CN101887990A - Lithium-ion secondary battery and manufacturing method thereof - Google Patents
Lithium-ion secondary battery and manufacturing method thereof Download PDFInfo
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- CN101887990A CN101887990A CN201010214223XA CN201010214223A CN101887990A CN 101887990 A CN101887990 A CN 101887990A CN 201010214223X A CN201010214223X A CN 201010214223XA CN 201010214223 A CN201010214223 A CN 201010214223A CN 101887990 A CN101887990 A CN 101887990A
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Abstract
The invention discloses a lithium-ion secondary battery and a manufacturing method thereof. The lithium-ion secondary battery comprises an anode material, a cathode material, a diaphragm and electrolyte, wherein, the anode material and the cathode material are coated in a metal casing, the diaphragm is arranged between the anode material and the cathode material, and the electrolyte is filled in the diaphragm; the anode material is prepared by mixing a Ni-Co-Mn ternary material with a lithium manganate material base on a proportion of 1-9:9-1 by weight parts; the cathode material is made of graphite; the electrolyte is prepared by mixing ethylene carbonate, dimethyl carbonate with methyl ethyl carbonate based on the volume ratio of 1:1:1; and the diaphragm is porous polypropylene, polyethylene or a modified polymer of the porous polypropylene and the polyethylene. The invention has the advantages of excellent safety performance, least production cost and larger specific capacity, and through safety tests such as overcharge, over-discharge, short circuit, needling, extrusion, heavy impact, hot box and the like, the safety performance meets the standard testing requirements of UL1642, IEC60949-3 and GB/T18287-2004, and products meet the requirements and reach RoHS instruction requirement.
Description
Technical field
The present invention relates to lithium ion battery, relate to especially that a kind of the cost of material is low, the lithium rechargeable battery with novel anode prescription of security performance excellence, the invention still further relates to the manufacture method of this battery.
Background technology
Lithium ion battery is nineteen nineties Sony corporation of Japan development and begins to realize commercial that its appearance is the once leap on the secondary cell development history.Lithium ion battery is in light weight with it, capacity is high, operating voltage is high, long service life and characteristics such as pollution-free are developed rapidly, and its global marketing volume has surpassed the summation of ni-mh, nickel-cadmium cell.China was having tremendous development aspect the lithium ion battery industrialization in recent years, and 2003 gross annual output amounts have surpassed 2.5 hundred million, reach 600,000,000 production scale in 2005, caught up with and surpassed the advanced world level.
Lithium ion battery is in the past produced positive electrode mostly simple employing cobalt acid lithium, ternary material, LiMn2O4, ferric phosphate lithium cell material, owing to the limitation that these positive electrodes are had separately, influenced production cost, product quality or the security performance of battery.Following several positive electrode commonly used that is: 1, cobalt acid lithium, the commercial anode material for lithium-ion batteries of the first generation, advantage is that drawing abillity is fine, density height, specific capacity are higher relatively, Stability Analysis of Structures, good cycle, voltage platform is higher and more stable; Shortcoming be cost an arm and a leg, capacity almost performed to the limit, resource scarcity, poor stability.2, LiFePO4, cheap, security performance is higher, has structural stability and superior cycle performance preferably; But its tap density is low, volume and capacity ratio is low, conductivity is low, and low temperature performance is poor, multiplying power discharging is poor.3, nickel-cobalt-manganese ternary material, capacity is higher, and its specific capacity exceeds more than 30% than the sour lithium of cobalt, and with cobalt acid lithium identical bound voltage is arranged, than being easier to the scale utilization, price is also relatively cheap, fail safe reaches the compatibility with electrolyte, cycle performance excellence; Shortcoming is synthetic difficulty relatively, and the density of material, voltage platform and efficiency for charge-discharge are lower; 4, LiMn2O4, material property and fail safe are better, and be cheap, but specific capacity is relatively low, and high temperature circulation is lower.Relatively find by above-mentioned, cobalt acid lithium material belongs to narrow resources, and price is higher, though and LiFePO 4 material cycle performance and security performance excellence, but its lower voltage platform and lower compacted density have all influenced the application on lithium rechargeable battery, and anodal ternary material nickel cobalt manganese all is to belong to the cheap material of price comparison with lithium manganate material, has relatively poor voltage platform and discharges and recharges bound voltage.
Summary of the invention
The object of the present invention is to provide a kind of lithium rechargeable battery, the present invention also provides the manufacture method of this battery, to solve existing lithium ion battery production cost height, the big problem of battery material selection utilization limitation, make lithium ion battery have higher security performance and longer useful life.
For achieving the above object, the present invention can take following technical proposals:
A kind of lithium rechargeable battery of the present invention, comprise being coated on positive electrode, the negative material in the metal shell and being arranged on barrier film between described positive electrode and the negative material and can electrolyte in it, described positive electrode by nickel-cobalt-manganese ternary material and lithium manganate material according to weight portion 1～9: 9～1 systems of mixing form; Described negative material is a graphite type material; Described electrolyte was mixed by ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate in 1: 1: 1 by volume; Described barrier film is that porous polypropylene, polyethylene or its are polymer-modified.
Electrolyte salt in the described electrolyte is lithium iodide, lithium perchlorate, and electrolyte solvent is ethylene carbonate, propene carbonate and cyclic ester thereof, and one or several in dimethyl carbonate, diethyl carbonate and chain ester and the butyrolactone mix; Described concentration of electrolyte is 0.5～5.0 mol.
The manufacture method of a kind of lithium rechargeable battery of the present invention comprises the steps:
The first step: positive electrode baking
Nickel-cobalt-manganese ternary material and lithium manganate material are put into vacuum drying oven vacuumize baking, baking temperature is 120～150 ℃, and the time is 4～6 hours;
Second step: make positive solution
Getting and being mixed with concentration after lithium battery binding agent and the solvent is 2-8% solution, after the adding conductive agent disperses, add by 1～9: nickel-cobalt-manganese ternary material and lithium manganate material that 9～1 weight portions take by weighing stir again, and the viscosity of adding solvent adjustment solution, obtaining the slurry solid content is 60～65%, the ratio of weight portion is 70～95: 2～20 between positive electrode, binding agent, the conductive agent three: 2～10 positive solution, the viscosity of described positive solution are 4000～20000mPaS;
The 3rd step: make negative solution
Get and be mixed with the solution that concentration is 1-3% after thickener and water mix, after the adding conductive agent disperses, adding powdered graphite again stirs, and interpolation negative pole binding agent, add entry again and adjust the viscosity of solution, obtaining the slurry solid content is 40～50%, and the ratio of weight portion is 85～95: 2～5 between powdered graphite, negative pole binding agent, conductive agent, the thickener: 1～4: 1～3 negative solution, the viscosity of described negative solution are 1500～4000mPaS;
The 4th step: make positive plate
Positive solution is coated on uniformly on the aluminium foil of thickness 0.016～0.020mm and oven dry, then it is carried out roll extrusion, cut into positive plate, and on positive plate soldering polar ear;
The 5th step: make negative plate
Negative solution is coated on uniformly on the Copper Foil of thickness 0.009～0.012mm and oven dry, then it is carried out roll extrusion, cut into negative plate, and on negative plate soldering polar ear;
The 6th step: reel
Reel after with barrier film positive plate and negative plate being separated and form electric core, in the metal shell of packing into, negative lug and metal shell are welded, positive pole ear and block are welded, be made into the semi-finished product battery; Send into the vacuum oven vacuum bakeout then, make its water content below 200ppm;
The 7th step: fluid injection, seal
At ambient humidity≤2%, under ℃ condition of temperature≤25, give in the dried semi-finished product battery and inject electrolyte, and seal, make the finished product battery;
The 8th step: change into, partial volume
Above-mentioned finished product battery is changed into activation with the order that little electric current strengthens gradually, and control voltage is between 3.80～4.20V.
The invention has the advantages that the security performance excellence, by overcharge, safety test such as overdischarge, short circuit, acupuncture, extruding, heavy impact, hot case, security performance satisfies the standard testing requirement of UL1642, IEC60949-3, GB/T18287-2004, the product compliance with environmental protection requirements reaches the RoHS command request.
Battery performance of the present invention contrasts as following table with the existing battery performance that is used alone positive electrode:
| Cobalt acid lithium | LiMn2O4 | Ternary material | LiFePO4 | The present invention | |
| Specific capacity (mAh/g) | ??140-150 | ??100-110 | ??145-155 | ??120-135 | ??110-150 |
| Resource | Scarce resource | Extensively | Generally | Extensively | Extensively |
| Production cost (unit/AH) | ??3.5-4.0 | ??2.5-3.0 | ??3.0-3.5 | ??3.0-3.5 | ??2.5-3.0 |
| Multiplying power discharging property | Good | Good | Good | Good | Good |
| Voltage platform | ??3.6-3.7 | ??3.7-3.8 | ??3.5-3.6 | ??3.2-3.4 | ??3.6-3.8 |
| Security performance | Generally | Good | Good | Very good | Good |
As can be seen, use ternary to mix battery that manganese is made into as positive pole material of secondary lithium battery with respect to gas material from above-mentioned chart, production cost is minimum, and specific capacity can accomplish greatlyyer, and the security performance excellence can satisfy customer requirements.
Description of drawings
Fig. 1 is the charging and discharging curve figure of battery of the present invention.
Fig. 2 is the cycle life curve chart of battery of the present invention.
Fig. 3 is the structural representation of battery of the present invention.
Embodiment
Lithium rechargeable battery of the present invention, comprise being coated on positive electrode 2, the negative material 3 in the metal shell 1 and being arranged on barrier film 4 between described positive electrode 2 and the negative material 3 and can electrolyte in it, described positive electrode 2 by nickel-cobalt-manganese ternary material and lithium manganate material according to weight portion 1～9: 9～1 (preferred 2: the 8) system of mixing forms; Described negative material 3 is a powdered graphite; Described electrolyte was mixed by ethylene carbonate (EC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) in 1: 1: 1 by volume; Described barrier film 4 is porous polypropylene (PP) or polyethylene (PE).
Electrolyte salt in the described electrolyte can be lithium iodide (LiI), lithium perchlorate (LiCIO
4), electrolyte solvent can be ethylene carbonate (EC), propene carbonate cyclic esters such as (PC), one or several in dimethyl carbonate (DMC), diethyl carbonate ester such as (DEC) chain and the butyrolactone (GBL) etc. mix; Described concentration of electrolyte is 0.5～5.0 mol.
The manufacture method of lithium rechargeable battery of the present invention comprises the steps:
The first step: positive electrode baking
Nickel-cobalt-manganese ternary material and lithium manganate material are put into vacuum drying oven vacuumize baking, baking temperature is 120～150 ℃, and the time is 4～6 hours, 120 ℃ of preferred temperature, stoving time 4 hours;
Second step: make positive solution
After getting lithium battery binding agent PVDF and solvent NMP and being mixed with the solution of concentration 5%, the employing high speed dispersor mixes, use the speed of revolution more than 30 rev/mins, rotation uses the speed more than 1000 rev/mins to stir 1 hour, add conductive agent SP, improve rotational velocity more than 1500 rev/mins, after carrying out the dispersion more than 0.5 hour, add the nickel-cobalt-manganese ternary material and the lithium manganate material that take by weighing by 2: 8 weight portions again, rotation uses the speed more than 1000 rev/mins to stir 1-5 hour, add the viscosity of solvent NMP adjustment solution, obtaining the slurry solid content is 60～65% (preferred 65%), positive electrode, binding agent, the ratio of weight portion is 95: 2.4: 2.6 a positive solution between the conductive agent three, uses the rotation viscometer tested viscosity, the viscosity of gained positive solution is 6000mPaS, this solution is crossed behind 200 mesh sieves directly used;
The 3rd step: make negative solution
After thickener CMC and water is mixed with the solution of concentration 1.5%, the employing high speed dispersor mixes, use the speed of revolution more than 30 rev/mins, rotation uses the speed more than 1000 rev/mins to stir 1 hour, add conductive agent (SP), improve rotational velocity more than 1500 rev/mins, after the time of carrying out more than 0.5 hour disperses, add powdered graphite again, rotation uses the speed more than 1000 rev/mins to stir 1-5 hour, and add negative pole binding agent (SBR) and stir more than 0.5 hour, add the viscosity that solution is adjusted in entry, obtaining the slurry solid content is 45%, powdered graphite, negative pole binding agent (SBR), conductive agent (SP), the ratio of weight portion is 95: 2.5: 1.0 between the CMC: 1.5 negative solution, use the rotation viscometer tested viscosity, the viscosity of negative solution is 3000mPaS, directly uses after this negative solution is crossed 200 mesh sieves;
The 4th step: make positive plate
Positive solution is coated on uniformly on the aluminium foil of thickness 0.016mm, adopts 120 ℃ hot air circulation to dry, 4 meters/minute of speed, the surface density of coating are 450g/m
2, control precision is at 8g/m
2In, adopt 300 tons pressure to carry out roll extrusion then, make compacted density be controlled at 3.0 (gram/cubic centimetres), and by the length and the wide pole piece that cuts into of technological requirement, to aluminium foil soldering polar ear (aluminium strip) on the pole piece, and carry out termination at the privileged site of lug and pole piece, generally adopt the adhesive plaster of acid and alkali-resistance and solution;
The 5th step: make negative plate
Negative solution is coated on uniformly on the Copper Foil of thickness 0.009mm, adopts 100 ℃ hot air circulation to dry; Speed is generally at 5 meters/minute, and the surface density of coating is 87g/m
2, control precision is at 5g/m
2Adopt 500 tons pressure to carry out roll extrusion then, make compacted density be controlled at 1.5 (gram/cubic centimetres), and by the length and the wide negative plate that cuts into of technological requirement, to Copper Foil soldering polar ear (nickel strap) on the pole piece, and carry out termination at the privileged site of lug and pole piece, generally adopt the adhesive plaster of acid and alkali-resistance and solution;
The 6th step: reel
Positive plate, negative plate and barrier film are reeled, guarantee that barrier film separates positive pole and cathode pole piece, form electric core, pack in the metal shell, the negative lug and the metal shell of electric core are welded, positive pole ear and block are welded, be made into the semi-finished product battery; Send into then and vacuumize baking in the vacuum oven and dried electric in-core portion moisture in 36 hours, guarantee that semi-finished product battery water content below 200ppm, makes it have good performance;
The 7th step: fluid injection, seal
At ambient humidity≤2%, under ℃ condition of temperature≤25, give in the dried semi-finished product battery and inject electrolyte, and adopt mechanical mode of sealing to seal, make the finished product battery;
The 8th step: change into, partial volume
Above-mentioned finished product battery is changed into activation with the order that little electric current 0.05C, 0.1C, 0.2C strengthen gradually, controls voltage between 3.80～4.20V,, adopt following system to activate and partial volume:
Activation: the 0.05C 120min that charge, change 0.1C charging 180min, change the 0.2C 120min that charges, upper voltage limit 3.85V;
Partial volume: the 1C 120min that charges shelves 10min, changes 1C discharge 90min, upper voltage limit 4.20V, lower voltage limit 2.75V.
Can perform to 115mAh/g (can increase) for above-mentioned anode gram specific capacity by the ratio gram specific capacity that increases ternary material, capability retention 95.0% circulates 100 times, its security performance excellence, can by overcharge, safety test such as overdischarge, short circuit, acupuncture, extruding, heavy impact, hot case.Fig. 1 is the charging and discharging curve figure of battery of the present invention.Fig. 2 is the cycle life curve chart of battery of the present invention.
Above-mentioned only is preferable case study on implementation of the present invention, and the doping proportioning of anodal ternary material and LiMn2O4 can change to some extent according to technological requirement, and promptly all equivalences of doing according to the content of the present patent application scope change and modify, and all should be technology category of the present invention.
Claims (3)
1. lithium rechargeable battery, comprise be coated on positive electrode (2), the negative material (3) in the metal shell (1) and be arranged on described positive electrode (2) and negative material (3) between barrier film (4) and can electrolyte in it, it is characterized in that: described positive electrode (2) by nickel-cobalt-manganese ternary material and lithium manganate material according to weight portion 1～9: 9～1 mixed systems form; Described negative material (3) is a graphite type material; Described electrolyte was mixed by ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate in 1: 1: 1 by volume; Described barrier film (4) is that porous polypropylene, polyethylene or its are polymer-modified.
2. lithium rechargeable battery according to claim 1, it is characterized in that: the electrolyte salt in the described electrolyte is lithium iodide, lithium perchlorate, electrolyte solvent is ethylene carbonate, propene carbonate and cyclic ester thereof, and one or several in dimethyl carbonate, diethyl carbonate and chain ester and the butyrolactone mix; Described concentration of electrolyte is 0.5～5.0 mol.
3. the manufacture method of lithium rechargeable battery according to claim 1, it is characterized in that: it comprises the steps:
The first step: positive electrode baking
Nickel-cobalt-manganese ternary material and lithium manganate material are put into vacuum drying oven vacuumize baking, baking temperature is 120～150 ℃, and the time is 4～6 hours;
Second step: make positive solution
Getting and being mixed with concentration after lithium battery binding agent and the solvent is 2-8% solution, after the adding conductive agent disperses, add by 1～9: nickel-cobalt-manganese ternary material and lithium manganate material that 9～1 weight portions take by weighing stir again, and the viscosity of adding solvent adjustment solution, obtaining the slurry solid content is 60～65%, the ratio of weight portion is 70～95: 2～20 between positive electrode, binding agent, the conductive agent three: 2～10 positive solution, the viscosity of described positive solution are 4000～20000mPaS;
The 3rd step: make negative solution
Get and be mixed with the solution that concentration is 1-3% after thickener and water mix, after the adding conductive agent disperses, adding powdered graphite again stirs, and interpolation negative pole binding agent, add entry again and adjust the viscosity of solution, obtaining the slurry solid content is 40～50%, and the ratio of weight portion is 85～95: 2～5 between powdered graphite, negative pole binding agent, conductive agent, the thickener: 1～4: 1～3 negative solution, the viscosity of described negative solution are 1500～4000mPaS;
The 4th step: make positive plate
Positive solution is coated on uniformly on the aluminium foil of thickness 0.016～0.020mm and oven dry, then it is carried out roll extrusion, cut into positive plate, and on positive plate soldering polar ear;
The 5th step: make negative plate
Negative solution is coated on uniformly on the Copper Foil of thickness 0.009～0.012mm and oven dry, then it is carried out roll extrusion, cut into negative plate, and on negative plate soldering polar ear;
The 6th step: reel
Reel after with barrier film positive plate and negative plate being separated and form electric core, in the metal shell of packing into, negative lug and metal shell are welded, positive pole ear and block are welded, be made into the semi-finished product battery; Send into the vacuum oven vacuum bakeout then, make its water content below 200ppm;
The 7th step: fluid injection, seal
At ambient humidity≤2%, under ℃ condition of temperature≤25, give in the dried semi-finished product battery and inject electrolyte, and seal, make the finished product battery;
The 8th step: change into, partial volume
Above-mentioned finished product battery is changed into activation with the order that little electric current strengthens gradually, and control voltage is between 3.80～4.20V.
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| CN102148405A (en) * | 2011-03-07 | 2011-08-10 | 重庆永通信息工程实业有限公司 | Method for manufacturing low-temperature lithium-ion battery |
| CN102956874A (en) * | 2011-08-17 | 2013-03-06 | 珠海银通新能源有限公司 | Positive electrode film and lithium ion power battery, and preparation method thereof |
| CN103296304A (en) * | 2013-05-03 | 2013-09-11 | 浙江超威创元实业有限公司 | Lithium ion battery with improved over charge performance |
| CN103647084A (en) * | 2013-12-20 | 2014-03-19 | 山东精工电子科技有限公司 | Method for efficiently preparing positive and negative electrode paste |
| CN104347847A (en) * | 2013-08-06 | 2015-02-11 | 中国人民解放军63971部队 | Preparation method of lithium manganate-ternary material composite positive electrode piece |
| CN104916866A (en) * | 2015-05-25 | 2015-09-16 | 潍坊天泽新能源有限公司 | Safe lithium ion cell |
| CN106125694A (en) * | 2016-08-19 | 2016-11-16 | 深圳市信宇人科技有限公司 | The intelligence control system of the complete automatic assembly line of electrodes of lithium-ion batteries and method |
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| CN106469829A (en) * | 2015-08-20 | 2017-03-01 | 郑州比克电池有限公司 | Lithium ion battery forming and capacity dividing method |
| CN107394197A (en) * | 2017-07-18 | 2017-11-24 | 宁波富理电池材料科技有限公司 | A kind of positive electrode, its preparation method and lithium ion battery |
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| CN107579209A (en) * | 2017-07-22 | 2018-01-12 | 深圳卓朗新能源科技有限公司 | A kind of high security ter-polymers lithium ion battery |
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| CN102148405A (en) * | 2011-03-07 | 2011-08-10 | 重庆永通信息工程实业有限公司 | Method for manufacturing low-temperature lithium-ion battery |
| CN102956874A (en) * | 2011-08-17 | 2013-03-06 | 珠海银通新能源有限公司 | Positive electrode film and lithium ion power battery, and preparation method thereof |
| CN102956874B (en) * | 2011-08-17 | 2014-12-31 | 珠海银隆新能源有限公司 | Positive electrode film and lithium ion power battery, and preparation method thereof |
| CN103296304A (en) * | 2013-05-03 | 2013-09-11 | 浙江超威创元实业有限公司 | Lithium ion battery with improved over charge performance |
| CN104347847A (en) * | 2013-08-06 | 2015-02-11 | 中国人民解放军63971部队 | Preparation method of lithium manganate-ternary material composite positive electrode piece |
| CN103647084B (en) * | 2013-12-20 | 2016-08-17 | 山东精工电子科技有限公司 | A kind of method efficiently preparing both positive and negative polarity electrode slurry |
| CN103647084A (en) * | 2013-12-20 | 2014-03-19 | 山东精工电子科技有限公司 | Method for efficiently preparing positive and negative electrode paste |
| CN104916866A (en) * | 2015-05-25 | 2015-09-16 | 潍坊天泽新能源有限公司 | Safe lithium ion cell |
| CN104916866B (en) * | 2015-05-25 | 2018-09-25 | 潍坊天泽新能源有限公司 | Safety lithium-ion electric core |
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