CN105531865B - The manufacture method of lithium rechargeable battery, the manufacture device of lithium rechargeable battery and lithium rechargeable battery - Google Patents

The manufacture method of lithium rechargeable battery, the manufacture device of lithium rechargeable battery and lithium rechargeable battery Download PDF

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Publication number
CN105531865B
CN105531865B CN201480049882.9A CN201480049882A CN105531865B CN 105531865 B CN105531865 B CN 105531865B CN 201480049882 A CN201480049882 A CN 201480049882A CN 105531865 B CN105531865 B CN 105531865B
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China
Prior art keywords
electrode material
electrode
rechargeable battery
lithium rechargeable
slurry
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CN201480049882.9A
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CN105531865A (en
Inventor
窪田千惠美
高原洋
高原洋一
西龟正志
森恭
森恭一
藤井武
松冈正兴
二乃宫荣作
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Hitachi Ltd
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Hitachi Ltd
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Priority claimed from JP2013202194A external-priority patent/JP6081333B2/en
Priority claimed from JP2013202989A external-priority patent/JP6021775B2/en
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Publication of CN105531865A publication Critical patent/CN105531865A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0419—Methods of deposition of the material involving spraying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The problem of the present invention is to prevent from, in the electrode layer of coating lithium ion secondary cell in collector foil and when coating forms the insulating materials of barrier film on electrode layer, the mixed layer of electrode material and insulating materials being formed in the near interface of electrode material layer and insulation material layer.As the method for solving the problem, following process is carried out：Use the process of the 1st coating part coating electrode material paste on the surface of collector foil；The solidify liquid of the composition separated out comprising the adhesive ingredients made contained by electrode material slurry is supplied to electrode material slurry, so that the process of the superficial layer solidification of electrode material slurry；The process of insulating materials slurry is coated with the electrode material slurry after superficial layer solidification using the 2nd coating part；And the process for making electrode material slurry and insulating materials slurry drying.In addition, as other methods, carry out following process：The process of electrode material (ES) of the coating comprising binding material on collector foil (EP) surface；The process of insulating materials (IF1) of the coating comprising the 1st composition for making binding material precipitation on electrode material (ES)；Spray liquid (LIQ) comprising the 2nd composition for making binding material precipitation is supplied to electrode material (ES), so that the process of electrode material (ES) solidification；And the process for drying electrode material (ES) and insulating materials (IF1).

Description

The manufacture method of lithium rechargeable battery, the manufacture device of lithium rechargeable battery and Lithium rechargeable battery
Technical field
The present invention relates to the manufacture method of lithium rechargeable battery, the manufacture device of lithium rechargeable battery and lithium ion two Primary cell, more particularly to positive pole, negative pole and by the lithium rechargeable battery of the electrically separated barrier film of positive pole and negative pole Manufacture method and manufacture device and the effective technology suitable for the lithium rechargeable battery.
Background technology
With the development of mancarried electronic aid, as the power supply source of these mancarried electronic aids, using can be repeatedly The small-sized secondary batteries of charging.Wherein, have energy density is high, have extended cycle life, self discharge is low and operating voltage height so The advantages of lithium rechargeable battery attract attention.Lithium rechargeable battery is used for number due to above-mentioned advantage The mancarried electronic aids such as camera, notebook personal computer or mobile phone.
And then in recent years, as battery for electric automobile, electric power storage battery, promoting can realize high power capacity, The research and development of the large-scale lithium rechargeable battery of height output and high-energy-density.Particularly in automobile industry, in order to tackle Environmental problem, promoting the electric automobile using motor as power source or using engine (internal combustion engine) and motor Both as power source hybrid vehicle exploitation.Lithium rechargeable battery is as this electric automobile, hybrid power The power supply of automobile also attracts attention.Similarly, lithium rechargeable battery is for effectively utilizing solar power generation or night electricity The importance in purposes such as electric power storage also gradually increase.However, lithium rechargeable battery operating voltage is high, energy density Height, it is taken as that needing sufficient countermeasure to tackle the abnormal heating because of caused by internal short-circuit, external short circuit etc..
Lithium rechargeable battery is one kind of rechargeable nonaqueous electrolytic battery, is that the lithium ion in electrolyte undertakes conduction Secondary cell.Known positive electrode (active material) uses lithium metal oxide, and negative material (active material) uses graphite etc. Carbon material, electrolyte use organic solvent and the lithium hexafluoro phosphate (LiPF such as ethylene carbonate6) etc. lithium salts.Lithium rechargeable battery Such as with layered product, the layered product is will to be coated with banding positive plate obtained by positive electrode and on metal foil on metal foil The banding negative plate obtained by negative material is coated with, across for forming positive plate and negative plate electrically separated barrier film is overlapping. The layered product is wound, it is in gyrate electrode coiling body that section is formed in the outer tinning of lithium rechargeable battery.
As the background technology of the art, there is patent document 1 (Japanese Unexamined Patent Publication 2003-045491 publications).Patent In document 1, following scheme is described：Using the die coating machine with solution discharge slit, applied on the two sides of positive pole tablet After cloth contains the solution of anode electrode material and the solution containing electrolysed substance and megohmite insulant, carry out shape by heating process Into anode electrode tablet.Additionally describe following scheme：Similarly applied using die coating machine on the two sides of negative pole tablet After cloth contains the solution of negative electrode material and the solution containing electrolysed substance and megohmite insulant, carry out shape by heating process Into negative electrode tablet.Here, two electrode sheet nitride layer of positive pole and negative pole are folded, electrode coiling body is formed.In addition, note Carry and folded two electrode sheet nitride layer to form the secondary cell manufacture method of electrode coiling body and secondary cell manufacture device.
In addition, following scheme is recorded in patent document 1：Anode electrode film and negative electrode film are formed respectively, it is right The film adhered membrane film of negative electrode, at this with being laminated the anode electrode film, shape on septate negative electrode film Into electrode coiling body.Here, describe by above-mentioned composition come improve be difficult to by the electrolysed substance of solution shape be uniformly injected into It is laminated with this respect and the more this respects of manufacturing process's number in the collector of polylith electrode coiling body.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2003-045491 publications
The content of the invention
Invent problem to be solved
Lithium rechargeable battery, such as possess electrode coiling body, the electrode coiling body is will to be applied on collector foil surface The positive plate obtained by positive active material is covered, the negative plate obtained by negative electrode active material is coated on collector foil surface and prevents What positive plate and the tabular membrane winding of negative plate contact formed.Herein, it is contemplated that with different parts, i.e. different object point Not Zhun Bei positive plate and negative plate and barrier film, but now, because causing metallic foreign body to be invaded the cut off operation such as positive plate Enter in the gap between positive plate and barrier film, produce positive pole and the problems such as negative pole short circuit.
On the other hand, it is contemplated that by the positive plate for coating positive active material and barrier film successively on collector foil surface and being formed, And coat negative electrode active material and barrier film successively on another collector foil surface and formed negative plate winding, formed lithium from Sub- secondary cell.If such lithium rechargeable battery, then can prevent because cut-out positive plate or negative plate and caused by Metallic foreign body is invaded between positive plate or negative plate and barrier film.
However, contain the electrode material of positive active material or negative electrode active material slurry when being coated with collector foil surface Material, when continuous coating forms the insulating materials slurry of barrier film on the slurry, in electrode layer and boundary's surface forming electrode of insulating barrier The mixed layer of material and insulating materials.Now, it is thinning to play the insulation material layer of the effect of barrier film, thus easily produce positive pole and The short circuit of negative pole, so as to produce the problem of reliability of lithium rechargeable battery reduces., can as above-mentioned short-circuit composition is prevented Consider the thickness of increase barrier film, but in this case, it is difficult to realize the miniaturization of lithium rechargeable battery.
In addition, in the painting process of the electrode material of lithium rechargeable battery, it is contemplated that as described in Patent Document 1, The electrode material of negative or positive electrode is coated with the surface as the collector foil of carrier material, coated film is formed, in the coated film It is upper to be coated with the insulating materials for forming barrier film, so as to form battery lead plate.Thereby, it is possible to prevent the short circuit problem caused by above-mentioned foreign matter Generation, and then, the raising of production efficiency and the miniaturization of manufacture device can be realized.
However, when the electrode material that negative or positive electrode is coated with the surface as the collector foil of carrier material, it is continuous to apply When cloth forms the insulating materials of barrier film, electrode material and insulating materials can be formed at the interface of electrode material layer and insulation material layer Mixed layer, therefore play barrier film effect insulation material layer it is thinning.Thus, the short circuit of positive pole and negative pole, production are easily produced Raw bad possibility improves, so as to produce the problem of reliability of lithium rechargeable battery reduces.As preventing the short circuit Form, it is contemplated that increase the thickness of barrier film, but in this case, be difficult to the miniaturization of lithium rechargeable battery.
The above-mentioned purpose and new feature of the present invention, it will be come by the record and accompanying drawing of this specification clear and definite.
For solving the method for problem
In embodiment disclosed herein, if the summary of simple declaration representative embodiments, as follows.
The manufacture method of the lithium rechargeable battery of representative embodiments has：Using the 1st coating part in collector foil The process of coating electrode material paste on surface；By comprising separating out in the electrode material slurry contained adhesive ingredients The 1st solidify liquid of composition supply to the electrode material slurry so that the superficial layer solidification of the electrode material slurry Process；The work of insulating materials slurry is coated with the electrode material slurry after superficial layer solidification using the 2nd coating part Sequence；And the process for making the electrode material slurry and the insulating materials slurry drying.
And then the manufacture method of the lithium rechargeable battery of representative embodiments has：It is coated with collector foil surface The process of electrode material comprising binding material；Coating includes the 1st composition for making binding material precipitation on electrode material The process of insulating materials；Spray liquid comprising the 2nd composition for making binding material precipitation is supplied to electrode material, so that electric The process of pole material solidification；And the process for drying electrode material and insulating materials.
And then the manufacture device of the lithium rechargeable battery of representative embodiments has：Applied on the surface of collector foil 1st coating part of cloth electrode material slurry；By comprising the adhesive ingredients that makes contained by the electrode material slurry separate out into The 1st solidify liquid divided is supplied to the electrode material slurry, so that the 1st of the superficial layer solidification of the electrode material slurry is solid Change room；The 2nd coating part of insulating materials slurry is coated with the electrode material slurry after superficial layer solidification；Make described The hothouse of electrode material slurry and the insulating materials slurry drying；The collector foil is transported to the 1st coating successively Portion, the 1st curing room, the transport portion of the 2nd coating part and the hothouse.
And then the manufacture device of the lithium rechargeable battery of representative embodiments has：Applied on the surface of collector foil Cloth includes the 1st coating part of the electrode material slurry of binding material；Coating, which includes, on electrode material slurry makes the binding material 2nd coating part of the insulating materials slurry of the 1st composition separated out；The solidification for the 2nd composition for making binding material precipitation will be included Liquid is supplied to electrode material slurry, so that the solidified portion of electrode material slurry curing；Make electrode material slurry and insulating materials The hothouse of slurry drying；Collector foil is transported to the transport of the 1st coating part, the 2nd coating part, solidified portion and hothouse successively Portion.
The effect of invention
It is as follows if simpling illustrate the effect obtained by representative invention in invention disclosed herein.
In accordance with the invention it is possible to improve the reliability of lithium rechargeable battery.
In addition, in accordance with the invention it is possible to improve the performance of lithium rechargeable battery.
Brief description of the drawings
Fig. 1 is the schematic diagram of the manufacture device for the lithium rechargeable battery for being denoted as embodiment of the present invention 1.
Fig. 2 is the schematic diagram of the manufacture device for the lithium rechargeable battery for being denoted as embodiment of the present invention 2.
Fig. 3 is the sectional view for the battery lead plate for forming lithium rechargeable battery.
Fig. 4 is the lithium rechargeable battery for being denoted as embodiment of the present invention 1 and the lithium ion as the 2nd comparative example Secondary cell is respective, the chart of the relation of mixed layer thickness and collector foil travelling speed.
Fig. 5 is the schematic diagram of the manufacture device for the lithium rechargeable battery for being denoted as the 1st comparative example.
Fig. 6 is the flow chart of the manufacturing process for the lithium rechargeable battery for being denoted as the 1st comparative example.
Fig. 7 is the schematic diagram for the manufacture device for representing the lithium rechargeable battery in the 2nd comparative example.
Fig. 8 is the amplification sectional view for the manufacture device for representing the lithium rechargeable battery in the 2nd comparative example.
Fig. 9 is the schematic diagram of the manufacture device for the lithium rechargeable battery for being denoted as embodiment of the present invention 3.
Figure 10 is the sectional view for the battery lead plate for forming lithium rechargeable battery.
Figure 11 be denoted as embodiment of the present invention 3 lithium rechargeable battery and as the 2nd comparative example lithium from Sub- secondary cell is respective, the chart of the relation of mixed layer thickness and collector foil travelling speed.
Figure 12 is the schematic diagram for the structure for representing lithium rechargeable battery.
Figure 13 is the flow chart of the manufacturing process for the lithium rechargeable battery for being denoted as the 3rd comparative example.
Figure 14 is the schematic diagram for the manufacture device for representing the lithium rechargeable battery in the 4th comparative example.
Embodiment
Hereinafter, based on accompanying drawing, embodiments of the present invention are explained.In addition, the whole for illustrating embodiment In accompanying drawing, identical symbol is assigned to the component with identical function, omits its explanation repeated.In addition, implementation below In, except especially need when in addition to, for same or like part, in principle not repeat specification.
In addition, thickness described in the application, refers to each structure in the collector foil with forming lithium rechargeable battery Length on the vertical direction in surface.
Embodiment 1
Hereinafter, using Fig. 1, the manufacture method and manufacture device of lithium rechargeable battery in present embodiment are said It is bright.Fig. 1 is the figure for the composition for representing the one side coating type electrode plate manufacturing device in present embodiment.That is, Fig. 1 is this reality of expression Apply the schematic diagram of the manufacture device of the lithium rechargeable battery in mode.
As shown in figure 1, the manufacture device of the lithium rechargeable battery in present embodiment has：Send out collector foil EP collection The electric metal paper tinsel roller RL1 and take-up roll RL4 for winding collector foil EP.As the collector foil EP of sheet metal paper tinsel, collecting Between electric metal paper tinsel roller RL1 and take-up roll RL4 while by multiple roller supports such as roller RL2, RL3 while being transported.Here, Collector foil EP is transported with constant speed, therefore the plurality of roller is referred to as roller delivery system, i.e. transport portion.
In collector foil EP transport path, it is configured with successively towards take-up roll RL4 sides from current collection with metal foil roller RL1 sides Spray nozzle NZ1, die coating machine DC2 and hothouse DRY in die coating machine DC1, curing room SD1.The collector foil EP transported passes through Between die coating machine DC1 and roller RL2, in curing room SD1, between die coating machine DC2 and roller RL3 and in hothouse DRY.
Although the positive pole and negative pole of composition lithium rechargeable battery each in collector foil EP material and are coated on collector foil EP material of film etc. is different, but can substantially be manufactured by same process.Therefore, below, regardless of positive pole With the respective manufacturing process of negative pole, illustrate.For example, the electrode material ES described later as coating material, comprising as just Situation of the pole by the use of material and the situation as negative pole material, in every case, are made up of different materials.Here, do not say and Analogy, in the manufacturing process of positive pole, using the collector foil EP and coating material being made up of positive electrode material, without using only in negative pole Manufacturing process in the material that uses.In the manufacturing process of negative pole similarly, without using only making in the manufacturing process of positive pole Material.
In the manufacturing process of lithium rechargeable battery in present embodiment, first, modulate for forming lithium ion secondary The electrode material ES of the negative or positive electrode of battery.Then, the 1st coating part configured in a manner of relative with roller RL2 is used i.e. Die coating machine DC1, by the electrode material ES of the pulp-like modulated it is thin and be equably coated on by current collection metal foil roller RL1 supply Collector foil EP surface on.Hereinafter, the process is referred to as the 1st painting process.In addition, will be by being applied by the 1st painting process The film that the electrode material ES being distributed on collector foil EP is formed is referred to as the 1st coated film.Such as slit can be used in above-mentioned 1st coating part Formula die coating machine, it is possible to use device of other devices as supply electrode material ES.
Then, the collector foil EP for being coated with electrode material ES is transported in curing room SD1, will be supplied by spray nozzle NZ1 The solidify liquid given is sprayed to the electrode material ES on collector foil EP, so that the table by electrode material ES the 1st coated films formed Surface layer solidifies.Hereinafter, the process is referred to as precuring process.In addition, solidify liquid described in the application is to include to make the 1st coating Curing materials, the liquid of the composition separated out as the adhesive ingredients of binding material contained by the slurry of film etc..That is, solidify Liquid and curing materials refer to respectively different material, and curing materials are supplied for example included in the 1st coated film by spray nozzle NZ1 Solidify liquid be free of curing materials.
Then, superficial layer solidification after the 1st coated film surface on, it is thin and be equably coated with by with roller RL3 phases To the insulating materials IF that supply of the i.e. die coating machine DC2 of the 2nd coating part that sets of mode.The process is referred to as the 2nd painting process.This Outside, the film being made up of the insulating materials IF being coated on by the 2nd painting process in the 1st coated film is referred to as the 2nd coated film. 2 coating parts can be used such as slit die coating machine.In addition, the 1st coated film and the 2nd coated film not shown in Fig. 1.
Then, the collector foil EP for being coated with the 2nd coated film by above-mentioned 2nd painting process is transported to and is used as heated-air drying In the hothouse DRY of stove.In hothouse DRY, the 1st coated film is neutralized to solvent composition and solidify liquid in the 2nd coated film Heating, them are evaporated, so that the 1st coated film and the 2nd coated film are dry, solidify, form electrode layer and insulating barrier in the lump.With Under, the process is referred to as drying process.That is, the 1st coated film turns into electrode layer, the 2nd coated film by drying process Insulating barrier, i.e. barrier film are turned into by drying process.Be consequently formed by collector foil EP and in collector foil EP one side successively The battery lead plate that the electrode layer and insulating barrier of stacking are formed, i.e. positive plate or negative plate.Then, the battery lead plate is wound in take-up roll RL4.In addition, in the application, electrode, positive pole and negative pole are referred to as battery lead plate, positive plate and negative plate sometimes.
Electrode material ES in present embodiment includes can release, absorb the positive electrode active material of lithium ion by discharge and recharge Matter powder or negative electrode active material powder.In addition, electrode material ES is included between bond powders composition after drying or cohesive Adhesive ingredients between powdered ingredients and collector foil.In addition, according to circumstances, electrode material ES includes the powder of conductive auxiliary agent.
Solidify liquid used in precuring process need with the adhesive included in insoluble 1st coated film into The property divided, and with the property dissolved each other with the solvent in the 1st coated film.If solidify liquid contacts with the 1st coated film, solidify While invading in the 1st coated film in the solvent that liquid can be dissolved in the 1st coated film.If in the superficial layer of the 1st coated film The increase of solidify liquid concentration, then the solubility of adhesive reduces, so that adhesive separates out, the superficial layer of only the 1st coated film is fixed Change.
Present embodiment has following feature：Between the 1st painting process and the 2nd painting process, precuring process is imported. Thereby, it is possible to the 2nd painting process is carried out under the immobilising state in surface of the 1st coated film.Therefore, as described later, can press down Make the mixed layer because the 1st coated film and the 2nd coated film being applied coating pressure and being formed as the die coating machine of above-mentioned 2nd coating part Generation.
Hereinafter, each material for manufacturing the lithium rechargeable battery in present embodiment is illustrated.
To positive active material used in present embodiment, cobalt acid lithium or the spinelle knot containing Mn (manganese) etc. can be used The lithium-contained composite oxide of structure or composite oxides containing Ni (nickel), Co (cobalt) or Mn (manganese) etc..In addition, positive electrode active material The olivine compounds such as olivine-type ferric phosphate can also be used in matter.But positive active material is not limited to these materials, can also make Use other materials.The lithium-contained composite oxide of spinel structure containing manganese may make up and for example be pacified due to excellent heat stability The high battery of full property.
In addition, the lithium-contained composite oxide of the spinel structure containing manganese can be also used only in positive active material, can also be used in combination Other positive active materials.As other positive active materials, can enumerate for example by Li1+xMO2(- 0.1 ＜ x ＜ 0.1) is represented Olivine compounds etc..As the example of the metal M in the formula, Co (cobalt), Ni (nickel), Mn (manganese), Al (aluminium), Mg can be enumerated (magnesium), Zr (zirconium) or Ti (titanium) etc..
In addition, the lithium-containing transition metal oxide of layer structure can be used in positive active material.As containing for layer structure The concrete example of lithium transition-metal oxide, LiCoO can be used2Or LiNi1-xCox-yAlyO2(0.1≦x≦0.3、0.01≦y≦ 0.2) etc..In addition, at least oxide containing Co, Ni and Mn etc. can be used in the lithium-containing transition metal oxide of layer structure.Make For the oxide containing Co, Ni and Mn, such as LiMn can be enumerated1/3Ni1/3Co1/3O2、LiMn5/12Ni5/12Co1/6O2Or LiNi3/ 5Mn1/5Co1/5O2Deng.
Such as native graphite (flaky graphite), artificial stone can be used in negative electrode active material used in present embodiment The graphite material such as ink or expanded graphite.In addition, negative electrode active material can be used by pitch burn till obtained by the easy graphitization such as coke Property carbonaceous material.In addition, negative electrode active material can be used furfuryl alcohol resin (PFA：Poly Furfuryl Alcohol) or poly- pair Penylene (PPP：) etc. Poly-Para-Phenylen the difficult graphitization carbon such as amorphous carbon obtained by being burnt till with phenolic resin low temp Material.
In addition, in addition to above-mentioned carbon material, Li (lithium) or lithium-containing compound etc. can also be used to be used as negative electrode active material Matter.As the lithium-containing compound, the lithium alloys such as Li-Al can be enumerated or can be closed containing Si (silicon), Sn (tin) etc. with Li (lithium) The alloy of the element of aurification.And then the oxide based material such as Sn oxides, Si oxides can also be used in negative electrode active material. The oxide based material can also be free of Li (lithium).
Above-mentioned conductive auxiliary agent be used as anode electrode film contained by electronics conductive auxiliary agent, preferably for example carbon black, acetylene black, The carbon materials such as graphite, carbon fiber or CNT.In above-mentioned carbon material, used from the effect and coating of addition and electric conductivity Set out in terms of the manufacturing of anode mixture slurry, particularly preferably acetylene black.The conductive auxiliary agent can also be included in negative electrode In film.
The adhesive used in the electrode of present embodiment, preferably comprise and be used for above-mentioned active material and conductive auxiliary agent Mutually cohesive adhesive.As the material of adhesive, such as polyvinylidene fluoride based polymer or rubber can be suitably used Based polymer etc..Kynoar based polymer contains the inclined fluorine second as monomer more than 80 mass % for such as main component The polymer of the fluorochemical monomer group of alkene.Above-mentioned polymer can and with two or more.In addition, the adhesive of present embodiment, preferably There is provided with the solution morphology being dissolved in solvent.
As for synthesizing the fluorochemical monomer group of above-mentioned Kynoar based polymer, vinylidene or inclined fluorine can be enumerated The mixture of ethene and other monomers, the mixture are monomer mixture of vinylidene containing more than 80 mass % etc..
As other monomers, can enumerate for example PVF, trifluoro-ethylene, CTFE, tetrafluoroethene, hexafluoropropene, Or vinyl ethers etc..
As above-mentioned rubber-based polymeric thing, such as butadiene-styrene rubber (SBR can be enumerated：Styrene-Butadiene Rubber), ethylene propylene diene rubber or fluorubber etc..
The content of electrode layer, adhesive i.e. in the 1st coated film, is 0.1 mass % on the basis of dried electrode layer More than, it is desirable to it is below 10 mass %.More preferably the content of adhesive is more than 0.3 mass %, it is desirable to is below 5 mass %. If the content of adhesive is very few, not only solidification becomes insufficient in the precuring process of present embodiment, and after drying Electrode film mechanical strength it is also insufficient, produce electrode layer from collector foil peel off the problem of.If the in addition, content mistake of adhesive More, then the active matter quality in electrode layer is reduced, and battery capacity is possible to step-down.
Aluminum oxide (Al can be used in insulating materials IF used in present embodiment2O3) or silica (SiO2) etc. nothing Machine oxide.In addition, by using the slurry that the particulate of polypropylene or polyethylene is mixed to gained, can also there is insulating barrier Closing property.Insulating barrier is porous film, and in the lithium rechargeable battery completed, electrolyte is held in the sky of insulating barrier In hole, the passage of conducting lithium ions between electrode is formed.Closing said here, refer in lithium rechargeable battery abnormal heating When, insulating barrier melts and the function of plugging hole.The transmission of the lithium ion in insulating barrier is blocked using the closing function, so as to electricity Reaction in pond stops, and can prevent the further rise of battery temperature.
In addition, the adhesive for the inorganic oxide particle used in cohesive insulation material IF is used as using resin. In negative pole also in the same manner as positive pole, adhesive can suitably use above-mentioned Kynoar based polymer or rubber-based polymeric thing Deng.
Collector foil EP used in present embodiment is not limited to the paper tinsel of sheet, and as its matrix, such as aluminium can be used (Al), simple metal or the alloy properties conductive material such as copper (Cu), stainless steel, titanium (Ti).Such as net, punching gold can be used in collector foil EP Category, foam metal are processed into paper tinsel of tabular etc..The thickness of composition collector foil EP conductive base, for example, 5~30 μm, More preferably 8~16 μm.
For the solidify liquid of present embodiment, it is important that for the solvent in the 1st coated film and adhesive rightly Select and use.The dissolubility for the adhesive ingredients that solidify liquid is contemplated that in the 1st coated film, solvent mutual dissolubility is entered Row selection.The solvent in the 1st coated film used in the slurry of in general solvent system, can enumerate 1-METHYLPYRROLIDONE, Aprotic polar solvents such as dimethyl sulfoxide (DMSO), propylene carbonate, dimethylformamide or gamma-butyrolacton or theirs is mixed Close liquid.If in view of the being mutually dissolved property to these solvents and the solubility of used adhesive, may be selected water, ethanol, The alcohols such as isopropanol or their mixed liquor are not limited to example listed herein as solidify liquid.
In addition, in order to which equably spray solidification liquid, the wetability that should further contemplate the 1st coated film and solidify liquid are solid to select Change liquid, preferably using water and the mixture of alcohol.Because when the wetability difference of the 1st coated film and solidify liquid, solidify liquid exists Many places are scattered on the surface of 1st coated film and adhered to island, the uniformly supply solidify liquid of no coated film of normal direction the 1st. The concentration of alcohol in the mixture is 20~80%, more preferably 40~60%.When the concentration of alcohol is less than above-mentioned concentration range, The worsened wettability of 1st coated film and solidify liquid.In addition, when the concentration of alcohol is higher than above-mentioned concentration range, due to flammable The concentration of alcohol rises, and causes the operation of solidify liquid to become difficult, the dangerous increase broken out in manufacturing process etc..
Here, the precuring process to present embodiment illustrates.
The precuring process of present embodiment is introduced into the process between the 1st painting process and the 2nd painting process.It is pre- solid In chemical industry sequence, to the surface spray solidify liquid of the 1st coated film, the superficial layer of the 1st coated film of solidification.The superficial layer of 1st coated film Refer to the 1st coated film of the near surface comprising the 1st coated film surface.
Now, it is important that rightly select the spray amount of solidify liquid and the spray particle diameter of solidify liquid to carry out precuring work Sequence.As the species of spray nozzle, the fluid tip for only spraying liquid can be used or liquids and gases are mixed to two sprayed Fluid tip.From the viewpoint of impact when water contacts with cured film is mitigated using spraying, it is desirable to use can spray more The second fluid nozzle of fine drop.
In addition, by the way that the average grain diameter D50 for the spray particle sprayed from nozzle is set into less than 20 μm, more preferably it is set to Less than 10 μm, so as to prevent coated film defect equivalent damage.Coated film defect, refer in the drop to coated film surface spray Atomisation pressure, spray hits power or the big situation of average grain diameter etc. when, because spray particle is hit on the surface of coated film, Cause the surface indentation of coated film.In this case, the problems such as insulating properties between electrode occurs produces deviation.In addition, When spray hits power described in this refers to drop is hit into object using spraying, pressure that the object per unit area is born Power.
Based on above content, it is necessary to select solidify liquid according to the adhesive for electrode material and the species of solidify liquid Appropriate spray amount.Specifically, it is set to below the solidify liquid concentration that whole adhesives in the 1st coated film separate out.More preferably It is set to make the 40~90% of the solidify liquid concentration that whole adhesives in the 1st coated film separate out.It is excessive in the spray amount of solidify liquid When, solidify liquid is accumulated in the 1st coated film, and the coating of insulating materials becomes difficult, and when solidifying hypovolia, solidify liquid is possible to not The 1st whole face of coated film can be diffused to.
By the available lithium rechargeable battery of present embodiment, except including the positive pole manufactured by the above method and negative Beyond pole, it can be manufactured by the process same with the lithium rechargeable battery of aftermentioned 2nd comparative example.For the container knot of battery Structure, size or using both positive and negative polarity as structure of the electrode body of main inscape etc., are not particularly limited.
The feature of the manufacture method of the lithium rechargeable battery of present embodiment is, as described above, being coated with the 1st layer i.e. After the 1st coated film of electrode layer, the process that solidifies by the superficial layer for only making electrode layer, the 2nd layer of coating becomes insulation 2nd coated film of layer.In addition, the feature of the manufacture device of the lithium rechargeable battery of present embodiment is, as described above, applying The 2nd layer of the 2nd coated film for becoming insulating barrier of 1st coating part of the 1st layer of the 1st coated film for becoming electrode layer of cloth and coating Between 2nd coating part, having only makes the mechanism that the superficial layer of the 1st coated film solidifies.In such manufacture device, by using Above-mentioned manufacture method, as described later, the thickness in mixed layer caused by the interface of electrode layer and insulating barrier can be made thinning, can Realize filming, highly reliableization of insulating barrier.
Hereinafter, an example of the manufacturing process of the lithium rechargeable battery of present embodiment is recorded.Here, on just The example of the formation process of pole illustrates.
Firstly, for modulator electrode material ES process, in the manufacturing process of positive pole, electrode material ES positive pole is formed The nickle cobalt lithium manganate as lithium-transition metal composite oxide can be used in active material.In the electrode material ES initially carried out tune In process processed, using above-mentioned positive active material, the conductive auxiliary agent containing powdered graphite and acetylene black and with as solidification material The effect of material and Kynoar (hreinafter referred to as PVdF) mixing for turning into adhesive.In addition, one is entered to their mixture 1st solvent of step addition present embodiment is METHYLPYRROLIDONE (hreinafter referred to as NMP).Will using planetary mixer Thus each composition of the positive active material, conductive auxiliary agent, curing materials and the 1st solvent that mix further is kneaded, and modulates positive pole Slurry is electrode material ES.
Here, by positive active material, powdered graphite, acetylene black, PVdF with weight ratio meter 85：8：2：5 ratio mixing. In anode sizing agent, the adhesive ingredients as curing materials is dissolved in NMP, and slurry is highly viscous liquid.It is viscous with rotation The viscosity of the slurry of degree meter measure is about 10Pas.
Then, the 1st painting process is carried out.Here, the collector foil EP use examples as the coating object in the 1st painting process Such as 20 μm of thickness, width 200mm aluminium foil.In 1st painting process, using the die coating machine DC1 as slit die coating machine, with thickness Electrode material ES is coated on collector foil EP surface by 100 μm of degree, width 150mm.Thus, formed on collector foil EP by electricity The 1st coated film that pole material ES is formed.Above process is the 1st painting process of present embodiment.In addition, current collection said here Paper tinsel EP and the 1st coated film width, it is orthogonal in the direct of travel of the collector foil EP with being transported and along current collection to refer to each structure Length on the direction of paper tinsel EP upper surface.
Then, precuring process is carried out.That is, the collector foil EP for being coated with the 1st coated film is transported in curing room SD1, Only solidify the superficial layer of the 1st coated film.Here, the solidify liquid supplied by spray nozzle NZ1, which uses, contains 40% ethanol water.Contain 40% ethanol water is the liquid for mixing ethanol with water, and ethanol forms the 40% of the liquid.
Spray nozzle NZ1 uses the second fluid nozzle of internal mix type.As the solidify liquid sprayed by second fluid nozzle The average grain diameter D50 of spray particle is 10 μm.In addition, it is adjusted to 100mm, spraying from spray nozzle to the distance of the 1st coated film Pressure is adjusted to 0.1MPa, spray hits power is adjusted to 1g/cm2.The spray amount of solidify liquid is set to make as adhesive PVdF all separates out required 50% amount containing 40% ethanol water.That is, the spray amount of solidify liquid is set to be used to make to glue The half for the amount that mixture all separates out.Thus, only the superficial layer of the 1st coated film is solidified.Above process is present embodiment Precuring process.
In addition, comprising as the 1st painting of the object of spray nozzle NZ1 spray solidification liquid, electricity as pole material paste On the face on the surface of cloth film, the spray area of solidify liquid has impartial flow distribution.That is, with regard to solidify liquid spray amount distribution and Speech, on the width of the 1st coated film, sprayed in the certain limit of spray nozzle NZ1 centers with the amount of equalization. Here, by making the whole width of the 1st coated film in the certain limit that can be sprayed with the amount of equalization, so as to the 1st The whole upper surface of coated film equably spray solidification liquid.
Therefore, the position as 50% flow of the flow at spray nozzle NZ1 centers is set to the width in the 1st coated film The position more outer than the end of the 1st coated film on direction, the width of the 1st coated film is the transport side with collector foil EP To orthogonal direction.Because than from spray nozzle NZ1 center to turning into solidify liquid bulk flow on the width The region of the position of 50% flow of amount in the outer part, it is possible to can not be with the amount spray solidification liquid of equalization.That is, if from spraying , then can be with the amount spray solidification liquid of equalization in the range of nozzle NZ1 center to 50% flow of the overall flow of solidify liquid.
Then, the 2nd painting process is carried out.Insulating materials IF uses silica (SiO2) powder.Here, by the insulation material Expect IF and as adhesive Kynoar (PVdF) with weight ratio meter 90：10 ratio is mixed, and then is progressively added METHYLPYRROLIDONE (NMP) is used as solvent, is kneaded these compositions with planetary mixer, modulates insulating materials slurry.Absolutely Edge material paste is highly viscous liquid, and the viscosity with the slurry of rotary viscosity design determining is about 2Pas.
Here, the die coating machine DC2 as slit die coating machine is used, will be above-mentioned in the 1st coated film after surface cure Insulating materials slurry is that insulating materials IF is coated into 80 μm of thickness, width 160mm.Thus, the 2nd will be made up of insulating materials IF Coated film is formed in the 1st coated film.Above process is the 2nd painting process of present embodiment.
Then, process is dried.Here, to the 1st coated film and the 2nd in the hothouse DRY as hot-air drying stove Coated film is heated 10 minutes with 120 DEG C, is dried.Thus, the 1st coated film is neutralized to solvent contained in the 2nd coated film Evaporative removal, so that the 1st coated film and the 2nd coated film are integrally fully cured.Manufacture the positive plate of lithium rechargeable battery. That is, positive plate has：Collector foil EP；Make the electrode layer that the 1st coated film comprising electrode material ES is dry, is solidified to form；With And make the insulating barrier that the 2nd coated film comprising insulating materials IF is dry, is solidified to form.Above process be from electrode material ES and Solvent composition and the drying process for the present embodiment being dried are removed in insulating materials IF.
After above-mentioned drying process, the manufacturing procedure such as collector foil EP is compressed or cut off, so as to manufacture film-form The battery lead plate of negative or positive electrode.
Here, to the thickness of the mixed layer formed in the manufacture method of present embodiment at the interface of electrode layer and insulating barrier Degree is evaluated.The evaluation is by cutting out the section of completed battery lead plate, from SEM (Scanning Electron Microscope) image of observation calculates the thickness of mixed layer to carry out.
Fig. 3 represents to form the sectional view of the battery lead plate of lithium rechargeable battery.As shown in figure 3, on collector foil EP, successively It is laminated with thickness L1 electrode layer EL, the thickness L2 insulating barrier SEL as barrier film.To this composition, above-mentioned present embodiment Lithium rechargeable battery, the lithium rechargeable battery of aftermentioned 2nd comparative example are all same.In addition, in electrode layer EL and insulation Layer SEL near interface, mixed layer MIX, the mixed layer MIX formed with thickness L3 by electrode layer EL constituent material and absolutely Edge layer SEL constituent material is mixed to form.In Fig. 3, mixed layer MIX top and bottom are represented with dotted line respectively.
In this case, the thickness L1 that the electrode layer of positive plate is formed after drying process is such as 50 μm, The thickness L2 of insulating barrier is such as 40 μm.Mixed layer MIX is the near interface in electrode layer EL and insulating barrier SEL, from electrode layer The layer that EL inside is formed to insulating barrier SEL inside.
In addition, being shown in Fig. 4, based on the sectional view shown in Fig. 3, mixed layer MIX thickness is entered by above-mentioned SEM observations The result of row evaluation.Fig. 4 is the lithium ion two of the lithium rechargeable battery and aftermentioned 2nd comparative example that represent above-mentioned present embodiment The chart of the relation of the thickness of the respective mixed layer MIX (reference picture 3) of primary cell and the travelling speed of collector foil.Shown in Fig. 4 The longitudinal axis of chart represents the thickness of mixed layer, and transverse axis represents the travelling speed of collector foil.The present inventor etc. carries out above-mentioned evaluation, knot Fruit finds：As shown in circular icon in Fig. 4, the mixed layer thickness L3 (reference picture 3) of the manufacture method of present embodiment, no analects How is the travelling speed of electric paper tinsel, is constantly in less than 5 μm, even if by insulating barrier SEL (reference picture 3) filming, produces short circuit Possibility is also low.
In addition, here, illustrate to be coated with positive electrode slurry and insulation material slurry successively in the one side of positive electrode collector foil Material, manufacture the example of positive plate.In the two sided coatings positive electrode slurry and insulating materials slurry of positive electrode collector foil, it is contemplated that After above-mentioned operation is carried out and before the manufacturing procedures such as the compression of collector foil or cut-out are carried out, make the positive pole for being wound in take-up roll Battery lead plate is overturn, and again passes by identical process to be coated with the back side.
Then, in the assembling procedure of electrode unit, in the process for being referred to as winding, from what is formed by above-mentioned operation The anode electrode plate and negative el of film-form cut out the positive pole and negative pole of size needed for battery unit.Now, as The insulating barrier of the barrier film of anode electrode plate and negative el is separated, is cut out together with anode electrode plate and negative el.Connect Get off, on electrode layer after the overlapping anode electrode plate and negative el for being laminated with barrier film, will include the anode electrode plate and The layered product of negative el intervolves.
Then, the group comprising positive pole, the electrode pair of negative pole intervolved is assembled and welded.In the welding sequence In, such as to positive collector electrode ear winding aluminum band, be connected the aluminium strip with positive pole current collections lug using ultrasonic fusing.Then, Assembling for these electrode pairs after welding is placed in battery can, is then injected into electrolyte.It is next, battery can is completely close Envelope, so as to form the battery unit of lithium rechargeable battery.
In battery unit inspection operation, to the unit of lithium rechargeable battery that is made in unit assembling procedure repeatedly Carry out discharge and recharge.Thus, the cell inspection operation of the Performance And Reliability about battery unit is carried out.Cell inspection In process, carrying out the curtage such as when the inspection or charging of the capacity or voltage of battery unit or when discharging Check.Thus, the battery unit of lithium rechargeable battery, i.e. cell are completed.
Hereinafter, the manufacturing process of the lithium rechargeable battery of the 1st comparative example is illustrated using Fig. 5 and Fig. 6.
Fig. 6 is the flow chart of the specific process schematically shown untill lithium rechargeable battery is manufactured.Such as Fig. 6 institutes Show, the manufacturing process of lithium rechargeable battery includes anode electrode plate manufacturing process and negative el manufacturing process and battery The assembling procedure of unit.
Fig. 5 represents the lithium rechargeable battery manufacture device of the 1st comparative example.That is, Fig. 5 is to represent the lithium in the 1st comparative example The schematic diagram of the manufacture device of ion secondary battery.In the manufacturing process of lithium rechargeable battery in the 1st comparative example, first Modulator electrode material ES.For formed form lithium rechargeable battery negative or positive electrode electrode layer electrode material ES be as The liquid of the highly viscous slurry shape of lower formation：The active material of lithium ion will can be released, absorb by discharge and recharge and conduction helps The powder of agent for bonding adhesive and solvent of these powder etc. with being kneaded, scattered (mixing, allotment process shown in Fig. 6).
Then, using the die coating machine DC1 as coating part, by the electrode material ES of pulp-like it is thin and be equably coated on by On surface of the current collection with the metal foil roller RL1 collector foil EP supplied.Then, using one side and collector foil EP rear-face contact on one side Collector foil EP roller delivery system, i.e. transport portion is transported with constant speed, makes to be coated with the electrode material ES structures by pulp-like Into coated film collector foil EP in the hot-air drying stove as hothouse DRY dry, solidify.In the drying process, pass through Solvent composition heating evaporation in coated film is made to electrode material drying, solidification, forms electrode layer.By so carrying out electrode Material ES coating and the series of processes of drying process, so as in the enterprising row electrode layers of collector foil EP (the coating work shown in Fig. 6 Sequence).Then, the process such as it is compressed to the collector foil formed with electrode layer, so as to manufacture the electricity of the negative or positive electrode of film-form Pole plate.
In the manufacturing process of the battery lead plate of 1st comparative example, a surface and side opposite with the surface to collector foil EP Surface carries out process as described above respectively, manufactures the electrode in positive pole of the collector foil EP two sides formed with electrode layer and negative pole Plate.
Then, in the assembling procedure of electrode unit, in the process for being referred to as winding, from the positive pole electricity of above-mentioned film-form Pole plate and negative el cut out the positive pole and negative pole (manufacturing procedure shown in Fig. 6) of size needed for battery unit.Now, with electricity Size needed for pool unit cuts out the barrier film to be formed for separating anode electrode plate and negative el from the diaphragm material of film-form, Sandwiched in anode electrode plate and negative el cut out barrier film carry out it is overlapping after, intervolved (the winding work shown in Fig. 6 Sequence).
Then, the group of the electrode pair of the positive pole intervolved, negative pole and barrier film is assembled, and is welded the (weldering shown in Fig. 6 Connect, assembling procedure).Then, assembling for these electrode pairs after welding is placed in battery can, is then injected into electrolyte (Fig. 6 institutes The fluid injection process shown).Next, (sealing process shown in Fig. 6) is fully sealed in battery can, so as to form lithium ion secondary electricity The battery unit in pond.
In battery unit inspection operation, to the unit of lithium rechargeable battery that is made by unit assembling procedure repeatedly Carry out discharge and recharge (the discharge and recharge process shown in Fig. 6).Thus, inspection (Fig. 6 of the Performance And Reliability about battery unit is carried out Shown cell inspection operation).In the cell inspection operation, the capacity or voltage of such as battery unit are carried out Check or the inspection of curtage etc. during charging or during electric discharge.Thus, it is cell to complete battery unit, terminates lithium The assembling procedure of the battery unit of ion secondary battery.
In the above-mentioned manufacturing process as the 1st comparative example, there are the following problems：Because before and after electrode coiling body is formed The process implemented, possibility of the metallic foreign body intrusion electrode roll around internal portion is caused to uprise.That is, due to positive plate and negative plate It is made up of with barrier film different parts, thus gap for example between positive plate and barrier film is present, easily intrusion should for metallic foreign body Gap.
Specifically, the above-mentioned of electrode coiling body is formed positive plate and negative plate and barrier film are wound around shaft core In 1st comparative example, positive plate and negative plate and barrier film are made up of different parts, thus are deposited for example between positive plate and barrier film In gap.In addition, in the manufacturing process of lithium rechargeable battery, before above-mentioned coiling body is formed, positive plate and negative plate are cut Predetermined size (manufacturing procedure shown in Fig. 6), this external cutting off positive plate and negative plate are broken into form positive pole and negative pole Current collection lug.
Then, after forming above-mentioned electrode coiling body, for example, will be formed in the positive pole current collections lug of positive plate with just The process of pole collector ring ultrasonic fusing, the negative collector electrode ear that will be formed in negative plate and negative pole collector ring ultrasonic fusing Process (welding, assembling procedure shown in Fig. 6).Next, electrode coiling body is inserted in outer tinning (container), to the outer tinning After middle injection electrolyte, in order to seal the inside of outer tinning, the process for being connected outer tinning with lid with welding etc. is carried out.
In above-mentioned welding, assembling procedure, the welding of positive pole current collections lug and positive pole current collections ring, such as be carried out as follows：It is right After positive pole current collections lug winding aluminum band, the aluminium strip is connected with positive pole current collections lug with ultrasonic fusing.It is now used super Sound wave welding is following method：Atom phase counterdiffusion caused by by being rubbed because of aluminium strip and positive pole current collections lug, by aluminium strip with Positive pole current collections lug connects.
Accordingly, when being connected positive pole current collections lug with aluminium strip with ultrasonic fusing, because of aluminium strip and positive pole current collections lug Phase mutual friction and produce metallic foreign body (aluminium).Same phenomenon is also produced in the process of connection negative collector electrode ear and copper strips. That is, when being connected negative collector electrode ear with copper strips with ultrasonic fusing, because of the phase mutual friction of copper strips and negative collector electrode ear and Produce metallic foreign body (copper).And then in the welding (electric arc welding) used in process of the outer tinning with lid is connected, such as hold It is also easy to produce weldering bits.
Based on case above, by forming before and after electrode coiling body the process implemented, metallic foreign body is caused to invade Possibility of the electrode roll around internal portion uprises.The 1st comparative example is such as described above, in positive plate and negative plate and barrier film by different portions When part is formed, gap between such as positive plate and barrier film be present, therefore caused metallic foreign body holds in above-mentioned manufacturing process Easily invade the gap.If it does, metallic foreign body invades electrode roll around internal portion, then the metallic foreign body invaded is broken through barrier film, led Positive pole and negative pole is caused to produce short circuit by metallic foreign body.In addition, for example, if the metallic foreign body in the gap of intrusion positive pole and barrier film is attached In positive pole, then accompanying metallic foreign body is dissolved in electrolyte, then produces the phenomenon separated out in negative pole.It is if also, logical Cross the metal grown from the precipitation of negative pole and reach positive pole, then produce the problem of positive pole is with negative pole short circuit.
And then assemble positive plate with different parts and when negative plate and barrier film, it is necessary to by positive plate and negative plate and Total four block piece materials of two pieces of barrier films intervolve simultaneously, the problem of contraposition difficulty of part be present.Furthermore, it is necessary to configure positive plate Total four film rolls of roller, negative plate roller and two barrier film rollers, manufacture device be present and become the problem of big such.
As the composition to solve the above problems, it is contemplated that the side for directly applying cloth diaphragm on positive plate and negative plate to be formed Case.Now, positive plate or negative plate are formed continuously with barrier film, make mutual integration so that positive plate or negative plate with every Gap between film disappears.Thereby, it is possible to prevent between metallic foreign body intrusion positive plate or negative plate and barrier film, so as to anti- The only short circuit of positive pole and negative pole.And then applied on metal after slurry of the coating comprising positive active material or negative electrode active material Cloth forms the insulating materials of barrier film, so as to can also realize productive raising and the diminution of manufacture device.
For directly applying cloth diaphragm so on positive plate and negative plate to form the method for battery lead plate, Fig. 7 used below, 2nd comparative example is shown to illustrate.Fig. 7 is the signal for the manufacture device for representing the lithium rechargeable battery in the 2nd comparative example Figure.
Fig. 7 represents the composition of the one side coating type electrode plate manufacturing device in the 2nd comparative example.The lithium ion of 2nd comparative example In the manufacturing process of secondary cell, collector foil EP is sent out by current collection with metal foil roller RL1.Collector foil EP be such as 20 μm of thickness, Width 200mm aluminium foil.Next, on collector foil EP surface, it is coated with by the die coating machine DC1 supply relative with roller RL2 Electrode material ES, formed the 1st coated film.1st coated film is such as 100 μm of thickness, width 150mm.
Next, coating is supplied by the die coating machine DC2 as coating part with roller RL3 relative positions in the 1st coated film The insulating materials IF given, form the 2nd coated film being made up of insulating materials IF.2nd coated film is such as 20 μm of thickness, width 160mm.Then, the 1st coated film on collector foil EP and the 2nd coated film are dried by hothouse DRY, are wound in winding Roller RL4, so as to manufacture battery lead plate.In the drying process, with 120 DEG C of progress drying in 10 minutes.
So, the composition of the 2nd comparative example with using Fig. 5 come above-mentioned 1st comparative example that illustrates compared with, with as the 2nd The die coating machine DC2 of coating part, directly it is formed into the 1st coated film by die coating machine DC2 on the 2nd coated film of barrier film this aspect It is different.
Described die coating machine DC1 (reference picture 7) uses such as slit die coating machine.Slit die coating machine is applied in thick film Cloth is coated with the apparatus for coating used in purposes of heavy viscous material etc..
In the die coating method of 2nd comparative example, as shown in figure 8, from the groove for being stored with the electrode material ES as grout material (not shown), electrode material ES is supplied to the manifold 3 of shower nozzle 1 by constant displacement pump (not shown).Here, in manifold 3, make electricity After pole material ES pressure distribution is uniform, electrode material ES is supplied to being arranged at the slit 4 of shower nozzle 1, and is spued.Spued Electrode material ES and keep constant interval h1 between the relative collector foil EP to advance with shower nozzle 1, formation is referred to as pearl (PVC ー De) electrode material reservoir 5, in this condition, with collector foil EP traveling, extraction electrode material ES is applied with being formed Film.Fig. 8 is the amplification sectional view for forming the die coating machine DC1 of the manufacture device of lithium rechargeable battery in the 2nd comparative example.
In painting process, by slit 4 supply with the electrode material ES because of the amount same amount that film is formed and consume so that continuously Ground forms film.Now, in order to stably be evaporated the film coated of fireballing organic solvent system, the electrode material accumulates Depositing the formation stabilisation of the i.e. downstream meniscus 9 of liquid level bending in portion 5 becomes important.Therefore, positive electrode is supplied to manifold 3 Pressure turns into downstream 8 crushings of lip+pressure of downstream meniscus 9 of 4 crushings of slit+shower nozzle 1.That is, in order to stably be coated with Electrode material ES to collector foil EP, it is necessary to be applied pressure to a certain degree by electrode material ES.It is such to be formed in die coating machine DC2 In and it is same.
In the manufacturing process illustrated using Fig. 7, then it is coated with absolutely by being used as the die coating machine DC2 of the 2nd coating part Edge material, die coating method herein are same with the condition in the die coating machine DC1 as the 1st coating part.That is, will By die coating machine DC2 slit 4 (reference picture 8) spue using megohmite insulant as the grout material of raw material, i.e. insulating materials IF, be coated with In on the electrode material ES being coated on using above-mentioned die coating machine DC1 on collector foil EP.
In the 2nd comparative example described above, the electrode material ES of the pulp-like shown in Fig. 7 and insulating materials IF are overlap After coating, by the heating using hothouse DRY, drying process, film layer drying, the set of both sides can be made simultaneously, therefore, The excellent in efficiency of manufacturing process compared with the 1st comparative example.Furthermore it is possible in electrode layer and as gapless between the insulating barrier of barrier film In the state of, the processing such as cut-out or welding of electrode is carried out, therefore can prevent internal caused by the intrusion of metallic foreign body Short circuit.
However, as the 2nd comparative example, in the electrode material and insulating materials of continuous coating sizing-agent shape in collector foil, As shown in figure 3, the near interface of the electrode layer EL and insulating barrier SEL on the collector foil EP of battery lead plate is coated on, forms and loses The mixed layer MIX of insulation function.The present inventor etc. has found, mixed layer MIX be because using Fig. 4 come the slit die coating machine that illustrates Coating pressure and caused layer.As shown in square icon in Fig. 4, the caused mixed layer MIX (reference pictures in the 2nd comparative example 3) thickness changes according to the travelling speed of collector foil.That is, the travelling speed of collector foil is slower, the pressure caused by die coating machine The time applied to the coated film of ad-hoc location is longer, therefore mixed layer MIX thickness is also bigger.Even if by the transport of collector foil Speed is set to faster 100m/min, and mixed layer MIX thickness also turns into more than 10 μm.
When forming mixed layer MIX with larger thickness, there are the following problems：The thickness of insulating barrier SEL with insulation function Degree becomes the thickness of thin intended than script, and during by insulating barrier SEL filmings, has and expose structure on insulating barrier SEL top Into the possibility of mixed layer MIX electrode material.
Specifically, in the value for the thickness L2 big 20% that mixed layer MIX thickness L3 is the insulating barrier SEL for being used for barrier film When, in the total film thickness of insulating barrier SEL between a positive electrode and a negative electrode, the region that insulation function is lost becomes big, therefore insulating barrier SEL Insulating properties reduce, producing the problem of short-circuit between positive pole and negative pole becomes notable.
That is, mixed layer MIX thickness L3 wishes less than 20% of the thickness L2 for the insulating barrier SEL as barrier film.Therefore, When insulating barrier SEL thickness L2 is 40 μm, mixed layer MIX thickness L3 is wished for less than 8 μm.In the 2nd comparative example, in order to Prevent the problem of as described above from occurring, it is ensured that insulating barrier SEL reliability, it is contemplated that insulating barrier is set into such as more than 50 μm thick Film.
2nd comparative example as described above is such, it is contemplated that is prevented by eliminating the gap of electrode layer and barrier film (insulating barrier) Only internal short-circuit, and the productivity of lithium rechargeable battery is improved, and by the manufacture device densification of lithium rechargeable battery, But in this composition, the problem of due to above-mentioned mixed layer, it is difficult to realize the filming of insulating barrier.That is, the 2nd comparative example In, the problem of high capacity for being difficult to lithium rechargeable battery and miniaturization be present.
Hereinafter, to being illustrated using Fig. 1 come the effect of the present embodiment illustrated.
Relative to above-mentioned 2nd comparative example, the feature of the manufacture method of the lithium rechargeable battery of present embodiment is to incite somebody to action After the 1st layer of the 1st coated film coating of electrode layer, the process that solidifies by the superficial layer for only making the 1st coated film is coated into For the 2nd layer of the 2nd coated film of insulating barrier.So, precuring process is carried out after the electrode material ES of coating negative or positive electrode, Only solidify the superficial layer of the 1st coated film, so as to as illustrated using Fig. 3 and Fig. 4, make mixed layer MIX's Thickness L3 is smaller than the 2nd comparative example.Specifically, mixed layer MIX thickness can be made turn into less than 5 μm.On the other hand, the 2nd In comparative example, under the travelling speed of the collector foil of practicality, mixed layer MIX thickness L3 also turns into more than 10 μm, therefore If making insulating barrier SEL thickness L2 thinning, the possibility for producing short circuit between a positive electrode and a negative electrode uprises.
Therefore, in the present embodiment, even if using as the membrane film of insulating barrier, the danger of short circuit can also be prevented Property, therefore the reliability of lithium rechargeable battery can be improved.Furthermore it is possible to using as insulating barrier while short circuit is prevented Membrane film, therefore the miniaturization of lithium rechargeable battery can be realized.So as to improve the property of lithium rechargeable battery Energy.
In addition, the effect above not only obtains in the anode electrode plate being made up of positive electrode, in negative el Also same effect can be obtained.Illustrated manufacture device and manufacture method in the present embodiment, only show reality Concrete example during present embodiment is applied, without departing from its technological thought or principal character, even in the reality of various form Apply in mode, can also obtain the effect above.
In addition, enumerating lithium rechargeable battery herein to illustrate, but it is not limited to lithium rechargeable battery, this implementation The effect of mode can be widely used in for example to be filled with positive pole, negative pole and by the electric power storage of the electrically separated barrier film of positive pole and negative pole Put.As the electrical storage device, can enumerate such as the battery or capacitor of other forms.
Embodiment 2
In present embodiment, following manufacture method and manufacture device are illustrated, the manufacture method is：With above-mentioned implementation Mode 1 is likewise arranged on the electrode layer of negative or positive electrode form insulating barrier in the lump after coated film is contacted with solidify liquid so that Its process being fully cured, then it is dried.
Figure 2 illustrates the schematic diagram of the manufacture device for the lithium rechargeable battery for representing present embodiment.This embodiment party In the manufacturing process of the lithium rechargeable battery of formula, after electrode material ES modulation is carried out in the same manner as embodiment 1, using with Die coating machine DC1 relative roller RL2, the electrode material ES of pulp-like is coated on to the collector foil supplied by current collection metal foil roller On EP surface.Thus, the 1st coated film being made up of electrode material ES is formed on collector foil EP.The coatings of collector foil EP and the 1st The respective thickness of film and width and above-mentioned embodiment 1 are same.
Then, in the same manner as above-mentioned embodiment 1, precuring process is carried out in curing room SD1.Here, only make the 1st painting The superficial layer solidification of cloth film.Solidify liquid and spray condition and above-mentioned embodiment 1 are same.The 1st coating after by surface cure On film, the 2nd coated film being made up of insulating materials IF is coated with using die coating machine DC2.The thickness and width of 2nd coated film with it is above-mentioned Embodiment 1 is same.
Then, following process is carried out, i.e.,：The collector foil EP for being coated with the 1st coated film and the 2nd coated film is transported to curing room In SD2, using spray nozzle NZ2 to the stacked film spray solidification liquid that is made up of the 1st coated film and the 2nd coated film, so that the 1st Coated film and the solidification of the 2nd coated film.Here, the process is referred to as curing process.Solidify liquid is using for example containing 40% ethanol water.It is right In solidify liquid as used herein, with above-mentioned embodiment 1 in curing room SD1 (reference picture 1) in the same manner as the solidify liquid of spraying, Alcohols or their mixed liquors such as water, ethanol or isopropanol can be used.
Spray nozzle NZ2 uses the second fluid nozzle of internal mix type.The spray particle sprayed by the second fluid nozzle Average grain diameter D50 is 10 μm.Here, the distance from spray nozzle NZ2 to the upper surface of the 2nd coated film is set to 100mm, solidify liquid Atomisation pressure be set to 0.1MPa, spray hits power is adjusted to 1g/cm2。
In order that be fully cured as the 1st coated film of electrode material layer and as the 2nd coated film of insulation material layer, will The spray amount of solidify liquid is set to 200% amount containing 40% ethanol water for making PVdF all separate out.That is, it is used to make by supply PVdF all separates out the solidify liquids of 2 times of amounts of the required amount containing 40% ethanol water as solidify liquid, makes each coated film complete All solidstate.In Fig. 2, spray nozzle NZ2 shows that much this is to increase nozzle number with as described above than spray nozzle NZ1 Supply substantial amounts of solidify liquid.
Then, the 1st coated film and the 2nd coated film are dried 10 minutes in hothouse DRY with 120 DEG C, so as to which the 1st be applied Cloth film neutralizes the solvent evaporative removal included in the 2nd coated film, manufactures the battery lead plate of lithium rechargeable battery.It is here, dry The thickness that the electrode layer of battery lead plate is formed after drying process is 50 μm, and the thickness of the insulating barrier on electrode layer is 40 μm.Above-mentioned operation It can be applied in positive plate and the respective manufacturing process of negative plate.
As described above, the composition of present embodiment is almost same with above-mentioned embodiment 1.But with above-mentioned embodiment 1 not Same point is：Between the die coating machine DC2 and hothouse DRY as the 2nd coating part, provided with different from the 1st curing room SD1 2nd curing room SD2, solidify the coated film on collector foil EP in curing room SD2.In addition, carried out in the 1st curing room SD1 In precuring process, only solidify the superficial layer of the 1st coated film, and inside uncured 1st coated film, and in contrast, solid the 2nd Change in the curing process carried out in the SD2 of room, overall all solidifications of the 1st coated film and the 2nd respective inside of coated film will be included. That is, the adhesive for making the 1st coated film and the 2nd coated film each contain all separates out.
For resulting battery lead plate in the above-mentioned manufacturing process of present embodiment, in electrode layer EL and insulating barrier SEL Near interface formed mixed layer MIX (reference picture 3) thickness, in the same manner as above-mentioned embodiment 1, no matter the fortune of collector foil How send speed, be constantly in less than 5 μm.Accordingly, even if by insulating barrier SEL filmings, can also reduce positive pole and negative pole it Between produce short circuit possibility.
In addition, as in the present embodiment, due to being fully cured each coated film before drying process, therefore even in height In the case of process is dried fastly, it can also suppress the insulation material in the electrode material and the 2nd coated film in the 1st coated film The movement of material.That is, in the case of without the curing process of the curing room SD2 of use the 2nd shown in Fig. 2, the 1st coated film it is interior Portion and the 2nd coated film are liquid when drying, therefore the composition such as adhesive in drying process in each film moves, so as to cause Convection current or diffusion are produced in each film.Therefore, dried electrode material ES is distributed with that there may be deviation.In this case, In order to suppress electrode material ES convection current or diffusion, it is necessary to suppress evaporation rate, thus produce asking for drying time long-timeization Topic.
On the other hand, in embodiment 2, each coated film is set to be fully cured inside it before drying process, therefore can prevent The only electrode material ES movements in hothouse DRY in drying process, it is possible to increase the evaporation rate of solvent etc..So as to reality The shortening of existing drying time, furthermore it is possible to realize the miniaturization of drying equipment.Thereby, it is possible to improve lithium rechargeable battery Output in manufacturing process.In addition, by the shortening of drying time or the miniaturization of drying equipment, lithium ion two can be reduced The manufacturing cost of primary cell.
Embodiment 3
Hereinafter, the manufacture method and manufacture device of the lithium rechargeable battery in present embodiment are said using Fig. 9 It is bright.In present embodiment, to will be set even in the miniaturization with lithium rechargeable battery as the insulation material layer of barrier film Count it is thin in the case of, the method that can also make the mixed layer of the near interface of electrode material layer and insulation material layer thin is said It is bright.Fig. 9 is the figure of the composition for the electrode plate manufacturing device for representing the one side coating type in present embodiment.That is, Fig. 9 is to represent this The schematic diagram of the manufacture device of lithium rechargeable battery in embodiment.
As shown in figure 9, the manufacture device of the lithium rechargeable battery in present embodiment has：Using as the collection of battery lead plate The collector foil outlet roller RL0 and winding current collecting paper tinsel EP take-up roll RL4 that electric paper tinsel EP is sent out.As laminal metal foil Collector foil EP, between collector foil outlet roller RL0 and take-up roll RL4, while being supported by multiple rollers such as roller RL2, RL3, one While it is transported.Here, in order to transport collector foil EP with constant speed, the plurality of roller is referred to as roller delivery system, that is, transported Portion.
In collector foil EP transport path, from collector foil outlet roller RL0 sides towards take-up roll RL4 sides, it is configured with successively Coating machine DC1, coating machine DC2, spray nozzle SPR and hothouse DRY in curing room SD.The collector foil EP transported leads to successively Cross between coating machine DC1 and roller RL2, between coating machine DC2 and roller RL3, in curing room SD and in hothouse DRY.
Form the positive pole of lithium rechargeable battery and each comfortable collector foil EP of negative pole material and be coated on collector foil EP's Material of film etc. is different, but can substantially be manufactured by same process.Therefore, below, regardless of positive pole and negative Extremely respective manufacturing process illustrates.For example, the electrode material ES described later as coating material, includes positive electrode material Situation and negative pole material situation, in every case, be made up of different materials.Herein, it goes without saying that in the system of positive pole Make in process, using the collector foil EP and coating material being made up of the material of positive pole, and without using only in the manufacture work of negative pole The material used in sequence.In the manufacturing process of negative pole similarly, without using the material only used in the manufacturing process of positive pole.
In the manufacturing process of lithium rechargeable battery in the present embodiment, first, modulate for forming lithium ion two The electrode material ES of the negative or positive electrode of primary cell.Then, use what is configured in a manner of relative with roller RL2 to be applied as the 1st The coating machine DC1 in cloth portion is thin and be equably coated on by collector foil outlet roller RL0 by the electrode material ES of the pulp-like modulated On the collector foil EP of supply surface.Hereinafter, the process is referred to as the 1st painting process.In addition, will be by passing through the 1st painting process The film that the electrode material ES being coated on collector foil EP is formed is referred to as electrode material layer or the 1st coated film.Above-mentioned 1st coating part can Using such as slit die coating machine, but device of other devices as supply electrode material ES can also be used.
Then, it is thin on the surface of the 1st coated film and equably be coated with insulating materials IF1, the insulating materials IF1 by with The mode relative with roller RL3 is provided as the coating machine DC2 supplies of the 2nd coating part.The process is referred to as the 2nd coating work Sequence.In addition, the film being made up of the insulating materials IF1 being coated on by the 2nd painting process in the 1st coated film is referred to as insulating materials Layer or the 2nd coated film.2nd coating part can be used such as slit die coating machine.In addition, the 1st coated film not shown and in Fig. 9 2 coated films.
Here, insulating materials IF1 contains the adhesive ingredients analysis for the superficial layer for making the 1st coated film as electrode material layer The composition gone out.Here, the composition for separating out adhesive ingredients is referred to as curing materials or solidify liquid.The lithium ion of present embodiment One of feature of secondary cell is, as described above, insulating materials IF1 includes curing materials.In 2nd painting process, comprising solid The insulating materials IF1 for changing material contacts with the surface of the 1st coated film.If the curing materials contact with the superficial layer of the 1st coated film, Then solidify liquid is while be dissolved in the solvent in the 1st coated film, while in the 1st coated film of intrusion.
Thus, if the solidify liquid concentration increase in the superficial layer of the 1st coated film, adhesive in the 1st coated film it is molten Xie Du reduces, thus adhesive separates out, and the superficial layer of only the 1st coated film is immobilized.That is, the superficial layer of the 1st coated film is passed through Adhesive separate out, fixed so as to form the active material of the 1st coated film as electrode material.Therefore, solidification the 1st is passed through The superficial layer of coated film, the active material that can prevent from forming the 1st coated film are mixed into the 2nd coated film in the 1st coated film.Separately Outside, the superficial layer of the 1st coated film refers to include the 1st coated film surface, the near surface the 1st coated film.
In addition, adhesive is with the composition acted on as follows, it is described to act as：After the drying of the 1st coated film, the will be formed Bond, and then will be bonded between powdered ingredients and collector foil between the powdered ingredients of 1 coated film.In addition, wrapped in electrode material In the case of conductive auxiliary agent, adhesive has the function that the powder and conductive auxiliary agent bonding.Form the powder of the 1st coated film End is such as positive electrode active material powder or negative electrode active material powder.
Then, by the spray nozzle SPR in curing room SD, by containing the adhesive made in electrode material layer separate out into Divide, i.e. the spray liquid LIQ of curing materials is supplied to the stacked film being made up of the 1st coated film and the 2nd coated film.Here, by spraying Atomizing nozzle SPR is sprayed spray liquid LIQ.Thus, separated out as the adhesive inside the 1st coated film of electrode material layer, So as to the superficial layer of not only the 1st coated film, the active material inside the 1st coated film is also fixed.That is, in the curing process, make Entirety for the 1st coated film of electrode material layer is cured.In addition, in the application, following form is referred to as solidified portion, the structure Turn into：Sprayed using the spray nozzle SPR in curing room SD as the spray liquid LIQ of curing materials, make the painting of spraying object Cloth film solidifies.
Then, collector foil EP is transported in the hothouse DRY as hot-air drying stove.In hothouse DRY, by the 1st Coated film neutralizes solvent composition and solidify liquid heating in the 2nd coated film, evaporates them, so that the 1st coated film and the 2nd Coated film is dry, solidification, and electrode layer and insulating barrier are formed in the lump.Hereinafter, the process is referred to as drying process.That is, 1st coated film turns into electrode layer by drying process, and the 2nd coated film turns into insulating barrier, i.e. barrier film by drying process.By This forms battery lead plate, i.e. positive plate or negative plate, the battery lead plate by collector foil EP and in collector foil EP one side successively The electrode layer and insulating barrier of stacking are formed.Then, the battery lead plate is wound in take-up roll RL4.In addition, sometimes by electricity in the application Pole, positive pole and negative pole are referred to as battery lead plate, positive plate and negative plate.
After above-mentioned drying process, the manufacturing procedure such as collector foil EP is compressed or cut off, so as to manufacture film-form The battery lead plate of negative or positive electrode.Then, in the assembling procedure of electrode unit, in the process for being referred to as winding, from by upper State the anode electrode plate of the film-form of process formation and negative el cuts out the positive pole and negative pole of size needed for battery unit.This When, as the insulating barrier of the barrier film for separating anode electrode plate and negative el, with anode electrode plate and negative el It is cut out together.Next, will electrode layer fold septate anode electrode plate and negative el it is overlapping after, will include The layered product of the anode electrode plate and negative el intervolves.
Then, the group comprising positive pole, the electrode pair of negative pole intervolved is assembled, welded.In the welding sequence, example Such as to positive collector electrode ear winding aluminum band, the aluminium strip is connected with positive pole current collections lug with ultrasonic fusing.Then, by after welding The assembling and be placed in battery can of these electrode pairs after, inject electrolyte.Next, battery can is fully sealed, so as to be formed The battery unit of lithium rechargeable battery.
In battery unit inspection operation, to the unit of lithium rechargeable battery that is made in unit assembling procedure repeatedly Carry out discharge and recharge.Thus, the cell inspection operation of the Performance And Reliability about battery unit is carried out.Examined in cell Look into process, carrying out the curtage such as when the inspection or charging of the capacity or voltage of battery unit or when discharging Inspection.Thus, the battery unit of lithium rechargeable battery, i.e. cell are completed.
Hereinafter, each material for manufacturing the lithium rechargeable battery in present embodiment is illustrated.
Electrode material ES in present embodiment, include the positive-active that can release, absorb lithium ion by discharge and recharge Material powder or negative electrode active material powder.In addition, electrode material ES includes adhesive ingredients, the adhesive ingredients is used for dry After dry between bond powders composition, or between bond powders composition and collector foil.In addition, according to circumstances, electrode material ES Powder comprising conductive auxiliary agent.
When forming positive plate, electrode material ES, the i.e. positive electrode being coated with the 1st painting process is included bag for example Active material containing lithium-contained composite oxide and the mixture of the carbon mixing as conductive auxiliary agent.The positive electrode is for example to make bag Binding material (adhesive) containing Kynoar is dissolved in N methyl pyrrolidones (NMP：N-methylpyrrolidone), exist The slurry obtained by the mixture is kneaded in resulting solution.
In the manufacturing process of positive pole, insulating materials IF1 uses the slurry obtained as follows, i.e. will be viscous comprising butadiene-styrene rubber Knot material (adhesive) be dissolved in the superficial layer for making electrode material adhesive ingredients separate out composition, i.e. be used as curing materials it One contains ethanol water, and silica (SiO is kneaded in resulting solution2) powder.In addition, in the solidification as solidified portion The solidify liquid supplied in the SD of room, i.e. spray liquid LIQ, using the composition for separating out the adhesive ingredients of electrode material, i.e., as solid That changes one of material contains ethanol water.
In addition, when forming negative plate, electrode material ES, the i.e. negative material being coated with the 1st painting process includes example Such as include the negative electrode active material of carbon material (carbon materials).The negative material is the bonding for for example making to include Kynoar Material (adhesive) is dissolved in N methyl pyrrolidones (NMP), is kneaded in resulting solution obtained by the negative electrode active material Slurry.
In the manufacturing process of negative pole, insulating materials IF1 uses the slurry obtained as follows, i.e. makes comprising butadiene-styrene rubber Binding material (adhesive) is dissolved in the composition of the adhesive ingredients precipitation for the superficial layer for making electrode material, is used as curing materials One of contain in ethanol water, silica (SiO is kneaded in resulting solution2) powder.In addition, supplied in curing room SD Solidify liquid, the i.e. spray liquid LIQ given, using the composition for separating out the adhesive ingredients of electrode material, i.e., as curing materials it One contains ethanol water.
Hereinafter, the concrete example of above-mentioned each material is shown.
Used positive active material in the present embodiment, cobalt acid lithium or the spinelle containing Mn (manganese) etc. can be used The lithium-contained composite oxide of structure, or composite oxides containing Ni (nickel), Co (cobalt) or Mn (manganese) etc..In addition, positive-active The olivine compounds such as olivine-type ferric phosphate can also be used in material.But positive active material is not limited to these materials, also may be used Use other materials.The lithium-contained composite oxide of spinel structure containing manganese can be formed due to excellent heat stability Such as safe battery.
In addition, the lithium-contained composite oxide of the spinel structure containing manganese can be used only in positive active material, can also be simultaneously With other positive active materials.As other positive active materials, can enumerate for example by Li1+xMO2(- 0.1 ＜ x ＜ 0.1) is represented Olivine compounds etc..As the example of the metal M in the formula, can enumerate Co (cobalt), Ni (nickel), Mn (manganese), Al (aluminium), Mg (magnesium), Zr (zirconium) or Ti (titanium) etc..
In addition, the lithium-containing transition metal oxide of layer structure can be used in positive active material.As containing for layer structure The concrete example of lithium transition-metal oxide, LiCoO can be used2Or LiNi1-xCox-yAlyO2(0.1≦x≦0.3、0.01≦y≦ 0.2) etc..In addition, the lithium-containing transition metal oxide of layer structure can be used including at least Co, Ni and Mn oxide etc..Make For the oxide comprising Co, Ni and Mn, such as LiMn can be enumerated1/3Ni1/3Co1/3O2、LiMn5/12Ni5/12Co1/6O2Or LiNi3/ 5Mn1/5Co1/5O2Deng.
Above-mentioned conductive auxiliary agent is used as the electronics conductive auxiliary agent being included in anode electrode film, preferably such as carbon black, acetylene The carbon materials such as black, graphite, carbon fiber or CNT.In above-mentioned carbon material, from the effect and painting of addition and electric conductivity From the viewpoint of manufacturing of the cloth with anode mixture slurry, particularly preferably acetylene black.The conductive auxiliary agent can also be included in negative In the electrode film of pole.
As the adhesive of above-mentioned binding material, preferably comprise for above-mentioned active material and conductive auxiliary agent are mutually bonded Adhesive.As the material of adhesive, such as Kynoar based polymer or rubber-based polymeric thing can be suitably used Deng.Kynoar based polymer contains the fluorine-containing of the vinylidenes as monomer more than 80 mass % for such as main component The polymer of monomer group.Above-mentioned polymer can and with two or more.In addition, the adhesive of present embodiment is preferably molten to be dissolved in Solution morphology in agent provides.
As the fluorochemical monomer group for synthesizing above-mentioned Kynoar based polymer, vinylidene or inclined fluorine can be enumerated Ethene and the mixture of other monomers and the monomer mixture of vinylidene containing more than 80 mass % etc..
As other monomers, can enumerate for example PVF, trifluoro-ethylene, CTFE, tetrafluoroethene, hexafluoropropene, Or vinyl ethers etc..
As above-mentioned rubber-based polymeric thing, such as butadiene-styrene rubber (SBR can be enumerated：Styrene-Butadiene Rubber), ethylene propylene diene rubber or fluorubber etc..
The content of electrode material layer, adhesive i.e. in the 1st coated film, is 0.1 matter on the basis of dried electrode layer Measure more than %, it is desirable to be below 10 mass %.More preferably the content of adhesive is more than 0.3 mass %, it is desirable to for 5 mass % with Under.If the content of adhesive is very few, the not only solidification in the precuring process of present embodiment becomes insufficient, dried The mechanical strength of electrode film is also insufficient, produce electrode layer from collector foil peel off the problem of.In addition, if the content of adhesive is excessive, Then the active matter quality in electrode layer is reduced, and battery capacity is possible to step-down.
In addition, aluminum oxide (Al can be used in the insulating materials IF1 used in the present embodiment2O3) or silica (SiO2) etc. inorganic oxide.In addition, by using the slurry for mixing the particulate of polypropylene or polyethylene, it can also make insulation Layer has closing property.Insulating barrier is porous film, and in the lithium rechargeable battery of completion, electrolyte is held in insulating barrier Emptying aperture in, form electrode between conducting lithium ions passage.Closing said here, refer to abnormal in lithium rechargeable battery Adstante febre, insulating barrier melting and by the function of hole plug.The transmission of the lithium ion in insulating barrier is blocked by the closing function, So as to which the reaction in battery stops, the further rise of battery temperature can be prevented.
In addition, the adhesive for bonding inorganic oxide particle used in insulating materials IF1 is used as using resin. To negative pole also in the same manner as positive pole, adhesive can suitably use above-mentioned Kynoar based polymer or rubber-based polymeric thing Deng.
In addition, in present embodiment, for the material for the solidify liquid that insulating materials IF1 is included, it is important that use The material rightly selected for the solvent in the 1st coated film and adhesive.Solidify liquid is contemplated that the bonding in the 1st coated film The dissolubility of agent composition, solvent mutual dissolubility is selected.The 1st used in the slurry of in general solvent system applies Solvent in cloth film, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), propylene carbonate, dimethylformamide or γ-fourth can be enumerated The aprotic polar solvents such as lactone or their mixed liquor.In view of the being mutually dissolved property to these solvents and used Adhesive solubility, as solidify liquid, alcohols or their mixed liquors such as water, ethanol, isopropanol may be selected, but be not limited to The example enumerated herein.
In addition, for the spray nozzle SPR out of curing room SD, equably spray solidification liquid is spray liquid LIQ, should be also The wetability of the stacked film that is made up of the 1st coated film and the 2nd coated film and solidify liquid is considered to select solidify liquid.Spray liquid LIQ It is preferred that the mixture using such as water and alcohol.Because when the stacked film being made up of the 1st coated film and the 2nd coated film and admittedly When changing the wetability difference of liquid, many places are scattered on the surface of the stacked film and adhered to island, no normal direction stacked film for solidify liquid Uniformly supply solidify liquid.That is, forming spray liquid LIQ solidify liquid needs to be good with the stacked film surface compatibility Composition.
Determining alcohol in the mixture, it is desirable to be such as 20~80%.But more preferably the concentration of the alcohol is 40~60%. When the concentration of alcohol is less than above-mentioned concentration range, the worsened wettability of above-mentioned stacked film and solidify liquid.In addition, the concentration in alcohol is higher than During above-mentioned concentration range, because the concentration of flammable alcohol raises, the operation of solidify liquid is caused to become difficult, it is quick-fried in manufacturing process etc. The dangerous increase of hair.
When the solidify liquid for forming spray liquid LIQ and the surface of above-mentioned stacked film, the wettability of the surface i.e. with the 2nd coated film Gao Shi, i.e., when compatibility is good, spray liquid LIQ only can be made up of water.In addition, when solidify liquid safely can be operated, spraying Liquid LIQ only can be made up of alcohol.
Specifically, when forming negative plate in the present embodiment, forming electrode material ES negative electrode active material can make With the graphite material such as native graphite (flaky graphite), Delanium or expanded graphite.In addition, negative electrode active material can make The easily graphitization carbonaceous material such as coke obtained by pitch is burnt till.In addition, negative electrode active material can be used furfuryl alcohol resin (PFA：Poly Furfuryl Alcohol) or polyparaphenylene (PPP：) etc. and phenolic resin low temp Poly-Para-Phenylen The difficult graphitization carbonaceous material such as amorphous carbon obtained by burning till.
In addition, in addition to above-mentioned carbon material, also Li (lithium) or lithium-containing compound etc. can be used to be used as negative electrode active material. As the lithium-containing compound, the lithium alloys such as Li-Al can be enumerated or can be with Li (lithium) alloying containing Si (silicon), Sn (tin) etc. Element alloy.And then the oxide based material such as Sn oxides, Si oxides can also be used for negative electrode active material.The oxidation Thing based material can be free of Li (lithium).
The collector foil EP used in present embodiment is not limited to the paper tinsel of sheet, as its matrix, usable such as aluminium (Al), Simple metal or the alloy properties conductive materials such as copper (Cu), stainless steel, titanium (Ti).Such as net, punch metal, bubble can be used in collector foil EP Foam metal is processed into paper tinsel of tabular etc..The thickness for the conductive base for forming collector foil EP is set to such as 5~30 μm.
Here, Figure 10 shows the mixing formed in the manufacture method of present embodiment at the interface of electrode layer and insulating barrier Layer, Figure 11 show to have carried out the result of the Thickness Evaluation of the mixed layer.The evaluation by cutting out the section of completed battery lead plate, The thickness of mixed layer is calculated from the image observed with SEM (Scanning Electron Microscope) to carry out.
Figure 10 represents to form the sectional view of the battery lead plate of lithium rechargeable battery.As shown in Figure 10, on collector foil EP, according to The secondary electrode layer EL for the being laminated with thickness L1 and thickness L2 insulating barrier SEL as barrier film.Electrode layer EL is to make the above-mentioned 1st The film that coated film is dry and is formed, insulating barrier SEL are the films for making above-mentioned 2nd coated film dry and being formed.
In addition, in electrode layer EL and insulating barrier SEL near interface, the mixed layer MIX formed with thickness L3, the mixing Layer MIX is mixed to form by electrode layer EL constituent material and insulating barrier SEL constituent material.In Figure 10, respectively with dotted line come table Show mixed layer MIX top and bottom.Mixed layer MIX is the region at the interface comprising electrode layer EL and insulating barrier SEL, from electrode Layer EL's is internally formed to insulating barrier SEL inside.In this case, the composition positive plate after drying process The thickness L1 of electrode layer is such as 30~500 μm, and the thickness L2 of insulating barrier is such as 10~20 μm.
In addition, Figure 11 is shown, based on the sectional view shown in Figure 10, mixed layer MIX thickness is entered by above-mentioned SEM observations The result of row evaluation.Figure 11 is the lithium ion of the lithium rechargeable battery and aftermentioned 4th comparative example that represent above-mentioned present embodiment The chart of the relation of the thickness of the respective mixed layer MIX (reference picture 10) of secondary cell and the travelling speed of collector foil.Figure 11 institutes The longitudinal axis of the chart shown represents the thickness of mixed layer, and transverse axis represents the travelling speed of collector foil.
The present inventor etc. carries out above-mentioned evaluation, as a result finds following items.
That is, as shown in square icon in Figure 11, in aftermentioned 4th comparative example, the thickness of mixed layer is according to the fortune of collector foil Send speed and change.That is, the travelling speed of collector foil is slower, and mixed layer MIX thickness is bigger.On the other hand, even if by collector foil Travelling speed is set to 100m/min, and the thickness of mixed layer is also at less than 10 μm.In addition, the transport of the collector foil even in practicality Under speed, the thickness of mixed layer also turns into more than 10 μm.
Mixed layer MIX is due to that electrode layer EL is mixed into insulating barrier SEL and loses the film of insulating properties.As mixed layer MIX During with larger thickness formation, there is the insulating barrier SEL of insulation function thickness to be possible to become the thickness of thin intended than script. In addition, during by insulating barrier SEL filmings, have expose the electrode material that forms mixed layer MIX on insulating barrier SEL top can Can property.That is, to by insulating layer of thin-film, then the possibility for producing short circuit uprises.
On the other hand, as shown in circular icon in Figure 11, the mixed layer MIX of the manufacture method of present embodiment thickness L3 (ginsengs According to Figure 10), the travelling speed regardless of collector foil, it is constantly in less than 4 μm.Thus, the present inventor etc. has found, if logical Cross the lithium rechargeable battery that the manufacture method of present embodiment is formed, then when by insulating barrier SEL (reference picture 10) filming, The generation of short circuit can be prevented.
For the above-mentioned manufacturing process illustrated using Fig. 9, describe and be coated with electricity successively in collector foil EP one side Pole material ES and insulating materials IF1, manufacture the example of the electrode slice of negative or positive electrode.Electricity is respectively coated on collector foil EP two sides When the material ES and insulating materials IF1 of pole, it is contemplated that after above-mentioned manufacturing process, the electrode slice for making to be wound in take-up roll RL4 turns over Turn, again pass by identical process to be coated with the face of the opposite side of collector foil EP above-mentioned one side.
Here, using Figure 12, the elemental motion principle to lithium rechargeable battery illustrates.Figure 12 is expression lithium ion The schematic diagram of the structure of secondary cell.
As shown in figure 12, lithium rechargeable battery is one kind of rechargeable nonaqueous electrolytic battery, be lithium in electrolyte from Son undertakes the secondary cell of conduction.Active material PA as positive electrode uses lithium metal oxide, as negative material Active material NA uses the carbon materials such as graphite.In addition, use the organic solvents such as ethylene carbonate comprising electrolyte solution ELQ With lithium hexafluoro phosphate (LiPF6) etc. lithium salts.In battery, lithium ion comes out from positive pole PE and enters negative pole NE during charging, discharges When then on the contrary, lithium ion comes out from negative pole NE and enters positive pole PE.Positive pole PE collector foil uses the Al paper tinsels being made up of Al (aluminium) AF, negative pole NE collector foil use the Cu paper tinsels CF being made up of Cu (copper).
Lithium rechargeable battery for example possesses electrode coiling body, and the electrode coiling body is by being coated with positive electrode Positive plate, the negative plate for being coated with negative material and prevent the barrier film SP such as the thin polymer film that positive plate contacts with negative plate Winding forms.Also, lithium rechargeable battery has following form：The electrode coiling body is inserted into outer tinning, and outer tinning Inside it is injected with electrolyte.That is, lithium rechargeable battery has layered product, and the layered product is formed as follows：It will apply on metal foil The positive plate that cloth positive electrode forms and the negative plate that coating negative material forms on metal foil are formed as banding, across barrier film Positive plate and the negative plate for being formed into banding are overlapping in a manner of being not directly contacted with.By winding the layered product, so as to be formed Above-mentioned electrode coiling body with swirl shape section.
Hereinafter, the manufacture method of the lithium rechargeable battery of the 3rd comparative example is illustrated.
Figure 13 is the flow chart of the specific process schematically shown untill lithium rechargeable battery is manufactured.Such as Figure 13 institutes Show, the manufacturing process of lithium rechargeable battery includes：Anode electrode piece manufacturing process, negative electricity pole piece manufacturing process, battery list The assembling procedure and module assembled process of member.
In the manufacturing process of lithium rechargeable battery in the 3rd comparative example, first, modulator electrode material.For being formed The liquid for the highly viscous slurry shape that the electrode material of the electrode layer of the negative or positive electrode of composition lithium rechargeable battery is formed as Body：The powder of the active material that can release, absorb lithium ion by discharge and recharge and conductive auxiliary agent is bonded into these powder with being used for The adhesive and solvent at end etc. are kneaded, scattered (mixing, allotment process shown in Figure 13).Then, in the metal foil of film-form The grout material is coated with, followed by drying (painting process shown in Figure 13).Then, to being coated with the metal of grout material Paper tinsel such as is compressed or cut off at the processing (manufacturing procedure shown in Figure 13), forms the anode electrode piece of film-form.
On the other hand, negative electricity pole piece manufacturing process is entered with above-mentioned anode electrode piece manufacturing process by same step OK.But the various materials that are used in above-mentioned anode electrode piece manufacturing process and used in negative electricity pole piece manufacturing process each Kind material is sometimes different.I.e., first, the various materials as negative material raw material are kneaded and allocated, it is (negative to make grout material Pole material) (mixing, allotment process shown in Figure 13).Then, the grout material is coated with the metal foil of film-form, is done Dry (painting process shown in Figure 13).Next, processing (the figure such as the metal foil for being coated with grout material is compressed or cut off Manufacturing procedure shown in 13), manufacture the negative electricity pole piece of film-form.
Then, in electrode unit assembling procedure, in the process for being referred to as winding, from above-mentioned anode electrode piece and negative electricity Pole piece cuts out the positive pole and negative pole of size needed for battery unit.In addition, at the same time, from for separate above-mentioned anode electrode piece and The film-form diaphragm material of negative electricity pole piece cuts out the barrier film of size needed for battery unit, sandwiches and is cut out in positive pole and negative pole Barrier film, it is overlapping to intervolve (rolling step shown in Figure 13).Then, assemble what is be made up of the positive pole after intervolving, negative pole and barrier film The group of electrode pair, and welded (welding, assembling procedure shown in Figure 13).Then, by the group of these electrode pairs after welding It is configured at and is injected with the battery can of electrolyte (the fluid injection process shown in Figure 13), (Figure 13 institutes then is fully sealed in battery can The sealing process shown).Thus, battery unit is made.
In battery unit inspection operation, the unit of the lithium rechargeable battery to being made in unit assembling procedure enters repeatedly Row discharge and recharge (the discharge and recharge process shown in Figure 13).Thus, the cell of the Performance And Reliability about battery unit is carried out Inspection operation (the cell inspection operation shown in Figure 13).In cell inspection operation, the appearance of such as battery unit is carried out The inspection of curtage when the inspection or charging of amount or voltage or when discharging etc..Thus, lithium rechargeable battery is completed Battery unit, i.e. cell.
Then, in module assembled process, multiple battery cells in series are combined, form battery module, and then and discharge charge Electric control is connected with controller, forms battery system (the module assembled process shown in Figure 13).Then, in module check process, Carry out the inspection (module check shown in Figure 13 of the Performance And Reliability of the battery module about being assembled in module assembled process Process).In the module check process, carry out such as battery module capacity or voltage inspection or charging when or electric discharge when Curtage etc. inspection.
In the manufacture method and manufacture device of the lithium rechargeable battery of present embodiment, in the electrode slice of negative or positive electrode In manufacturing process, insulation material layer is coated with electrode material layer, process is then dried, so as to formed electrode layer and The battery lead plate that insulating barrier as barrier film is integrally formed.Therefore, for above-mentioned 3rd comparative example, in battery unit assembles process, In the process of winding barrier film, the process for preparing processed barrier film can be omitted.Thereby, it is possible to improve lithium rechargeable battery The output of manufacturing process.
Hereinafter, the manufacture method of the lithium rechargeable battery of the 4th comparative example is illustrated using Figure 14.Figure 14 is expression The schematic diagram of the manufacture device of lithium rechargeable battery in 4th comparative example.
Figure 14 represents the composition of the one side coating type electrode plate manufacturing device in the 4th comparative example.Represent as carrier material The collector foil EP of material coated on one side electrode material ES and insulating materials IF2 manufacturing process's example.The manufacturing process of 4th comparative example It is the process being coated to the one side of electrode slice.In the manufacturing process of the 4th comparative example, first, to by collector foil outlet roller The face for the collector foil EP that RL0 is sent out, it is coated with by the electrode material ES of the coating machine DC1 supply relative with roller RL2.
Next, on electrode material ES after coating, be coated with by with the coating machine DC2 of roller RL3 relative positions supplies Insulating materials IF2.Then, collector foil EP is made by hothouse DRY, so as to be carried out to electrode material ES and insulating materials IF2 Dry, and be wound in take-up roll RL4, manufacture anode electrode piece.In the drying process, by electrode material ES form the 1st coating Film is dried, and so as to turn into electrode layer, the 2nd coated film being made up of insulating materials IF2 is dried, so as to turn into insulating barrier, i.e. barrier film.
As described above, by after the positive electrode of pulp-like and the overlapping coating of insulating materials, by being entered using hothouse DRY Capable heating, drying process, the coated film of both sides can be made while dried, set, therefore the 4th comparative example and the 3rd comparative example phase Than the efficiency high of manufacturing process.
However, as the 4th comparative example, when the electrode material and insulating materials of the continuous coating sizing-agent shape in collector foil When, as shown in Figure 10, the near interface of electrode layer EL and insulating barrier SEL on the collector foil EP of battery lead plate is coated on, formed Lose the mixed layer MIX of insulation function.The present inventor etc. has found, mixed layer MIX be because using Figure 11 come the slit that illustrates The coating pressure of die coating machine and caused layer.As shown in square icon in Figure 11, the caused mixed layer MIX in the 4th comparative example The thickness of (reference picture 10), changes according to the travelling speed of collector foil.That is, the travelling speed of collector foil is slower, coating machine institute The time that caused pressure applies to the coated film of ad-hoc location is longer, also bigger so as to mixed layer MIX thickness.Even if will collection The travelling speed of electric paper tinsel is set to faster 100m/min, and mixed layer MIX thickness also turns into more than 10 μm.
When mixed layer MIX is with larger thickness formation, there are the following problems：The thickness of insulating barrier SEL with insulation function Degree becomes thicker than the thickness that script is intended；And during by insulating barrier SEL filmings, have and expose structure on insulating barrier SEL top Into the possibility of mixed layer MIX electrode material.
It is contemplated that the 4th comparative example as described above is such, prevented by eliminating the gap of electrode layer and barrier film (insulating barrier) Only internal short-circuit, and the productivity of lithium rechargeable battery is improved, and the manufacture device densification by lithium rechargeable battery, But for this composition, the problem of due to above-mentioned mixed layer, the filming of insulating barrier is caused to become difficult.That is, the 4th comparative example In, the problem of high capacity and miniaturization difficult of lithium rechargeable battery be present.
Hereinafter, to being illustrated using Fig. 9 come the effect of the present embodiment illustrated.
Relative to above-mentioned 4th comparative example, in the manufacture method of the lithium rechargeable battery of present embodiment, such as Fig. 9 institutes Show, after the 1st layer of the 1st coated film as electrode layer is coated with, insulating materials IF1 of the coating comprising curing materials, which is used as, to be turned into 2nd layer of the 2nd coated film of insulating barrier.Thus, the superficial layer of the 1st coated film is cured.So, in coating insulating materials IF1 When, the superficial layer of the 1st coated film is solidified, thickness is formed so as to prevent electrode material ES and insulating materials IF1 from mixing Big mixed layer MIX (reference picture 10).
In addition, in present embodiment, after above-mentioned painting process, using as the spray liquid of curing materials in curing room SD LIQ is supplied to the 1st coated film and the 2nd coated film, so that the 1st coated film and the 2nd coated film are fully cured.Thus, in drying In drying process in the DRY of room, can prevent because of the adhesive flow of electrode material ES and the respective inside of insulating materials IF1 and Cause electrode material ES and insulating materials IF1 to mix, form the big mixed layer MIX (reference picture 10) of thickness.
As described above, in present embodiment, the thickness L3 of mixed layer MIX shown in Figure 10 can be made smaller than the 4th comparative example. Specifically, mixed layer MIX thickness can be made to be less than 5 μm.On the other hand, in the 4th comparative example, even in the current collection of practicality Under the travelling speed of paper tinsel, mixed layer MIX thickness L3 is also at more than 10 μm, if therefore make insulating barrier SEL thickness L2 thinning, The possibility for then producing short circuit between a positive electrode and a negative electrode uprises.
Therefore, in the present embodiment, even if using as the membrane film of insulating barrier, the danger of short circuit can also be prevented Property, so as to improve the reliability of lithium rechargeable battery.Furthermore it is possible to while short circuit is prevented, insulating barrier will be used as Membrane film, therefore the miniaturization of lithium rechargeable battery can be realized.So as to improve lithium rechargeable battery Performance.
In addition, in the present embodiment, as shown in figure 9, spray liquid LIQ is supplied before drying process, so that each coating Film is fully cured, therefore in the case of process is dried at high speed, can also suppress the electrode material in the 1st coated film The movement of insulating materials in material and the 2nd coated film.That is, in the case of without the curing process using curing room SD, the 1st The inside of coated film and the 2nd coated film are liquid when drying, therefore the composition such as adhesive in drying process in each film moves It is dynamic, so as to cause that convection current or diffusion are produced in each film.Thus, dried electrode material ES distribution produces deviation, and having can The big mixed layer MIX (reference picture 10) of thickness can be formed.In this case, in order to suppress because above-mentioned adhesive movement or melt again Deng and caused electrode material ES convection current or diffusion, it is necessary to suppress evaporation rate.If however, reducing evaporation rate, produce The problem of drying time long-timeization.
On the other hand, in present embodiment, each coated film is fully cured until in it in curing room SD before drying process Portion, so as to prevent that electrode material ES is moved in hothouse DRY drying process, it is possible to increase the evaporation speed of solvent etc. Degree.So as to realize the shortening of drying time, furthermore it is possible to realize the miniaturization of drying equipment.Thereby, it is possible to improve lithium from The output of the manufacturing process of sub- secondary cell.In addition, by the shortening of drying time or the miniaturization of drying equipment, can drop The manufacturing cost of low lithium rechargeable battery.
In addition, the effect above not only obtains in the anode electrode plate comprising positive electrode, also can in negative el Access same effect.Illustrated manufacture device and manufacture method, which are only shown, in present embodiment implements this implementation Concrete example during mode, without departing from its technological thought or principal character, in the embodiment of various form, Also the effect above can be obtained.
In addition, being illustrated here, enumerating lithium rechargeable battery, but it is not limited to lithium rechargeable battery, this reality The effect for applying mode can be widely used in and for example possess positive pole, negative pole and the storage by the electrically separated barrier film of positive pole and negative pole Electric equipment.As the electric energy storage device, can enumerate such as the battery or capacitor of other forms.
More than, the invention completed based on embodiment to the present inventor etc. is illustrated, but self-evident, this Invention is not limited to above-mentioned embodiment 1~3, in the range of its purport is not departed from, can carry out various changes.
Industrial applicability
The present invention is effectively applied to be applied layer of cloth and forms the lithium rechargeable battery of battery lead plate on electrode layer In manufacturing technology.
Symbol description
1：Shower nozzle, 3：Manifold, 4：Slit, 5：Electrode material reservoir, 8：Lip, 9：Downstream meniscus (liquid level it is curved It is bent), AF：Al paper tinsels, CF：Cu paper tinsels, DC1：Die coating machine, coating machine (the 1st coating part), DC2：Die coating machine, coating machine (the 2nd coating Portion), DRY：Hothouse, EL：Electrode layer, ELQ：Electrolyte, EP：Collector foil, ES：Electrode material, IF：Insulating materials, IF1：Absolutely Edge material, LIQ：Spray liquid, MIX：Mixed layer, NA：Active material, NE：Negative pole, NZ1：Spray nozzle, NZ2：Spray nozzle, PA：Active material, PE：Positive pole, RL0：Collector foil outlet roller, RL1：Current collection metal foil roller, RL2：Roller, RL3：Roller, RL4：Take-up roll, SD：Curing room, SD1：Curing room, SD2：Curing room, SEL：Insulating barrier, SP：Barrier film, SPR：Spray nozzle.

Claims (18)

1. a kind of manufacture method of lithium rechargeable battery, it has：
(a1) process for using the 1st coating part coating electrode material paste on the surface of collector foil；
(b1) by the 1st solidify liquid of the composition separated out comprising the adhesive ingredients that makes contained by the electrode material slurry supply to The electrode material slurry, so that the process of the superficial layer solidification of the electrode material slurry；
(c1) after (b1) process, insulating materials slurry is coated with the electrode material slurry using the 2nd coating part Process；
(c2) after (c1) process, the electrode material slurry and insulating materials slurry supply, which are included, makes the electricity 2nd solidify liquid of the respective composition that contained adhesive ingredients separates out of pole material paste and the insulating materials slurry, so as to Make the electrode material slurry and the insulating materials slurry curing；
(d1) process for making the electrode material slurry and the insulating materials slurry drying.
2. the manufacture method of lithium rechargeable battery as claimed in claim 1,
Solvent contained by the electrode material slurry is aprotic polar solvent,
Solvent for the 1st solidify liquid is water or alcohols or their mixed liquor.
3. the manufacture method of lithium rechargeable battery as claimed in claim 1,
Solvent contained by the electrode material slurry is 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), propylene carbonate, dimethyl Formamide or gamma-butyrolacton or their mixed liquor,
Solvent for the 1st solidify liquid is water, ethanol or isopropanol or their mixed liquor.
4. the manufacture method of lithium rechargeable battery as claimed in claim 1,
The determining alcohol of the 1st solidify liquid supplied in (b1) process is 20~80%.
5. a kind of manufacture device of lithium rechargeable battery, it has：
The 1st coating part of coating electrode material paste on the surface of collector foil；
1st solidify liquid of the composition separated out comprising the adhesive ingredients made contained by the electrode material slurry is supplied to described Electrode material slurry, so that the 1st curing room of the superficial layer solidification of the electrode material slurry；
The 2nd coating part of insulating materials slurry is coated with the electrode material slurry after superficial layer solidification；
2nd curing room, the 2nd curing room are described comprising making to the electrode material slurry and insulating materials slurry supply 2nd solidify liquid of the composition that the adhesive ingredients contained by electrode material slurry and the insulating materials slurry separates out, so that The electrode material slurry and the insulating materials slurry curing；
Make the electrode material slurry and the hothouse of the insulating materials slurry drying；And
The collector foil is transported to the 1st coating part, the 1st curing room successively, the 2nd coating part, the described 2nd consolidated Change the transport portion of room and the hothouse.
6. the manufacture device of lithium rechargeable battery as claimed in claim 5,
Solvent contained by the electrode material slurry is aprotic polar solvent,
Solvent for the 1st solidify liquid is water or alcohols or their mixed liquor.
7. the manufacture device of lithium rechargeable battery as claimed in claim 5,
Solvent contained by the electrode material slurry is 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), propylene carbonate, dimethyl Formamide or gamma-butyrolacton or their mixed liquor,
Solvent for the 1st solidify liquid is water, ethanol or isopropanol or their mixed liquor.
8. the manufacture device of lithium rechargeable battery as claimed in claim 5,
The spray nozzle that the 1st curing room possessed supplies the 1st solidify liquid is the second fluid nozzle of internal mix type,
The spray area of the spray nozzle has impartial flow distribution, turns into 50% flow of the spray nozzle centralized traffic Position, it is outer in the end than the electrode material slurry on the direction orthogonal with the carriage direction of the collector foil Position,
The spray particle diameter of the 1st solidify liquid supplied by the spray nozzle is less than 10 μm,
The spray hits power of 1st solidify liquid is 1g/cm2Below.
9. a kind of lithium rechargeable battery, the manufacture device of the lithium rechargeable battery described in usage right requirement 6 is formed.
10. lithium rechargeable battery as claimed in claim 9, it has：
The electrode layer for making the electrode material slurry drying in the collector foil and being formed；
The insulating barrier for making the insulating materials slurry drying on the electrode material slurry and being formed；And
The mixed layer of electrode layer formed in the near interface of the electrode layer and the insulating barrier, described and the insulating barrier,
The thickness of the mixed layer is less than the 20% of the thickness of insulating layer.
11. lithium rechargeable battery as claimed in claim 9, it has the overlapping structure of more electrode plates, the battery lead plate Have：
The collector foil,
The electrode layer that makes the electrode material slurry drying in the collector foil and formed and
The insulating barrier for making the insulating materials slurry drying on the electrode material slurry and being formed.
12. a kind of manufacture method of lithium rechargeable battery, it has：
(a) process of the electrode material slurry comprising binding material is coated with the surface of collector foil using the 1st coating part；
(b) it is coated with using the 2nd coating part on the electrode material slurry comprising the 1st composition for separating out the binding material The process of insulating materials slurry；
(c) after (b) process, the solidify liquid comprising the 2nd composition for making the binding material precipitation is supplied to the electricity Pole material paste, so that the process of the electrode material slurry curing；
(d) after (c) process, the process that makes the electrode material slurry and the insulating materials slurry drying.
13. the manufacture method of lithium rechargeable battery as claimed in claim 12,
1st composition and the 2nd composition contain water or alcohol.
14. the manufacture method of lithium rechargeable battery as claimed in claim 13,
The alcohol contains methanol, ethanol, propyl alcohol, butanol, hexanol, enanthol or octanol.
15. the manufacture method of lithium rechargeable battery as claimed in claim 12,
In (d) process, make the electrode material slurry drying and form electrode layer, make on the electrode material slurry The insulating materials slurry drying and form insulating barrier,
Further with (e) by the overlapping work of battery lead plate of the polylith with the collector foil, the electrode layer and the insulating barrier Sequence.
16. a kind of manufacture device of lithium rechargeable battery, it has：
The 1st coating part of electrode material slurry of the coating comprising binding material on the surface of collector foil；
On the electrode material slurry coating comprising the insulating materials slurry for making the 1st composition that the binding material separates out the 2 coating parts；
Solidify liquid comprising the 2nd composition for making the binding material precipitation is supplied to the electrode material slurry, so that institute State the solidified portion of electrode material slurry curing；
Make the electrode material slurry and the hothouse of the insulating materials slurry drying；And
The collector foil is transported to the 1st coating part, the 2nd coating part, the solidified portion and the hothouse successively Transport portion.
17. the manufacture device of lithium rechargeable battery as claimed in claim 16, the 1st composition and the 2nd composition contain There are water or alcohol.
18. the manufacture device of lithium rechargeable battery as claimed in claim 17, the alcohol contains methanol, ethanol, propyl alcohol, fourth Alcohol, hexanol, enanthol or octanol.
CN201480049882.9A 2013-09-27 2014-06-26 The manufacture method of lithium rechargeable battery, the manufacture device of lithium rechargeable battery and lithium rechargeable battery Expired - Fee Related CN105531865B (en)

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