CN1645650A - Production for positive electrode piece of cylindrical winding lithium-ferrite disulfide battery - Google Patents
Production for positive electrode piece of cylindrical winding lithium-ferrite disulfide battery Download PDFInfo
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- CN1645650A CN1645650A CNA2004100510157A CN200410051015A CN1645650A CN 1645650 A CN1645650 A CN 1645650A CN A2004100510157 A CNA2004100510157 A CN A2004100510157A CN 200410051015 A CN200410051015 A CN 200410051015A CN 1645650 A CN1645650 A CN 1645650A
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- ferrous disulfide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The pole piece of anode is composed of pyrite, acetylene black, black lead, binding agent and additive. After the pyrite is taken by heat treatment, it mixes with compression-treated acetylene black, black lead and additive. Two methods are used in making the anode powder piece. One is slurry method: after the anode powder mixes with deionized water and industrial spirit, the Teflon liquid cream is added to form a cream; first pressing it to form film and then making it into piece. The second method is rolling forming: after the industrial spirit, Teflon liquid cream are added into the anode powder, first pressing it into film; then making it into pieces; the pieces are put into bake oven to remove water and then put into vacuum case for drying.
Description
Technical field
The invention belongs to the battery technology field, the preparation method of the column type coiling type lithium battery anode pole piece that particularly a kind of its positive active material is a ferrous disulfide.
Background technology
Lithium battery is that later 1950s is at first by the battery of the brand-new generation of American Studies exploitation.Japan has developed lithium carbon monofluoride battery the earliest in 1973, so far the history of existing three more than ten years.The civilian lithium battery to 1975 of a Japan year input is produced in batches.And China has also just realized Li/MnO in the 1980s
2The production of button cell.
Zhang Xiqing, Shen Yongpei, Shen Songjian at first mention with difference and force agent and high density polyethylene (HDPE) blend in " the poly modification of li-Mn button cell " (" battery " 1994 the 3rd phases), to improve his leak resistance of button electricity.
Zhang Mao has designed the make-up machine of positive plate clearly in " design of button type lithium-manganese battery positive plate automatic moulding machine " (the 2nd phase of " battery " nineteen ninety-five) literary composition.
Liu Ruihua, Changqing, osmanthus " button type lithium-manganese battery life-span fast detecting " (" battery " 1996 the 4th phases) according to lnt=A-1.15lni, adopt big electric current earlier, discharge with specified little current condition then, with the fast detecting battery life.
Lithium-poly-fluorocarbons battery, lithium-thionyl chloride battery, lithium sulfur dioxide cell, lithium-copper oxide cell, lithium-iodine battery technical maturity in succession in recent years.
Suzhou Battery Plant Qiu Miaoyun, Huang Jinwen in " lithium battery lecture " (" battery " 2-5 phase in 1992) literary composition, the technology of lithium-poly-fluorocarbons battery, lithium-thionyl chloride battery, lithium sulfur dioxide cell is narrated.
The fertile willow of the Li Chengfang of department of chemistry of Fudan University, Wu Haoqing and the Changjiang river power supply factory is to the discharge mechanism of lithium-copper oxide cell, and the research carried out of the preparation technology of battery.
The Li Cheng virtue king of department of chemistry of Fudan University builds bright influence to binding agent in lithium-copper oxide cell and studies.
It is longer than other type cell that battery of lithium-iron disulphide has useful life, and be particularly suitable for the advantage of heavy-current discharge.Its high and low temperature function admirable, operating voltage is high steadily, discharge curve is level and smooth, and anti-seepage is good, and shelving performance is good, and is in light weight, do not have the mercury, cadmium or the lead that add.
The Li Min of Fudan University, Jiang Zhiyu is at " button Li/FeS and Li/FeS
2The development of battery " in (" battery " 1989 the 1st phases) literary composition, the button type battery of lithium-iron disulphide is studied.But but do not relate at column type takeup type battery of lithium-iron disulphide.
The present invention is to the preparation of column type takeup type lithium-ferrous disulfide battery anode pole piece and propose.
Column type takeup type battery of lithium-iron disulphide, its structure is made up of battery case, electrode, barrier film, electrolyte, encapsulant; The utmost point group inside of its battery is three layers, and one deck is a positive plate, and one deck is a negative plate, and the intermediate layer is a barrier film; This utmost point group is inserted in the box hat of nickel plating, the negative lug of utmost point group contacts with the battery case bottom, and positive plate can contact with battery cover by positive pole ear; Between loam cake and housing, be inserted in the sealing ring of the macromolecular material of insulation, seal the back and form cell.
Summary of the invention
Select the natural pyrite of 200～300 purposes for use, feed inert gases such as nitrogen, argon gas as protective gas in 300～400 ℃ of hot environments, heat treatment time is 7～10 hours, is cooled to room temperature then under protective gas feeds.
The acetylene black compression method is that (it is looked specific volume and is about 11～16ml/g with commercially available acetylene black.) even by 1: 1 mixed with industrial alcohol, compacting is crossed 60 purpose moto-vibro screens in flakes on roller press then, looks specific volume and reaches 4～6ml/g.
The binding agent that adopts can be ptfe emulsion, concentration 40%～80%.
Added proper additive in the positive electrode, generally selected from following metal, they comprise the oxide of niobium, cobalt, cadmium, molybdenum, tin, lead, lithium, sodium, potassium, magnesium, aluminium, calcium, zinc, zirconium and titanium etc. and copper.Its purpose mainly is the high-tension phenomena that occurs of avoiding battery to begin to discharge and the phenomenon that has reduced lithium battery discharge back cell expansion effectively.
Aluminium net thickness is 0.30～0.45mm, and mesh is a rhombus, aperture size: (1.2～2.0) * (2.0～2.5) mm.
The preparation method of positive plate has following two kinds:
1) grout coating process: after the pyrite after the heat treatment, compression acetylene black, graphite, additive fully mixed, formation mixes closes powder, this is closed powder pours in the mixer, the heating of mixer partition can be adopted Steam Heating or water-bath heating or electric heating, heating-up temperature can be controlled at 40～90 ℃, add deionized water and industrial alcohol successively, stirred 20～70 minutes, add ptfe emulsion then and stir into cream 2 fast.The cream that to become reconciled is coated on the aluminium net 1, through twin rollers 3 pressurization slabbings, again through 180～200 ℃ of continuous tunnel furnace oven dry or additive method oven dry.Be rolled into certain thickness powder sheet 4 then on roller press repeatedly, its thickness can be controlled at 0.3～0.55 millimeter, and preferred thickness is controlled at 0.4-0.45 and is advisable.
Its method is seen attached illustrated in Figure 1.
2) roll embrane method: after fully mixing back processing industry alcohol, ptfe emulsion ptfe emulsion is uniformly dispersed the pyrite after the heat treatment, compression acetylene black, graphite, additive, adds deionized water and stirring then and become cream.On the twin rollers of band heater 6, be rolled into film 5, thickness 0.2～0.3mm after becoming cream.Film 5 is put into 100～180 ℃ of high temperature ovens toasted 6～12 hours, remove moisture content.Film 5 and aluminium net 1 are rolled into repeatedly the positive powder sheet 4 of even compact on roller press 3, its thickness can be controlled at 0.3～0.55 millimeter again, and preferred thickness is controlled at 0.4-0.45 and is advisable.Its method is seen attached illustrated in Figure 2.
Positive powder sheet after rolling is cut into the positive plate of certain size, through normal pressure air blast heat drying, vacuum and heating drying.Can obtain the positive plate that is used to reel.
The present invention adopts natural pyrite (ferrous disulfide) as positive electrode active materials, and a kind of manufacture method of with low cost, production technology is simple, electrical property is good, capacity is high column type takeup type lithium-ferrous disulfide battery anode sheet is provided.
Description of drawings
Fig. 1 is the process schematic representation of positive plate linked network method of the present invention;
Fig. 2 is the process schematic representation that positive plate of the present invention rolls embrane method;
Fig. 3 is the anode pole piece schematic diagram of column type coiled battery;
Fig. 4 is the end view of Fig. 3;
Fig. 5 is the discharge characteristic curve of AA type battery, the discharge system of battery: constant current 200mA, cut-ff voltage are 1.0V;
Fig. 6 is that AA type battery is shelved the discharge curve after 1 year, the discharge system of battery: constant current 200mA, cut-ff voltage are 1.0V.
Embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments:
The positive active material of the battery of lithium-iron disulphide in the present embodiment is natural pyrite; through making its granularity be about 200 orders after fragmentation, the screening; its logical nitrogen in 350 ℃ high temperature oven was toasted 10 hours, under nitrogen protection, naturally cool to below 50 ℃ then.(it is looked specific volume and is about 11～16ml/g with commercially available acetylene black.) with industrial alcohol by after 1: 1 the mixed, on twin rollers, roll and make sheet, cross 60 purpose moto-vibro screens then, look specific volume and reach about 4ml/g.With pyrite, acetylene black, graphite and the additive of above-mentioned processing ball milling 3 hours in ball mill, form the powder that closes that mixes.Close at this that to pour concentration in powder into be to stir 20min after 37% industrial alcohol, concentration are 60% ptfe emulsion ptfe emulsion is uniformly dispersed, add deionized water and stirring then and become cream.On the twin rollers of band heater, be rolled into film, thickness 0.2mm after becoming cream.This film is put into 180 ℃ of high temperature oven bakings 10 hours, remove moisture content.Film and the aluminium net roll extrusion on roller press of tiltedly drawing of cleaning are in the same place again, are rolled into the positive powder sheet of even compact repeatedly, its thickness is 0.3mm.With cut-off knife cathode film is cut into the pole piece of 145mm (length) * 41mm (wide), with the pole piece spot welding positive pole ear of spooling, shown in accompanying drawing 3,4, wherein 7 is long ear-poles, the 8th, and short lug, 9 is positive plate, the 10th, high tempreture tape, the 11st, adhesive tape.
Size as AA type battery is (145～165) * (41～42) mm, point burn-on cut out good positive plate behind the positive pole ear and carry out dried, at first carry out the normal pressure forced air drying, soon positive plate is tiled in and puts into 200～220 ℃ a conventional oven in the stainless steel disc, dry 24 hours; Carry out vacuumize subsequently, be about to positive plate and be tiled in the vacuum tank of putting into 0.1MPa in the stainless steel disc, baking temperature is 180 ℃, after being 24 hours drying time, cut off pumped vacuum systems, feed relative humidity simultaneously and be 0.1～3% dry air, after air pressure reaches constant pressure, take out and reel immediately.
This pole piece is made AA type battery through operations such as coilings.Just having carried out battery will wear out.
To carry out discharge test with the AA type lithium battery of as above flow process making: be discharged to 1.0V with 200mA.Discharge curve as shown in Figure 4, its discharge platform is that capacity is more than 3200mAh more than the 1.40V.
The AA type lithium battery that the method for using is made is shelved after 1 year and is done discharge test: be discharged to 1.0V with 200mA.Discharge curve as shown in Figure 5, its discharge platform about 1.40V, capacity about 3200mAh, self-discharge rate is 1%/year.
Claims (8)
1, a kind of manufacture method of column type takeup type lithium-ferrous disulfide battery anode pole piece, it is characterized in that: described ferrous disulfide is the pyrite of certain particle size after Overheating Treatment, the positive electrode of described positive plate also comprises acetylene black, graphite, additive after the compacting.
2, the manufacture method of lithium-ferrous disulfide battery anode pole piece according to claim 1; it is characterized in that: described pyritous heat treatment; be under nitrogen or the protection of other inert gas atmosphere; in temperature 300～400 degree Celsius; in 7～10 hours processing times, be cooled to the following temperature of 60 degree Celsius then.
3, the manufacture method of lithium-ferrous disulfide battery anode pole piece according to claim 1, it is characterized in that: the acetylene black after the described compacting, it is compressed processing, raw material and industrial alcohol is even by 1: 1 mixed, compacting is in blocks on roller press then, cross 60 purpose moto-vibro screens, apparent density reaches 4～6 milliliters/gram.
4, the manufacture method of lithium-ferrous disulfide battery anode pole piece according to claim 1 is characterized in that: described graphite, its outward appearance is an isometric particle, has high relatively isotropic conductivity and outstanding electrolyte absorption amount.
5, the manufacture method of lithium-ferrous disulfide battery anode pole piece according to claim 1, it is characterized in that: described additive, generally select from its oxide of following metal, they comprise niobium, cobalt, cadmium, molybdenum, tin, lead, lithium, sodium, potassium, magnesium, aluminium, calcium, zinc and copper etc. and oxide thereof.
6, the manufacture method of lithium-ferrous disulfide battery anode pole piece according to claim 1, it is characterized in that: composition and ratio that the positive pole of described positive plate closes powder are pyrite: acetylene black: graphite; Additive=(60～90): (5～20): (5～20): (0.5～5).
7, the method for lithium-ferrous disulfide battery anode pole piece according to claim 1, it is characterized in that: this method may further comprise the steps:
A. positive pole is closed powder to going in the mixer, the heating of mixer partition can be adopted Steam Heating or water-bath heating or electric heating, heating-up temperature can be controlled at 40～90 ℃, and adding deionized water and industrial alcohol add ptfe emulsion again and are cross-linked into cream after mixing;
B. it is online positive mix to be become to be coated in behind the cream aluminium, through the twin rollers extrusion forming, through 180～200 degree continuous tunnel furnaces oven dry Celsius, is rolled into thick 0.3～0.55 millimeter positive powder sheet then repeatedly on roller press again, and preferred thickness is controlled at 0.4-0.45 and is advisable.
8, the manufacture method of lithium-ferrous disulfide battery anode pole piece according to claim 1, it is characterized in that: this method may further comprise the steps:
A. industrial alcohol, ptfe emulsion are added positive pole and close in the powder, add deionized water and stirring then and become cream;
B. on the twin rollers of band heater, be rolled into film after positive mix being become cream, thickness can be controlled 0.2～0.5 millimeter, film is put into 100～180 ℃ of environment to be toasted 6～12 hours, remove moisture content, again film and aluminium net are rolled into repeatedly the positive powder sheet of even compact on roller press, its thickness can be controlled at 0.3～0.55 millimeter, and preferred thickness is controlled at 0.4-0.45 and is advisable.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100510157A CN1645650A (en) | 2004-08-09 | 2004-08-09 | Production for positive electrode piece of cylindrical winding lithium-ferrite disulfide battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100510157A CN1645650A (en) | 2004-08-09 | 2004-08-09 | Production for positive electrode piece of cylindrical winding lithium-ferrite disulfide battery |
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| CN1645650A true CN1645650A (en) | 2005-07-27 |
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| CNA2004100510157A Pending CN1645650A (en) | 2004-08-09 | 2004-08-09 | Production for positive electrode piece of cylindrical winding lithium-ferrite disulfide battery |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386907C (en) * | 2006-06-23 | 2008-05-07 | 清华大学 | Lithium-iron disulfide anode materials and method for preparing same |
| CN102024953A (en) * | 2010-11-06 | 2011-04-20 | 广州市鹏辉电池有限公司 | Positive electrode material of lithium-iron disulfide battery and battery |
| WO2013029282A1 (en) * | 2011-09-02 | 2013-03-07 | 惠州市惠德瑞锂电科技有限公司 | Nonaqueous electrical chemical battery and method for preparing same |
| CN103050660A (en) * | 2012-12-20 | 2013-04-17 | 中银（宁波）电池有限公司 | Method for preparing lithium-iron disulfide battery anode piece |
| CN103367751A (en) * | 2012-04-06 | 2013-10-23 | 广州市华南新能源研究院 | Lithium battery containing transition metal and its oxide and its preparing method |
| CN106044867A (en) * | 2016-06-24 | 2016-10-26 | 中国科学院地球化学研究所 | Preparation method of pyrite electrode |
| CN110048083A (en) * | 2019-04-30 | 2019-07-23 | 哈尔滨工业大学 | A kind of preparation method of anode of solid lithium battery |
-
2004
- 2004-08-09 CN CNA2004100510157A patent/CN1645650A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386907C (en) * | 2006-06-23 | 2008-05-07 | 清华大学 | Lithium-iron disulfide anode materials and method for preparing same |
| CN102024953A (en) * | 2010-11-06 | 2011-04-20 | 广州市鹏辉电池有限公司 | Positive electrode material of lithium-iron disulfide battery and battery |
| WO2013029282A1 (en) * | 2011-09-02 | 2013-03-07 | 惠州市惠德瑞锂电科技有限公司 | Nonaqueous electrical chemical battery and method for preparing same |
| CN103367751A (en) * | 2012-04-06 | 2013-10-23 | 广州市华南新能源研究院 | Lithium battery containing transition metal and its oxide and its preparing method |
| CN103050660A (en) * | 2012-12-20 | 2013-04-17 | 中银（宁波）电池有限公司 | Method for preparing lithium-iron disulfide battery anode piece |
| CN106044867A (en) * | 2016-06-24 | 2016-10-26 | 中国科学院地球化学研究所 | Preparation method of pyrite electrode |
| CN110048083A (en) * | 2019-04-30 | 2019-07-23 | 哈尔滨工业大学 | A kind of preparation method of anode of solid lithium battery |
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