CN1280940C - Lithium/polyparrole secondary button cell and its preparation method - Google Patents

Lithium/polyparrole secondary button cell and its preparation method Download PDF

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Publication number
CN1280940C
CN1280940C CNB2004100203055A CN200410020305A CN1280940C CN 1280940 C CN1280940 C CN 1280940C CN B2004100203055 A CNB2004100203055 A CN B2004100203055A CN 200410020305 A CN200410020305 A CN 200410020305A CN 1280940 C CN1280940 C CN 1280940C
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lithium
polypyrrole
button cell
carbon black
composite material
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CN1599118A (en
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任丽
王立新
朱嫦娥
安灏媛
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Hebei University of Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The present invention relates to a secondary lithium/polypyrrole button cell and a preparation method thereof, which belongs to a secondary lithium/polymer button cell using polypyrrole/silicon dioxide or a carbon black nano composite material, and a preparation technology for the secondary lithium/polymer button cell. The present invention provides a novel secondary button cell in order to enhance the property of a secondary cell and meet the requirements of the society. The secondary button cell is mainly composed of a positive plate coated with a positive electrode coating material containing polypyrrole/silicon dioxide or a carbon black nano composite material, a negative electrode lithium plate, three layers of micropore composite membranes and an electrolyte, and is manufactured by that the secondary button cell is assembled in an argon gas glove box, a lithium plate is put into a negative electrode case, a membrane is laid on the lithium plate, and an electrolyte is dipped into the negative electrode case, a manufactured positive plate is placed on a membrane, a pad is pressed on the positive plate, a spring plate is put on the pad, a positive electrode case is covered, and the cell is processed through sealing forming on a press machine. The cell has the advantages of high discharge capacity and coulomb efficiency, long cycle life and good stability of still standing. The present invention has the advantages of simple technology and easy industrialized production, and adds a new species for a secondary lithium/polymer battery.

Description

The preparation method of lithium/polypyrrole secondary button cell
Technical field
The invention belongs to a kind of novel lithium/polymer secondary battery and technology of preparing thereof, particularly a kind of lithium/polypyrrole secondary button cell and technology of preparing thereof.
Background technology
Along with the communication technology and fast development of computer technology, various information electronics such as mobile phone, notebook computer all stride forward towards the target of " light, thin, short, little ", and electric automobile, space industry and sophisticated weapon equipment are very urgent to the demand of high-performance secondary cell in addition.Novel secondary cell technology is counted as the dual-use technology that 21 century has strategic importance.Yet present secondary cell is in shape, the charge and discharge fail safe, and environmental problem, capacity density discharges and recharges stability and leaves standstill aspect such as stability and is still waiting to improve.
In order to improve the secondary cell performance, it is crucial selecting suitable positive electrode.Polymer has been compared following advantage as secondary battery positive electrode material with other secondary battery positive electrode material: 1. processability is good.Can be processed into suitable shape to battery as required, also can be made into hull cell; 2. weight specific energy maximum; 3. do not resemble easy generation dendrite the metal electrode and internal short-circuit takes place; 4. the electrode of polymer making is that so the specific area of electrode is big, specific power is big in the inner generating electrodes reaction of the macromolecule matrix of whole porous.Polypyrrole (PPy) have air stability good, be easy to film forming, be easy to mix, advantage such as nontoxic.After tested, make positive pole with the polypyrrole nano composite material that conductivity is high, higher specific discharge capacity is arranged, cycle performance is good, is a kind of more satisfactory lithium secondary battery positive active material.Since the theoretical capacity density of lithium/polymer secondary battery than lithium ion battery () big, therefore of greatest concern, from the angle of development in science and technology, in case technology maturation, the former will become new substitute products.Though therefore in shape, discharge and recharge, aspects such as fail safe and environmental problem all also have sizable development space.
As at " Susumu Kuwabata, Shingo Masui, Hiroshi Yoneyama.Charge-dischagreg properties of composites of LiMn 2O 4And polypyrrole aspositive electrode materials for 4v class of rechargeable Li batteries.Electrochimica Acta., 1999,44:4593-4600 " in reported with PPy/LiMn 2O 4Composite material is made anodal lithium secondary battery, and composite material and acetylene black force together with the Ni net under the polytetrafluoroethylene (PTFE) effect and makes pole piece, electrolyte employing LiClO 4/ EC-DEC.At " Ali H.Gemeay, HiroshiNishiyama, Susumu Kuwabata.Chemical preparation of manganesedioxide/polypyrrole composites and their use as cathode active materialsfor rechargeable lithium batteries, J.Electrochem.Soc., 1995,142 (12): 4190-4195 " reported with PPy/MnO in 2Composite material is made anodal lithium secondary battery, and composite material is with to be pressed in Ni after carbon black and polytetrafluoroethylene (PTFE) mix online, electrolyte employing LiClO 4/ PC-DME.At " Susumu Kuwabata, Shingo Masui, Hidemasa Tomiyori.Charge-discharge properties of chemically prepared composites of V 2O 5Andpolypyrrole as positive electrode materials in rechargeable Li batteries.Electrichimica Acta, 2000,46:91-97 " in reported with PPy/V 2O 5Composite material is made anodal lithium secondary battery, and carbon black is served as in the effect of PPy, only accounts for very little ratio, and pole piece is that composite material and Ni net force together, and electrolyte adopts LiClO 4/ EC-DEC.Above bibliographical information for polypyrrole/carbon black nano composite material provides foundation as cathode plate for lithium secondary battery, but all is that positive electrode and stripping electrode difficulty are not suitable for industrial production in enormous quantities with the electrochemical process preparation.
With chemical oxidization method original position adsorpting polymerization, the polypyrrole/silicon dioxide of preparation (carbon black) (PPy/SiO 2(C)) nano composite material is made cathode plate for lithium secondary battery, does not appear in the newspapers as yet.
Summary of the invention
The problem that solves:
At above-mentioned situation, for the coulombic efficiency, discharge capacity, the cycle life that improve secondary cell, discharge and recharge stability and leave standstill stability, adapt to current demand to the secondary minicell, the invention provides a kind of lithium/polypyrrole secondary button cell and preparation technology thereof, will adopt the PPy/SiO of original position adsorpting polymerization method preparation 2(C) nano composite material is selected the negative pole and the electrolyte assembling button cell that are complementary with it as the positive electrode active materials of lithium secondary battery, makes it that higher discharge capacity, coulombic efficiency and cycle life be arranged.
Technical scheme:
The present invention mainly by coating contain the positive plate 4, lithium sheet 2 of the anodal coating material of polypyrrole/silicon dioxide or carbon black nano composite material, barrier film 3, anode shell 7 and the battery cathode shell 1 that is soaked into by electrolyte constitutes; Its combination is that lithium sheet 2 is placed in the battery cathode shell 1, above the barrier film 3 that soaked into by electrolyte of lay, then positive plate 4 is placed on the barrier film 3 that is soaked into by electrolyte, press pad 5, put spring leaf 6 again, buckle anode shell 7 at last.
Need to prove:
Positive plate 4 is to apply anodal coating material on the aluminium foil of 0.015mm to make at thickness, and wherein the constituent content of anodal coating material is by ratio of weight and the number of copies:
Positive electrode active materials 1
Carbon black 0～0.05
Kynoar PVDF 0.1
N-methyl pyrrolidone 10.
Above-mentioned positive electrode active materials is a polypyrrole/silicon dioxide nano composite material, or polypyrrole/carbon black nano composite material, and wherein polypyrrole/silicon dioxide nano composite material is No. 01136948.5 material described in the patent application.Polypyrrole/carbon black nano composite material is that matrix is a polypyrrole, and strengthening body is the original position adsorpting polymerization thing of carbon black.Polypyrrole and carbon black ratio of weight and number are in this polymer: 1: 0.01-0.15.Each component sum is 100% in this polymer.
In addition, in this lithium/polypyrrole secondary button cell, barrier film 3 is three layers of microporous compound film of polypropylene, polyethylene/polypropylene (PP/PE/PP); Electrolyte is lithium hexafluoro phosphate/ethylene carbonate-dimethyl carbonate-methyl ethyl carbonate (LiPF 6/ EC-DMC-EMC); Pad 5 is a steel shim.
The preparation method of lithium/polypyrrole secondary button cell, its concrete preparation technology is as follows:
The preparation of positive electrode active materials:
Positive electrode active materials is polypyrrole/silicon dioxide or carbon black nano composite material.
Wherein, the material that provides in No. 01136948.5 patent application is provided in the preparation of polypyrrole/silicon dioxide nano composite material.
The preparation method of polypyrrole/carbon black nano composite material is as follows:
Under 25 ℃, its used material is by ratio of weight and the number of copies with 7-11 part oxidant FeCl 36H 2O; 4-6 part dopant benzene sulfonic acid sodium salt and 0.01-0.15 part particle diameter are that the carbon black of 33nm adds in 100 parts of deionized waters; inject 1 part of pyrroles with needle tubing after stirring; polymerization centrifugation after 12 hours is stirred in nitrogen protection down; the gained precipitation is through ultrasonic wave repeating dispersion in deionized water; be neutral until system, 40-60 ℃ of following vacuumize 24 hours promptly obtains polypyrrole/carbon black nano composite material.
The preparation of positive plate 4:
The polypyrrole/silicon dioxide of said method gained or carbon black nano composite material and carbon black, adhesive and N-methyl pyrrolidone NMP are mixed by 1: 0～0.05: 0.1: 10 ratio of weight and number, make the slurry of being convenient to apply.The slurry that makes is coated on the collector electrode (thickness is the aluminium foil of 0.015mm), put into 50 ℃ of vacuum tanks dry 1～2 hour, take out, be washed into disk, put into 50 ℃ of vacuum tanks again, dry by the fire taking-up in 24 hours; Then, to its 10-30MPa typing of cutting out, pressurize, making positive plate thickness is 0.1～0.2mm, and last vacuum is preserved, and is standby;
The packaging technology of lithium/polypyrrole secondary button cell:
In 25 ℃ of following argon gas glove boxes, lithium sheet 2 is done negative pole, be placed in the battery cathode shell 1, lay polypropylene, polyethylene/polypropylene diaphragm 3 splashes into lithium hexafluoro phosphate/ethylene carbonate-dimethyl carbonate-methyl ethyl carbonate electrolyte number droplet, makes it soak into barrier film 3; And then above-mentioned made positive plate 4 placed on the barrier film 3, press steel shim 5, put spring leaf 6 again; Buckle anode shell 7 at last, on press,, make button cell the battery seal moulding.
Beneficial effect:
Lithium of the present invention/polypyrrole secondary button cell, adopt the organic and inorganic compound system, and selection original position adsorpting polymerization technology, compound with nano silicon or carbon black, obtaining the higher polypyrrole/silicon dioxide of conductivity (carbon black) nano composite material is positive electrode active materials, and optimize negative pole and the electrolyte that is complementary with it, be assembled into lithium/polypyrrole secondary button cell.After tested, this battery has higher discharge capacity, coulombic efficiency and cycle life, and has and leave standstill stability preferably, is a kind of novel lithium/polymer secondary battery that DEVELOPMENT PROSPECT is arranged very much.Technology of the present invention is simple, environmental pollution is little, be easy to suitability for industrialized production.This product is that lithium/polymer secondary battery has increased new varieties, thus satisfy better various information electronics such as the communication technology and fast development of computer technology, mobile phone, notebook computer all towards the target of " light, thin, short, little " stride forward, to the demand of high-performance secondary cell.
Description of drawings
Fig. 1: button cell structural representation of the present invention
Fig. 2: button cell charging and discharging curve of the present invention
Fig. 3: button cell time of repose of the present invention is to the influence of voltage
Embodiment
Embodiment 1:
The preparation technology of lithium/polypyrrole secondary button cell is as follows:
The preparation of positive electrode active materials:
Positive electrode active materials is a polypyrrole/silicon dioxide nano composite material.The material that provides in 01136948.5 patent application is provided this material.
The preparation of positive plate 4:
1 gram polypyrrole/silicon dioxide nano composite material of said method gained and conductive black, 0.1 gram adhesive Kynoar and the 10mlN-methyl pyrrolidone (NMP) of 0.05 gram particle footpath 33nm are mixed, make the slurry of being convenient to apply, be coated on the collector electrode (thickness is the aluminium foil of 0.015mm), put into 50 ℃ of vacuum tanks dry 1 hour, take out, be washed into disk, put into 50 ℃ of vacuum tanks again, dry by the fire taking-up in 24 hours; Then, to its 10MPa typing of cutting out, pressurize, making positive plate thickness is 0.2mm, weighing, and last vacuum is preserved, and is standby.
The packaging technology of lithium/polypyrrole secondary button cell:
As shown in Figure 1, in 25 ℃ of following argon gas glove boxes, lithium sheet 2 is done negative pole, be placed in the battery cathode shell 1, make lithium sheet 2 be in the center position of battery cathode shell 1; The lay barrier film 3 in the above, and promptly three layers of microporous compound film of polypropylene, polyethylene/polypropylene (PP/PE/PP) splash into lithium hexafluoro phosphate/ethylene carbonate-dimethyl carbonate-methyl ethyl carbonate (LiPF 6/ EC-DMC-EMC) electrolyte number droplet makes it soak into barrier film 3; And then above-mentioned made positive plate 4 placed on the barrier film 3, press steel shim 5, put spring leaf 6 again; Buckle anode shell 7 at last, on press,, make button cell the battery seal moulding.
Lithium secondary button cell cycle charge-discharge curve is stable as seen from Figure 2, and the battery normal circulation has still kept higher capacity and near 100% efficiency for charge-discharge after 148 hours.
Leave standstill under 25 ℃ as seen from Figure 3 the self-discharge of battery of made of the present invention is investigated, voltage is along with the time descends gradually, and the range of decrease reduces gradually, is stabilized in 3.68V at last.The voltage of battery was compared with its peak and was only descended 3.16% this moment, as can be seen its to leave standstill stability very high.
Embodiment 2:
After the slurry of making is coated on the collector electrode, put into 50 ℃ of vacuum tanks dry 1.5 hours, take out, be washed into disk, put into 50 ℃ of vacuum tanks again, dry by the fire taking-up in 24 hours; Then, to its 20MPa typing of cutting out, pressurize, making positive plate thickness is 0.15mm, weighing, and last vacuum is preserved, and is standby.Other is with embodiment 1.
Embodiment 3:
After the slurry of making is coated on the collector electrode, put into 50 ℃ of vacuum tanks dry 2 hours, take out, be washed into disk, put into 50 ℃ of vacuum tanks again, dry by the fire taking-up in 24 hours; Then, to its 30MPa typing of cutting out, pressurize, making positive plate thickness is 0.1mm, and last vacuum is preserved, and is standby.Other is with embodiment 1.
Embodiment 4:
The preparation of positive electrode active materials:
Positive electrode active materials is polypyrrole/carbon black nano composite material.
The preparation method of polypyrrole/carbon black nano composite material is as follows:
Restrain oxidant FeCl with 7 under 25 ℃ 36H 2O; 2 gram dopant benzene sulfonic acid sodium salts and 0.01 gram particle directly add in the 100ml deionized water for the carbon black of 33nm; inject 1ml pyrroles with needle tubing after stirring; polymerization centrifugation after 12 hours is stirred in nitrogen protection down; the gained precipitation is through ultrasonic wave repeating dispersion in deionized water; be neutral until system, 60 ℃ of following vacuumize 24 hours promptly obtains polypyrrole/carbon black nano composite material.
Conductive black, 0.1 gram Kynoar adhesive and the 10mlNMP of 1 gram polypyrrole/carbon black nano composite material, 0.05 gram particle footpath 33nm are mixed, make the slurry of being convenient to apply.Other is with embodiment 1.
Embodiment 5:
The preparation of positive electrode active materials:
Positive electrode active materials is polypyrrole/carbon black nano composite material.
The preparation method of polypyrrole/carbon black nano composite material is as follows:
Restrain oxidant FeCl with 11 under 25 ℃ 36H 2O; 8 gram dopant benzene sulfonic acid sodium salts and 0.15 gram particle directly add in the 100ml deionized water for the carbon black of 33nm; inject 1ml pyrroles with needle tubing after stirring; polymerization centrifugation after 12 hours is stirred in nitrogen protection down; the gained precipitation is through ultrasonic wave repeating dispersion in deionized water; be neutral until system, 50 ℃ of following vacuumize 24 hours promptly obtains polypyrrole/carbon black nano composite material.
Conductive black, 0.1 gram adhesive Kynoar and the 10mlNMP of 1 gram polypyrrole/carbon black nano composite material, 0.03 gram particle footpath 33nm are mixed, make the slurry of being convenient to apply.Other is with embodiment 2.
Embodiment 6:
The preparation of positive electrode active materials:
Positive electrode active materials is polypyrrole/carbon black nano composite material.
The preparation method of polypyrrole/carbon black nano composite material is as follows:
Restrain oxidant FeCl with 9 under 25 ℃ 36H 2O; 5 gram dopant benzene sulfonic acid sodium salts and 0.07 gram particle directly add in the 100 gram deionized waters for the carbon black of 33nm; inject 1ml pyrroles with needle tubing after stirring; polymerization centrifugation after 12 hours is stirred in nitrogen protection down; the gained precipitation is through ultrasonic wave repeating dispersion in deionized water; be neutral until system, 40 ℃ of following vacuumize 24 hours promptly obtains polypyrrole/carbon black nano composite material.
1 gram polypyrrole/carbon black nano composite material, 0.1 gram Kynoar adhesive and 10mlNMP are mixed, make the slurry of being convenient to apply.Other is with embodiment 3.

Claims (1)

1. the preparation method of lithium/polypyrrole secondary button cell, its concrete preparation technology is as follows:
The preparation of positive electrode active materials:
Positive electrode active materials is polypyrrole/carbon black nano composite material, and the preparation method of polypyrrole/carbon black nano composite material is as follows: under 25 ℃, its used material by ratio of weight and the number of copies, with 7-11 part oxidant FeCl 36H 2O, 4-6 part dopant benzene sulfonic acid sodium salt and 0.01-0.15 part particle diameter are that the carbon black of 33nm adds in 100 parts of deionized waters, inject 1 part of pyrroles with needle tubing after stirring, polymerization centrifugation after 12 hours is stirred in nitrogen protection down, the gained precipitation is through ultrasonic wave repeating dispersion in deionized water, be neutral until system, 40-60 ℃ of following vacuumize 24 hours promptly obtains polypyrrole/carbon black nano composite material;
The preparation of positive plate (4):
Polypyrrole/carbon black the nano composite material of said method gained and conductive black, adhesive Kynoar and N-methyl pyrrolidone NMP are mixed by 1: 0～0.05: 0.1: 10 ratio of weight and number, make slurry, being coated in collector electrode is that thickness is on the aluminium foil of 0.015mm, put into 50 ℃ of vacuum tanks dry 1～2 hour, take out, be washed into disk, put into 50 ℃ of vacuum tanks again, dry by the fire taking-up in 24 hours; Then, to its 10-30MPa typing of cutting out, pressurize, making positive plate thickness is 0.1～0.2mm, and last vacuum is preserved, and is standby;
The packaging technology of lithium/polypyrrole secondary button cell is as follows:
In 25 ℃ of following argon gas glove boxes, lithium sheet (2) is done negative pole, be placed in the battery cathode shell (1), in the above lay polypropylene, polyethylene/polypropylene diaphragm (3), splash into lithium hexafluoro phosphate/ethylene carbonate-dimethyl carbonate-methyl ethyl carbonate electrolyte number droplet, make it soak into barrier film (3); And then above-mentioned made positive plate (4) placed on the barrier film (3), press steel shim (5), put spring leaf (6) again; Buckle anode shell (7) at last, on press,, make button cell the battery seal moulding.
CNB2004100203055A 2004-08-12 2004-08-12 Lithium/polyparrole secondary button cell and its preparation method Expired - Fee Related CN1280940C (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN102469838A (en) * 2009-08-19 2012-05-23 尚和手套株式会社 Work glove

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CN102544432A (en) * 2010-12-13 2012-07-04 依诺特生物能量控股公司 Positive electrode and battery with same
CN104409689A (en) * 2014-11-17 2015-03-11 天津大学 Polypyrrole coated hard carbon cathode material and preparation method thereof
CN104393353B (en) * 2014-11-28 2016-08-24 南开大学 A kind of high magnification and long-life fill room temperature sode cell and preparation method thereof
CN105161723B (en) * 2015-06-18 2018-03-06 浙江工业大学 polypyrrole-3-formic acid and application thereof as lithium ion battery anode material
CN110186808A (en) * 2019-05-14 2019-08-30 欣旺达电子股份有限公司 The test method of half-cell and anode material for lithium-ion batteries high temperature gas generation property
CN113394405B (en) * 2021-05-24 2022-07-12 西安交通大学 Preparation method of electrode coating for actively preventing thermal runaway of lithium ion battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102469838A (en) * 2009-08-19 2012-05-23 尚和手套株式会社 Work glove

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