CN1151576C - Method for manufacturing flexible-packaged lithium secondary cell - Google Patents
Method for manufacturing flexible-packaged lithium secondary cellInfo
- Publication number
- CN1151576C CN1151576C CNB021148457A CN02114845A CN1151576C CN 1151576 C CN1151576 C CN 1151576C CN B021148457 A CNB021148457 A CN B021148457A CN 02114845 A CN02114845 A CN 02114845A CN 1151576 C CN1151576 C CN 1151576C
- Authority
- CN
- China
- Prior art keywords
- battery
- cell
- lithium secondary
- pressure
- secondary cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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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
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a method for manufacturing a flexible-packaged lithium secondary cell. In the forming procedure of the cell, a solid electrolyte intermediate phase SEI film is generated on the surface of an exposed cathode, and if the SEI film is not complete, part of the cathode still directly contacts organic solution. If the SEI film is not uniform, the SEI film following the expansion and the contraction of an electrode can not crack in the process of charging and discharging electricity of the cell and expose a new cathode, and the cell can generate harmful reaction in later using and storing period and generate new gas. The contact of each layer of the cell becomes bad, the inner resistance of the cell is increased, and the integral performance of the cell is seriously lowered. In the method for manufacturing a flexible-packaged lithium secondary cell, a pressurized forming method is used after the encapsulating process of an aluminum plastic film, and the cell after the forming process passes the process of vacuum-pumping closure; in the pressurized forming method, the cell is fixed between two flat plates with pressurized devices, and the pressurized devices apply the pressure of 0.5 to 2.5MPa on the flat plates.
Description
Technical field
The present invention relates to a kind of manufacture method of battery, especially a kind of method of making flexible-packaged lithium secondary cell.
Background technology
For a long time, people are pursuing high-octane battery, have carried out the exploitation and the improvement of multiple battery for this reason.In battery up to now, lithium secondary battery has the high power capacity that can expect most, still energetically it is being improved now.Traditional lithium secondary battery comprises positive pole, barrier film, negative pole, and lamination is reeled successively, electrically contacts for keeping electrolyte and effective each interlayer, and it is sealed in the canister.
But canister was both thick and heavily, as nonactive composition, its existence has had a strong impact on the overall performance of battery, not only increased the weight of lithium secondary battery, made miniaturization, lightweight become difficult, and, because the outspoken nature of metal-back, arbitrary shapeization and become impossible.
In view of the situation, lighium polymer secondary battery has been proposed.This battery adopts aluminum plastic film to make packaging material, light weight, and soft variable.But aluminum plastic film exerts pressure for the positive and negative electrode and the barrier film of inside battery, each interlayer is electrically contacted die down, even disconnects separation.People have carried out more research to the structure and the composition of battery for this reason.
U.S. Pat 5460904 discloses a kind of method of making the colloidal polymer lithium ion battery.In the method, make positive and negative electrode material film and electrolyte membrance by knifing or coating, then respectively with positive electrode material film and aluminium collector, negative material film and the hot pressing of copper collector, form positive pole and negative pole, again barrier film is positioned between positive and negative electrode, the three arrives together through the hot pressing close adhesion together, forms micropore by the plasticizer that extracts in each tunic, and reinjecting contains the organic electrolyte of lithium salts.Each step before the fluid injection all can greatly reduce equipment investment and maintenance cost operating under the environment usually.But electrolyte membrance just immerses in the electrolyte after being integral with the positive and negative electrode heat pressure adhesive earlier in this method, for the electrolyte membrance in the middle of making can immerse enough electrolyte, collector must be an expanded metal, and the intensity of wire netting is much worse than metal forming greatly.
For making its unlikely fracture or distortion when the pressurized, must guarantee to have certain thickness, this has strengthened the weight of battery on the other hand.Because active material is distributed in the hole of net and the both sides of net matrix, distance does not wait, and CURRENT DISTRIBUTION also is difficult for evenly.In addition, if pressure distribution is inhomogeneous during hot pressing, colloidal electrolyte barrier film intensity is low, then causes internal short-circuit easily, especially is unfavorable for suitability for industrialized production.
Another kind method is as described in the Chinese patent 99801523,00129272, anodal and negative pole is by general active material and conductive agent, adhesive two surfaces evenly being coated to collector separately, and dryer roll is suppressed, but collector net or paper tinsel.Be coated to two surfaces of positive pole and negative pole after then certain organic solvent, lithium salts, matrix polymer being mixed equably, the dry back of desolvating of removing forms solid-state electrolyte layer on the electrode two sides.The last mutual overlay of both positive and negative polarity, coiling or lamination and battery.This method requires to make electrolyte membrance each step afterwards all carries out in dry atmosphere, improved production cost, and the electronic conductivity of solid electrolyte is lower, makes battery efficiency not high, and this also is one and hinders its practical problem.
The method of Chinese patent 00104502 disclosed making solid state battery and for example.Earlier make positive and negative electrode with active material, conductive agent, bonding agent respectively, then Kynoar and certain organic solvent are made into certain density glue with the paper tinsel collector.After the positive and negative electrode of winding and barrier film are placed in the housing that laminated film makes, outside is injected housing with glue and is made it to be full of whole inner chamber, dry out solvent then with the thickness of pressure apparatus limit battery, make each layer of inside battery stick into one mutually, remaining valid electrically contacts.In the method, each step before the fluid injection all can carry out under normal conditions, equipment cost is not high, but in operation, because glue can only be by entering in the latasuture, then difficult penetrating between the close bed of both positive and negative polarity and barrier film even soaked into, also is difficult in the later dry run and fully organic solution is evaporated.
Above-described various manufacture method, all make great efforts to make the contact of each interlayer of inside battery of aluminum plastic film packing closely even, battery path is maximized the use, but adopt colloidal electrolyte or glue to make adhesive linkage no matter be, all probably improve interlayer bonding in, increase the internal resistance of cell and improve cost of manufacture.
But organic electrolyte in the battery and negative terminal surface are very unstable, and organic solution can react on negative pole.Consume organic solution, generate gas, cause problems such as flatulence even leakage.And battery why can safety and stability depositing and using, and can the flatulence leakage in its process, just be the formation process of battery.In this operation, exposed negative terminal surface generates SEI (Solid ElectrolyteInterphase, phase in the middle of the solid electrolyte) film, negative pole and organic solution have effectively been isolated, if but the SEI film is imperfect, still have the part negative pole directly to contact with organic solution, or if the SEI film is inhomogeneous, then in battery charge and discharge process, can not expands to shrink with electrode and ftracture, expose the negative pole that makes new advances, the capital cause battery afterwards use and bad reaction takes place in the stage of depositing, produce new gas, make each layer of battery contact variation, even separate, the internal resistance of cell increases, and this vicious circle will make cell integrated performance sharply descend.
Summary of the invention
At the problems referred to above, the present invention proposes a kind of method, make the battery of aluminum plastic film packing not need extra adhesive linkage, apply certain pressure to battery when on the make paying attention to changing into, make it forming SEI (SolidElectrolyte Interphase, phase in the middle of the solid electrolyte) fully reacts during film, avoid producing in the circulation afterwards new gas, adopt the way of general Vacuum Package to make the battery poor effect that in its use, is under pressure all the time at last, keep good interlayer contact, raise the efficiency and cycle life.
The technical solution adopted in the present invention is: a kind of method of making flexible-packaged lithium secondary cell, comprise positive pole, barrier film and negative pole are provided, encapsulate with aluminum plastic film behind coiling or the lamination, under drying condition, inject electrolyte, seal up the fluid injection limit, vacuumize again after changing into and seal, make battery, when changing into battery is pressurizeed, promptly battery is fixed between two flat boards of band pressue device, apply the pressure of 0.5～2.5MPa, battery plus-negative plate is connected on the formation device, under condition, change into the battery pressurization.
Described pressue device adopts air pressure, hydraulic pressure or machinery to press and exerts pressure, machinery exert pressure comprise that spiral compresses, spring compression, weight compress.
The invention has the beneficial effects as follows: in changing into, pressurize to battery, in the time of discharging the encapsulation of each interlayer of inside battery residual gas and when changing into the newly-generated gas of reaction, make it tight contact, electrolyte is evenly distributed comprehensively, finish changing into of battery and be included in negative terminal surface and form fine and close SEI uniformly (phase in the middle of the Solid Electrolyte Interphase, solid electrolyte) film necessary condition is provided for guaranteeing high-quality.
Description of drawings
Fig. 1 is a kind of front view of flexible-packed battery;
Fig. 2 is a kind of pressurization chemical synthesizing method of battery shown in Figure 1;
Fig. 3 is the another kind pressurization chemical synthesizing method of battery shown in Figure 1.
Execution mode
The present invention is described in detail below in conjunction with accompanying drawing.
With reference to Fig. 1,1., 2. lug draws the battery positive and negative electrode respectively, 3. is the aluminum plastic film packaging bag, and positive and negative electrode, barrier film and the electrolyte of battery is placed in sealing in the bag; With reference to Fig. 2, a kind of pressurization chemical synthesizing method of battery, this pressurization chemical synthesizing method makes battery anyhow, is the flat board of isolating battery and exerting pressure 4., 5., 6., 7., and dull and stereotyped quantity is more than 2, is flexible-packed battery 8., 9., 10.; With reference to Fig. 3, the another kind of battery pressurization chemical synthesizing method, this pressurization chemical synthesizing method makes battery vertical, is the flat board of isolating battery and exerting pressure 4., 5., 6., 7., is flexible-packed battery 8., 9., 10..
Battery is the aluminum plastic film battery pack, it comprises positive pole, negative pole and places barrier film therebetween etc., and positive and negative electrode all comprises collector and electrode substance respectively, and inorganic salts are dissolved in and constitute electrolyte in the organic solution, be penetrated into each interlayer of positive pole, negative pole and barrier film, activated batteries.The negative electrode active material of this battery can be any in following each material: lithium, lithium alloy and embeddability compound such as natural or Delanium, coke, mesophase-carbon micro-beads etc.; Positive active material can be from LiMn
2O
4, LiCoO
2, LiNiO
2, LiCo
0.5Ni
0.5O
2, choose in the oxyvanadium compound, tin compound; Need, can in electrode, add conductive agent such as carbon black, acetylene black and bonding agent such as Kynoar, polytetrafluoroethylene; Pole piece be by with active material with make mixing paste after conductive agent, bonding agent fully mix by a certain percentage, be coated on the collector with methods such as roller coat, blade coating or sprayings, drying and roll-in are made then, pole piece thickness is preferably 100～400 microns; The shape of collector and thickness depend on how cell shapes and pole piece are placed in battery, usually, negative pole is used aluminium with copper or nickel, positive pole, and preferable alloy paper tinsel of the present invention is made collector; Package casing is an aluminum plastic film, is made of trilamellar membrane at least, is respectively PETG or nylon layer, aluminium foil layer, polyethylene or polypropylene layer, innermost layer polyethylene or polypropylene have heat sealability, can be bonding under uniform temperature and pressure, constitute closely knit bag, have sealing property.The general before use system earlier of this film pouch comprises the inner chamber of placing battery and the airbag that holds issuable gas of the stage of changing into; Barrier film can adopt microporous barriers such as microporous polyethylene, capillary polypropylene; Draw lug by spot welding or supersonic welding from the pole piece collector, but positive pole ear aluminium, and negative lug can be copper or nickel; Barrier film is placed between the positive and negative electrode, put into packaging bag behind coiling or the lamination, packaging bag three limits can be comprised that the emersion lug seals with heat sealing machine this moment on one side, make fluid injection usefulness Yi Bian only stay; The electrolyte that the present invention adopts is that electrolytic salt is dissolved in nonaqueous electrolyte in the organic solvent, about containing the electrolytic salt of lithium, for example: LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiSO
3CF
3And LiN (CF
3SO
2)
2, these electrolytic salts can use separately, also can two or more mixing use; About organic solvent, electrolytic salt must can be dissolved but adhesive on the insoluble electrode, and electrochemical window is enough wide, the energy stable existence is in lithium rechargeable battery, for example, the carbonates of ethylene carbonate, propene carbonate, butylene, diethyl carbonate, ethylene methyl esters, or oxolane, gamma-butyrolacton, sulfolane, dimethoxy-ethane, diethoxyethane, ethyl diethylene glycol dimethyl ether, these solvents can use separately, also can two or more mixing use; Usually the concentration of electrolyte in electrolyte is preferably 1mol/l, and near the conductivity it is the highest, and battery injects electrolyte under low-pressure state, and heating and pressurization make packaging bag edge adhesive seal, and fluid injection needs to carry out under dry atmosphere (relative humidity≤2%).
With reference to Fig. 1, Fig. 2, Fig. 3, battery is after the fluid injection sealing finishes, battery is fixed between the flat board of pressue device, number of batteries is n (n 〉=1), and dull and stereotyped quantity is n+1, clips 1 battery between per 2 flat boards, there is pressue device in the outside at 2 flat boards of ragged edge, can once pressurize like this and change into many batteries, and its both positive and negative polarity is connected on the battery formation device, improve the essential step of battery---change into; But pressure air pressure, oil pressure, machinery are pressed etc., machinery exert pressure comprise that spiral compresses, spring compression, weight compress; Shown in Fig. 2,3, the battery modes of emplacement can horizontal and perpendicular putting, and good vertically to be placed as, pressure is advisable between 0.5～2.5MPa, and if pressure then can not make each layer of battery effectively contact low excessively; Hypertonia may be pushed too quicklyly, punctures barrier film, causes problems such as short circuit, micro-short circuit; Pressure is preferably between 1.0～1.5MPa; Battery after changing into need seal through vacuumizing again, used air extractor is generally vacuum pump, make the packaging bag inside and outside have pressure differential, can reach an atmospheric pressure, because of battery using and depositing in the process and can not produce new gas afterwards, this pressure differential is enough to guarantee the tight contact between pole piece, realizes the excellent properties of battery with this; Experimental results show that, the battery formation efficiency that changes into without pressurization is about 60%, cobalt acid lithium specific discharge capacity can only reach 70-80mAh/g, cycle life mostly is 20 times most, and the battery through pressurizeing and changing into, formation efficiency is more than 87%, and cobalt acid lithium specific discharge capacity is more than the 140mAh/g, cycle life is 〉=300 times at present, and the overall performance of flexible-packed battery is significantly improved.
Claims (4)
1. method of making flexible-packaged lithium secondary cell, comprise positive pole, barrier film and negative pole are provided, with the aluminum plastic film encapsulation, under drying condition, inject electrolyte behind coiling or the lamination, seal up the fluid injection limit, vacuumize again after changing into and seal, make battery, when it is characterized in that changing into battery is pressurizeed, promptly battery is fixed between two flat boards of band pressue device, apply the pressure of 0.5～2.5MPa, battery plus-negative plate is connected on the formation device, under condition, change into the battery pressurization.
2. according to the described a kind of method of making flexible-packaged lithium secondary cell of claim 1, it is characterized in that pressue device applied pressure on flat board is 1.0～1.5MPa.
3. according to the described a kind of method of making flexible-packaged lithium secondary cell of claim 1, it is characterized in that described pressue device adopts air pressure, oil pressure or machinery to press and exerts pressure, machinery exert pressure comprise that spiral compresses, spring compression, weight compress.
4. according to the described a kind of method of making flexible-packaged lithium secondary cell of claim 1, it is characterized in that described number of batteries is n (n 〉=1), dull and stereotyped quantity is n+1, clip 1 battery between every adjacent 2 flat boards, there is pressue device in the outside at 2 flat boards of ragged edge, and can once pressurize like this changes into many batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021148457A CN1151576C (en) | 2002-01-31 | 2002-01-31 | Method for manufacturing flexible-packaged lithium secondary cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021148457A CN1151576C (en) | 2002-01-31 | 2002-01-31 | Method for manufacturing flexible-packaged lithium secondary cell |
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| CN1367547A CN1367547A (en) | 2002-09-04 |
| CN1151576C true CN1151576C (en) | 2004-05-26 |
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| CNB021148457A Expired - Fee Related CN1151576C (en) | 2002-01-31 | 2002-01-31 | Method for manufacturing flexible-packaged lithium secondary cell |
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Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100350668C (en) * | 2005-03-15 | 2007-11-21 | 深圳市比克电池有限公司 | Soft-packaged lithium ion battery manufacturing method |
| CN101281983B (en) * | 2007-04-02 | 2010-10-06 | 深圳邦凯新能源股份有限公司 | Combined production method for flexible package lithium cell |
| US8535818B2 (en) * | 2008-11-19 | 2013-09-17 | GM Global Technology Operations LLC | Method and apparatus for rejuvenation of degraded pouch-type lithium ion battery cells |
| CN101533927B (en) * | 2009-03-17 | 2010-09-29 | 林道勇 | Method for manufacturing lithium ion battery |
| CN102340031A (en) * | 2011-08-03 | 2012-02-01 | 珠海锂源动力科技有限公司 | Follow-up process treatment method for manufacturing battery by taking lithium titanate as cathode |
| CN102456861B (en) * | 2011-12-21 | 2013-12-11 | 万向电动汽车有限公司 | Exhaust device for flexibly-packaged lithium ion battery |
| CN102610860B (en) * | 2012-02-27 | 2015-03-18 | 宁德新能源科技有限公司 | Flexible package lithium ion battery and packaging method thereof |
| CN102800892B (en) * | 2012-08-21 | 2015-04-22 | 杭州万好万家动力电池有限公司 | Pre-formation method of soft-package lithium ion battery and device thereof |
| CN102856590B (en) * | 2012-09-21 | 2014-11-26 | 深圳市美拜电子有限公司 | Forming and capacity grading method of lithium ion secondary battery |
| CN103779613B (en) * | 2014-02-19 | 2016-01-20 | 广州丰江电池新技术股份有限公司 | The battery of ultrathin lithium ion battery formation system, chemical synthesizing method and making |
| CN104953181B (en) * | 2015-05-06 | 2017-12-12 | 中国科学院青岛生物能源与过程研究所 | A kind of technique suppressed using lithium titanate as the lithium ion battery flatulence of negative pole |
| CN106935913B (en) * | 2015-12-31 | 2019-06-28 | 深圳市比克动力电池有限公司 | The preparation method of lithium ion battery |
| CN106198123B (en) * | 2016-08-12 | 2020-04-17 | 合肥国轩高科动力能源有限公司 | Gas collection method for analysis of gas produced in lithium ion battery |
| CN106654428B (en) * | 2017-02-27 | 2019-04-12 | 多氟多新能源科技有限公司 | A kind of manganate lithium ion battery chemical synthesizing method |
| CN108054436A (en) * | 2017-12-13 | 2018-05-18 | 桑顿新能源科技有限公司 | Improve chemical conversion and the verification method of ferric phosphate lithium cell cycle performance |
| CN108565498B (en) * | 2017-12-14 | 2020-06-23 | 多氟多新能源科技有限公司 | Formation method of soft package lithium ion battery |
| CN109065772A (en) * | 2018-03-19 | 2018-12-21 | 东莞纵城智能科技有限公司 | A kind of movement packaging technology of soft-package battery |
| CN109256591B (en) * | 2018-09-04 | 2020-11-06 | 中宁县智才技术服务有限公司 | Soft packet of lithium cell encapsulation supports robot |
| CN109148989A (en) * | 2018-09-04 | 2019-01-04 | 海口博澳国兴新能源科技有限公司 | Novel lithium ion battery production and application method |
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2002
- 2002-01-31 CN CNB021148457A patent/CN1151576C/en not_active Expired - Fee Related
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