such as background art, summary of invention, brief description of drawings, description of embodiments, and other original content. On the other hand, users can also determine the specific scope of protection of the technology through the list of claims; as well as understand the changes in the life cycle of the technology with the presentation of the patent timeline. Login to view more.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine

Login to view more

Method and system for providing an uplink structure and minimizing pilot signal overhead in a wireless communication network

ActiveUS20110261781A1Low densityUniform spreadingModulated-carrier systemsTransmission path divisionVIT signalsContinuation

Owner:APPLE INC

Method for preparing porous silicon-nitride ceramic material

ActiveCN102320856AHigh open porosityLow densityCeramicwareSilicon nitrideVolatile substance

Owner:SHANGHAI INST OF CERAMIC CHEM & TECH CHINESE ACAD OF SCI

Classification and recommendation of technical efficacy words

Low density
Strong combination

Preparation method of tin of lithium ion battery and conductive polymer composite cathode material membrane

A conductive polymer and lithium-ion battery technology, applied in battery electrodes, lithium batteries, non-aqueous electrolyte batteries, etc., can solve the problems of cumbersome process and difficult large-scale production, and achieve the effect of firm combination and low density

AI-Extracted Technical Summary

Problems solved by technology

Method used

Abstract

Image

Examples

Example Embodiment

Example Embodiment

Example Embodiment

PUM

Description & Claims & Application Information

Similar technology patents

Plastic film

Preparation method of low-thermal-conductivity silicon-nitride-bonded silicon carbide porous ceramic

Void-containing polyester shrink film with improved density retention

Method and system for providing an uplink structure and minimizing pilot signal overhead in a wireless communication network

Method for preparing porous silicon-nitride ceramic material

Classification and recommendation of technical efficacy words

Thin-film device and method of fabricating the same

Nitride semiconductor laser device

Constant cluster seeding

Insulated stud panel and mehod of making such

Fluid-assisted medical devices, systems and methods

Method for processing high-temperature alloy furnace tube

Preparation method for organic/inorganic hybridization cladding aluminum composite particle

Preparation method of macroporous aluminum oxide with diplopore distribution

Lithium ion battery anode and preparation method thereof

Preparation method of high-performance anti-fingerprint agent