CN100397700C - Thin type lithium ion battery and preparing method - Google Patents
Thin type lithium ion battery and preparing method Download PDFInfo
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- CN100397700C CN100397700C CNB2005101105393A CN200510110539A CN100397700C CN 100397700 C CN100397700 C CN 100397700C CN B2005101105393 A CNB2005101105393 A CN B2005101105393A CN 200510110539 A CN200510110539 A CN 200510110539A CN 100397700 C CN100397700 C CN 100397700C
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- lithium ion
- ion battery
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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
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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
- 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 provides a thin type lithium ion battery and a preparing method, which has excellent electrochemical performance and can be used for built-in power supplies of super smart cards. The lithium ion battery comprises a cathode 3, an anode 2 and electrolyte 4 which are arranged in a metal foil shell 1, wherein the metal foil not only is a sealing shell, but also is an anode current collector, and a sealing cement layer and a hot melting macromole diaphragm are arranged between the metal foil shells for sealing. A cathode conductive terminal is connected with the metal foil shell, and the anode conductive terminal is directly connected with the anode current collector and is in compact hot pressing on the macromole diaphragm so as to prevent short circuit.
Description
Technical field
The present invention relates to a kind of is the thin lithium ion battery and the preparation method of housing with the metal forming.More specifically, prepared a kind of high-energy-density, long circulation life and the thickness thin lithium ion battery less than 0.5mm, this battery can be used as the built-in power of supper-intelligent card.The invention belongs to the lithium ion battery field.
Background technology
Since nineteen ninety Japan Sony company take the lead in succeeding in developing lithium ion battery and with its commercialization since, obtained fast development as the lithium ion battery of battery of new generation.Nowadays lithium ion battery has been widely used in various electronic equipments, many equipment manufacturers also with lithium ion battery as standard energy supply parts.Simultaneously, along with the continuous progress of science and technology, the more new development of electronic equipment and device has proposed more higher requirements to the performance of battery.Require battery microminiaturization, power lithium-ion battery to require the high power of battery as pure electric vehicle, the automobile-used lithium ion battery capacity required maximization of hybrid electrically, system-on-chip, supper-intelligent card built-in power then requires the battery slimming.
Smart card (Smart Card) refers generally to a plastic cards of giving sizing, has encapsulated integrated circuit (IC) chip above, adopts microelectric technique to carry out storage, the processing of information.Form structure according to it, smart card can be divided into non-encrypted storage card, encrypt storage card, central processing unit card and supper-intelligent card.The main application fields of smart card has financial circles, telecommunications industry, communications, medical institutions, pay TV, identification system etc. at present.
General smart card only carries out accessing operation or simple process to information, therefore need not expend a lot of electric power.Can provide required electric power with contact that card reader (as ATM) contacts as contact intelligent IC (Integrate Circuit) when being stuck in work, finish corresponding operation; The electric power that untouchable intellective IC card (as the public transport radio-frequency card) then can rely on induction coil to be produced when being subjected to responding to carries out work.And supper-intelligent card (Super Smart Card) generally has microprocessor and memory, and parts such as keyboard and LCD are housed, and also has identity recognition device etc. on the card that has, and therefore needs built-in power to satisfy its demand of sophisticated functions day by day.Built-in power has been arranged, and the supper-intelligent card of a new generation just can be supported many brand-new functions: (1) is supported random asccess memory and is kept the CPU running, can do proof of identity, the finance data transmission of encryption, more complicated cryptographic calculation etc.; (2) for the parts on the smart card provide energy, for example keyboard, LCD, sound equipment etc.; (3) strengthen the ability of smart card, farther distance of reaction etc. is provided.
(85.6mm * 54.0mm * 0.83mm) and the restriction of flexible performance, the flexible thin lithium battery becomes unique available built-in power because the physical size of smart card own.Integrated function element is not quite similar on the supper-intelligent card of different company at present, also do not form general international standard, therefore built-in thin battery does not have fixing dimensions yet, and cell area is no more than 1/4 of smart card area usually, and cell thickness should be less than 0.5mm.
Commercial now casing of lithium ion battery is generally metal-back (as stainless steel case, aluminum hull etc.) or plastic-aluminum encapsulating film.With the package parts of common metal shell as battery, its thickness is too thick, can not satisfy the requirement of supper-intelligent card.And the plastic-aluminum encapsulating film that generally uses in ALB (Aluminum Laminated batteries) has three laminations that are made of inboard thermoplastic resin, middle metal foil layer and outside insulator layer at least, add the adhesive layer between superimposed layer, thickness has 80 μ m～120 μ m at least.Like this concerning integral battery door, the thickness of encapsulated layer just accounts for 160 μ m～240 μ m at least, add parts such as both positive and negative polarity collector that inside battery is essential and barrier film, therefore the active matter mass-energy occupation space of battery is just smaller, cause the capacity of battery to be restricted, can't bring into play the high characteristics of lithium ion battery energy density.
Many in recent years companies such as Cymbet Corporation, Infinite Power Solutions, Solicore Inc. and Varta Battery have announced commercialization one after another and have been applicable to the slim lithium battery of smart card.
Wherein, Cymbet Corporation and Infinite Power Solutions adopt technologies such as radio frequency (direct current) magnetron sputtering and vacuum thermal evaporation to assemble flat, flexible all solid-state thin-film lithium battery, and area is from 0.1 μ m
2To 10m
2, thickness from 5 to 25 μ m do not wait.It can be in a lot of substrates deposition of wire (lug), positive pole, solid electrolyte, negative pole in order, deposit special packaging film at last and finish entire cell.The negative pole of entire cell adopts metal Li, the anodal LiCoO that adopts
2, solid electrolyte adopts the LiPON of U.S.'s Oak Ridge National Laboratory exploitation.Because the various piece of deposition is fine and close evenly, and the shared ratio of special packaging film is little, and entire cell demonstrates the energy density 200Wh/kg of superelevation, volume and capacity ratio 500Wh/L, and cycle life surpasses 70000 times, self-discharge rate＜1% every year.
Adopt the film lithium cell of all solid state technology preparation to have ultra-thin characteristic, thickness can have superpower cycle performance below 0.1mm, and high rate charge-discharge is functional.But just because of the ultra-thin characteristic of its electrode, also brought simultaneously the battery capacity problem of smaller on the unit are, and adopt the speed of process deposits films such as magnetron sputtering quick inadequately, more complicated on the technology, be difficult to extensive industrialization, preparation cost that it is higher and technology barriers make large-scale application be subjected to certain restriction.
The product of German in addition Varta Battery is Li/MnO
2Disposable lithium-battery (patent No. US 20030118894 and US 20030232241).Concrete preparation process is as follows: at first with MnO
2360 ℃ of following thermal activations, press mass ratio 77%MnO
2, 6% graphite, 2% conductive carbon black Super P, 7% Kynoar (PVDF-HFP), 8% propene carbonate (PC), in acetone soln, mix, slurry is coated on the polypropylene diaphragm oven dry in 48 hours of 110 ℃ of vacuum.Subsequently product is immersed in 0.96M LiClO
4In/PC+EMC (volume ratio 87: the 13) solution, obtain the polymer positive pole.Then that negative pole (the Li thermal evaporation is on the Cu paper tinsel), polymer is anodal and to scribble the conduction Cu paper tinsel of graphite stacked together, prevent Cu paper tinsel contact short circuit with insulating material, the ultrasonic bonding encapsulation obtains the lithium battery of thickness 0.4mm at last.The battery of Varta adopts Copper Foil as encapsulating material, and thickness is compared the plastic-aluminum encapsulating film and significantly reduced, and the active material occupation space increases relatively, helps improving battery capacity.Because both positive and negative polarity has adopted MnO respectively
2And Li, so the lithium battery of Varta preparation is disposable, can not continue charging behind the discharge off again, the energy that can provide can not satisfy the needs of supper-intelligent card fully, and the process route slightly complicated of taking.
Summary of the invention
The object of the present invention is to provide that a kind of preparation method is simple, chemical property is good and can be applied to thin lithium ion battery of supper-intelligent card built-in power and preparation method thereof, related material all is a material commonly used in the lithium ion battery production process in the preparation process, preparation technology is simple to operation, easy realization of large-scale production.
The thin lithium ion battery that the present invention proposes comprises a negative electrode, anode and electrolyte, is included in the housing that is formed by metal forming.Wherein metal forming is not only as housing but also as negative current collector, and the metal forming housing seals with adhesive layer and hot melt macromolecule layer, and anodal conducting terminal directly connects plus plate current-collecting body, and the negative pole conducting terminal then is connected with the metal forming housing.Described metal foil layer is a copper foil layer, and thickness is 10-20 μ m.
The thin lithium ion battery that the present invention proposes can adopt relative simple technology to prepare, and has reduced preparation cost, is fit to large-scale production, concrete preparation process following (as attached Fig. 1 and 2 illustrative):
(a) anode active material, conductive agent and binders for electrodes are mixed into uniform slurry in proportion, are coated on the metal forming (1) of cutting out in advance, vacuum and heating drying obtains anode (2); The applying solid content of material is 10-15g/cm
2
(b) cathode active material, conductive agent and binders for electrodes are mixed into uniform slurry in proportion, dual coating is on aluminium foil (5), vacuum and heating drying also is cut into corresponding size and obtains negative electrode (3), the positive pole conduction of burn-oning again lug (7), (8) are the resin sheet attached to lug face seal part; The double spread solid matter content is 45-55g/cm
2
(c) apply sealing cement layer (10) in the edge of metal forming part, be stained with one deck hot melt macromolecule membrane (6) after the drying, in the middle of two parts anode, be stained with one deck polyimides (9) and take place when preventing that metal forming is folding damaged;
(d) cover barrier film (4) at cathode surface, make negative electrode, anode surface relative along the center line doubling metal forming, add negative pole conduction lug (11),, again metal forming and negative lug are welded battery top and a side vacuum heat-sealing;
(e) inject a certain amount of lithium-ion battery electrolytes toward inside battery, another side vacuum heat-sealing with remaining promptly obtains thin lithium ion battery.According to the coating thickness of electrode slice, the about 0.35～0.5mm of the thickness of battery.
Described anode, cathode active material comprise the material that can reversibly embed or deviate from lithium ion; Particularly, anode is formed by a kind of material that can reversibly introduce or remove lithium ion; Negative electrode is formed by the material that can reversibly introduce or remove lithium ion;
But described anode is graphite-like material with carbon element, tin class alloy or other removal lithium embedded alloy or silicon is any one in the negative material.
Described negative electrode is LiCoO
2, LiCo
1-xNi
xO
2, LiCo
1-x-yNi
xMn
yO
2, spinel structure LiMn
2O
4Perhaps olivine structural LiFePO
4In any one.
Described conductive agent comprises acetylene black, carbon black;
Described binders for electrodes comprises Kynoar, butadiene-styrene rubber;
Described metal forming mainly refers to Copper Foil;
Described sealing cement is the lithium ion battery special seal gum, is the HJX-02 lithium ion battery fluid sealant of the smart prosperous adhesive technology in Harbin Development Co., Ltd production;
Described hot melt macromolecule membrane is a polyimide film;
Described lithium-ion battery electrolytes is the anhydrous liquid electrolyte, as 1mol/LiPF
6/ EC ethylene carbonate+DMC dimethyl carbonate (volume ratio 1: 1), and be added with a spot of functional additive.
The thin battery that with the metal forming is shell is very responsive to the gas that inside battery produces, therefore the electrolyte content that needs the control battery, and in electrolyte, add the gas that produces when certain quantity of additive suppresses battery and changes into, add the suitable parameters such as both positive and negative polarity Capacity Ratio of adjusted, the thin battery that the present invention prepares has high-energy-density and long circulation life, cell thickness meets the requirement of supper-intelligent card fully, and its flexible metal forming shell can allow battery pass through the international testing standard of the bending property of smart card.
Description of drawings
Fig. 1 is the structural representation before thin battery provided by the invention does not encapsulate, and for the sake of clarity, has omitted battery diaphragm.
Fig. 2 is the generalized section of thin battery after the encapsulation of Fig. 1 dotted line intercepting.
Fig. 3 is the typical charging and discharging curve of the thin battery in the embodiment of the invention 1.
Fig. 4 is the cycle performance curve of the thin battery in the embodiment of the invention 1.
Embodiment
Below in conjunction with accompanying drawing, further specify substantive distinguishing features of the present invention and obvious improvement, but the present invention is not limited to present embodiment.
1 and 2 present embodiments are described in conjunction with the accompanying drawings.Take by weighing mass ratio 88% carbonaceous mesophase spherules, 5% acetylene black, 7% Kynoar (being dissolved in methyl pyrrolidone NMP in advance), evenly stir into slurry, be coated in the Copper Foil (1) that cuts in advance and go up (basic size 50mm * 68mm, thickness 15 μ m, negative lug is reserved in the relevant position), the about 12mg/cm of applying solid content of material
2, vacuum and heating drying obtains negative pole (2), and two parts active material is the center line symmetry, basic size 22mm * 32mm (particular location is as shown in Figure 1), negative pole thickness is about 100 μ m after the roll-in.
Apply the lithium ion battery fluid sealant (10) of one deck width 7mm in Copper Foil edge part, be stained with the hot melt polyimides film (6) of one deck width 7mm slightly after the drying again, be stained with one deck polyimides (9) at the midline position of Copper Foil and take place when preventing the Copper Foil doubling damagedly, prevent the leakage of battery electrolyte.
Take by weighing mass ratio 85% cobalt acid lithium, 8% acetylene black, 7% Kynoar (being dissolved in methyl pyrrolidone NMP in advance), evenly stir into slurry, dual coating goes up as anodal (3), the about 51mg/cm of double spread solid matter content at the aluminium foil (5) of thickness 15 μ m
2Vacuum and heating drying also is cut into basic size 20mm * 30mm (relevant position reservation lug), the about 170 μ m of anodal thickness after the roll-in, the anodal conducting terminal (7) of ultrasonic bonding, exposed aluminum foil current collector between positive active material and the anodal conducting terminal resin sheet is made insulation processing be short-circuited, coat the lithium ion battery polypropylene diaphragm (4) of thickness 20 μ m then on anodal surface to prevent to contact with Copper Foil.
The positive pole that coats barrier film is put in the appropriate location makes both positive and negative polarity surface relative (particular location as shown in Figure 1), along the doubling of Copper Foil center line, put negative pole conducting terminal (11) in the relevant position, with top and side vacuum heat-sealing of battery, with Copper Foil lug and the ultrasonic bonding of reserving of negative pole conducting terminal.
Be to inject about 0.2g lithium-ion battery electrolytes toward inside battery under the dry air ambient, placement a period of time makes the electrolyte wetting electrode, again with another side vacuum heat-sealing of battery, promptly obtains the thin lithium ion battery of the about 0.4mm of thickness.
Thin lithium ion battery is aging through 40 ℃ of following 24h, on the blue electric battery test system in Wuhan, carry out battery change into and constant current charge-discharge (discharge and recharge standard: constant current 7mA is charged to 4.2V, constant voltage 4.2V charges to electric current less than 0.7mA, left standstill 3 minutes, constant current 7mA discharges into 3.0V), the result shows the about 36mAh of battery capacity under the normal temperature 0.2C electric current, battery bulging not after 200 charge and discharge cycles, capability retention about 83%.Have now and studies show that a lot of materials all have the performance of reversible removal lithium embedded ion, just removal lithium embedded current potential, removal lithium embedded capacity and removal lithium embedded invertibity separately has very big difference.In order to guarantee that thin battery has good electrochemical, the suggestion negative pole is selected the graphite-like material with carbon element for use, and is anodal then can select the electrode material of comparative maturity in the market such as the sour lithium of cobalt for use, can certainly select some rich lithium materials such as layer structure LiCo for use
1-xNi
xO
2, LiCo
1-x-yNi
xMn
yO
2, spinel structure LiMn
2O
4Perhaps olivine structural LiFePO
4Deng material.Adopt other poor lithium material, but as tin class alloy, other removal lithium embedded alloy or silicon is negative material, equally also can prepare thin lithium ion battery, just want more inferior at aspects such as the overall performances of battery especially cycle characteristics according to the method for embodiment 1.
Claims (10)
1. thin lithium ion battery, negative electrode, anode and the electrolyte of forming battery is included in the housing that is formed by metal forming, anodal conducting terminal directly connects plus plate current-collecting body, it is characterized in that metal forming is again as negative current collector, the negative pole conducting terminal then is connected with the metal forming housing, and the metal forming housing seals with adhesive layer and hot melt macromolecule membrane.
2. by the described thin lithium ion battery of claim 1, it is characterized in that described metal foil layer is a copper foil layer, thickness is 10～20 μ m.
3. by the described thin lithium ion battery of claim 1, it is characterized in that the binding agent that the metal forming housing seal is used is the lithium ion battery fluid sealant: the hot melt macromolecule membrane that described metal forming housing seal is used is a polyimide film.
4. the method for preparing thin lithium ion battery as claimed in claim 1, its concrete processing step is:
(a) anode active material, conductive agent and binders for electrodes are mixed into uniform slurry in proportion, are coated on the metal forming (1) of cutting out in advance, vacuum and heating drying obtains anode (2);
(b) cathode active material, conductive agent and binders for electrodes are mixed into uniform slurry in proportion, dual coating is on aluminium foil (5), and vacuum and heating drying also is cut into corresponding size and obtains negative electrode (3), the anodal conduction lug (7) of burn-oning again;
(c) apply sealing cement layer (10) in the edge of metal forming part, be stained with one deck hot melt macromolecule membrane (6) after the drying, two parts anode centre position is stained with one deck polyimides (9);
(d) cover barrier film (4) at cathode surface, make negative electrode, anode surface relative along the center line doubling metal forming, add negative pole conduction lug (11),, again metal forming and negative lug are welded battery top and a side vacuum heat-sealing;
(c) inject lithium-ion battery electrolytes toward inside battery, with another remaining side vacuum heat-sealing.
5. by the preparation method of the described thin lithium ion battery of claim 4, it is characterized in that anode is formed by a kind of material that can reversibly introduce or remove lithium ion; Negative electrode is formed by the material that can reversibly introduce or remove lithium ion.
6. press the preparation method of the described thin lithium ion battery of claim 4, but it is characterized in that described anode is that graphite-like material with carbon element, tin class alloy or other removal lithium embedded alloy or silicon are any one in the negative material.
7. by the preparation method of the described thin lithium ion battery of claim 4, it is characterized in that described negative electrode is LiCoO
2, LiCo
1-xNi
xO
2, LiCo
1-x-yNi
xMn
yO
2, spinel structure LiMn
2O
4Perhaps olivine structural LiFePO
4In any one.
8. by the preparation method of the described thin lithium ion battery of claim 4, it is characterized in that applying sealing cement width 5～10mm, the width that is stained with the hot melt macromolecule membrane thereon again is 5～10mm, and the width that both select for use is identical.
9. by the preparation method of the described thin lithium ion battery of claim 4, it is characterized in that the solid matter content that described step (a) applies is 10-15g/cm
2
10. by the preparation method of the described thin lithium ion battery of claim 4, it is characterized in that the solid matter content of described step (b) dual coating is 45-55g/cm
2
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| CNB2005101105393A CN100397700C (en) | 2005-11-18 | 2005-11-18 | Thin type lithium ion battery and preparing method |
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|---|---|---|---|
| CNB2005101105393A CN100397700C (en) | 2005-11-18 | 2005-11-18 | Thin type lithium ion battery and preparing method |
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| CN100397700C true CN100397700C (en) | 2008-06-25 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105576280A (en) * | 2014-10-09 | 2016-05-11 | 东莞新能源科技有限公司 | Flexible cell and preparation method thereof |
| CN105406086B (en) * | 2015-10-28 | 2018-09-11 | 广东烛光新能源科技有限公司 | Electrochemical cell and preparation method thereof |
| CN105390628A (en) * | 2015-10-28 | 2016-03-09 | 广东烛光新能源科技有限公司 | Electrochemical cell and preparation method thereof |
| CN105529501A (en) * | 2016-01-21 | 2016-04-27 | 东莞市海量能源科技有限公司 | Preparation method of thin lithium battery |
| CN106960976A (en) * | 2017-05-05 | 2017-07-18 | 杭州金色能源科技有限公司 | Thin-type secondary battery and preparation method thereof |
| CN109585896A (en) * | 2017-09-29 | 2019-04-05 | 辉能科技股份有限公司 | Flexible battery |
| CN111129367A (en) * | 2019-12-30 | 2020-05-08 | 广东微电新能源有限公司 | Energy storage device and assembling method thereof |
| CN117558996A (en) * | 2024-01-11 | 2024-02-13 | 北京郅航科技有限公司 | Full-tab battery and preparation method thereof |
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| CN1192058A (en) * | 1997-02-26 | 1998-09-02 | 索尼株式会社 | Thin type cell |
| CN2410745Y (en) * | 2000-03-17 | 2000-12-13 | 深圳市比亚迪实业有限公司 | Thin lithium ion battery |
| US6203941B1 (en) * | 1998-12-18 | 2001-03-20 | Eveready Battery Company, Inc. | Formed in situ separator for a battery |
| CN1398012A (en) * | 2001-07-13 | 2003-02-19 | 比亚迪股份有限公司 | Method for manufacturing thin lithium ion battery |
| US20030118894A1 (en) * | 2001-12-20 | 2003-06-26 | Varta Microbattery Gmbh | Galvanic element having a thin, flat, and flexible metal housing |
-
2005
- 2005-11-18 CN CNB2005101105393A patent/CN100397700C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1192058A (en) * | 1997-02-26 | 1998-09-02 | 索尼株式会社 | Thin type cell |
| US6203941B1 (en) * | 1998-12-18 | 2001-03-20 | Eveready Battery Company, Inc. | Formed in situ separator for a battery |
| CN2410745Y (en) * | 2000-03-17 | 2000-12-13 | 深圳市比亚迪实业有限公司 | Thin lithium ion battery |
| CN1398012A (en) * | 2001-07-13 | 2003-02-19 | 比亚迪股份有限公司 | Method for manufacturing thin lithium ion battery |
| US20030118894A1 (en) * | 2001-12-20 | 2003-06-26 | Varta Microbattery Gmbh | Galvanic element having a thin, flat, and flexible metal housing |
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| CN1767254A (en) | 2006-05-03 |
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Application publication date: 20060503 Assignee: Shenzhen Wisewod Technology Co., Ltd. Assignor: Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences Contract record no.: 2010440020017 Denomination of invention: Thin type lithium ion battery and preparing method Granted publication date: 20080625 License type: Exclusive License Record date: 20100421 |
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