CN109314208A - Partition powder, partition slurry, lithium ion battery and its manufacturing method - Google Patents
Partition powder, partition slurry, lithium ion battery and its manufacturing method Download PDFInfo
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- CN109314208A CN109314208A CN201780035343.3A CN201780035343A CN109314208A CN 109314208 A CN109314208 A CN 109314208A CN 201780035343 A CN201780035343 A CN 201780035343A CN 109314208 A CN109314208 A CN 109314208A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
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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
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Improve the characteristic of partition used in lithium ion battery.Keep negative paste S (Nb) and partition slurry S (SPn) dry, negative electrode tab NS is formed on metal foil Na, negative electrode tab NS has the partition SPn formed by negative paste S (Nb) the negative electrode layer Nb formed and on negative electrode layer Nb by partition slurry S (SPn).The solvent of the second inorganic oxide particles, the binder and dissolution binder that bond the particle in the mixture of the first inorganic oxide particles and the second inorganic oxide particles that aforementioned barriers slurry S (SPn) has the first inorganic oxide particles, shape different from the first inorganic oxide particles.For example, the first inorganic oxide particles are spherical silicon dioxide, the second inorganic oxide particles are unsetting silica.Relative to the mixed weight of spherical silicon dioxide and unsetting silica, the ratio of unsetting silica is 25 weight % or more, 75 weight % or less.
Description
Technical field
Partition powder, partition slurry used in partition the present invention relates to lithium ion battery, lithium ion battery and
Its manufacturing method.
Background technique
It is used along with the prosperity of portable electronic device as the power supply source of these portable electronic devices
The small battery that can be charged repeatedly.Wherein, energy density is high, cycle lie is long and self discharge is low and operating voltage
High lithium-ions battery attracts attention.Lithium-ions battery has above advantages, therefore is widely used in digital camera, pen
Remember the portable electronic devices such as this computer, mobile phone.
The electrode group of main element as lithium-ions battery is made of partition, anode and cathode.
For example, disclosing a kind of used in patent document 1 (Japanese Unexamined Patent Publication 2015-99801 bulletin) contains resin
The nonaqueous electrolyte battery of material and the partition of inorganic oxide filler.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2015-99801 bulletin
The present inventor is engaged in the exploitation of lithium ion battery, and the characteristic for being conceived to partition improves, and carries out to the structure of partition
Further investigation.
Partition refers to: among battery be isolated positive electrode and negative electrode and keep electrolyte and ensure between positive electrode and negative electrode from
The conductive component of son.However, there is a situation where that the dipped type of electrolyte is poor, on the contrary, being electrolysed in the high material of insulating properties
In the high material of the dipped type of liquid, there is a situation where that insulating properties is low etc., it is difficult to which selection meets insulating properties, electrolysis in the ideal range
The material of the dipped type of liquid.
In this regard, inorganic oxide particles are selected as the constituent material of partition by the present inventor, by aftermentioned various researchs,
To have found such as lower clapboard: ensuring insulating properties in order to which positive electrode and negative electrode are isolated, and have and immersed for electrolysis liquid
And ensure the hole of ionic conductance.
Summary of the invention
It is an object of the present invention to improve the characteristic of the partition of lithium ion battery.
If the summary of the representative content in disclosed embodiment in this application is briefly described, following institute
It states.
Partition in one embodiment has the first inorganic oxide particles, shape and the described first inorganic oxygen with powder
The second different inorganic oxide particles of compound particle and make first inorganic oxide particles and described second inorganic
The binder of particle bonding in the mixture of oxide particle.
Partition in one embodiment has the first inorganic oxide particles, shape and the described first inorganic oxygen with slurry
The second different inorganic oxide particles of compound particle make first inorganic oxide particles and second inorganic oxide
The binder of particle bonding in the mixture of composition granule and the solvent of the dissolution binder.
Lithium ion battery in one embodiment has the positive-active comprising being occluded and being discharged to lithium ion
The anode layer of substance, is laminated in institute at the negative electrode layer comprising the negative electrode active material that the lithium ion is occluded and discharged
State at least one party of anode layer and the negative electrode layer partition and can be mobile for the lithium ion electrolyte, it is described every
The second inorganic oxide that plate has the first inorganic oxide particles, shape different from first inorganic oxide particles
Grain and bond the particle in the mixture of first inorganic oxide particles and second inorganic oxide particles
Binder.
The manufacturing method of lithium ion battery in one embodiment includes (a) coated electrode on the surface of metal foil
Apply the process of partition slurry on the electrode slurry with the process of slurry, (b), (c) make the electrode slurry with
And the partition process that slurry is dry and electrode slice is formed in the metal foil, which has is used by the electrode
The electrode layer and there is the partition formed by partition slurry, (b) process on the electrode layer that slurry is formed
The used partition has the first inorganic oxide particles, shape different from first inorganic oxide particles with slurry
The second inorganic oxide particles, make the mixing of first inorganic oxide particles and second inorganic oxide particles
The binder of particle bonding in object and the solvent of the dissolution binder.
Invention effect
If being briefly described to by the representative content in invention disclosed in this application come the effect obtained,
As described below.
Partition powder or partition slurry according to embodiment of the present invention, can make the characteristic of partition
It improves.
Lithium ion battery according to embodiment of the present invention can be such that the characteristic of lithium ion battery improves.
The manufacturing method of lithium ion battery according to embodiment of the present invention, can the good lithium of manufacturing characteristics from
Sub- battery.
Detailed description of the invention
Fig. 1 is the synoptic diagram for indicating a part of the structure of lithium ion battery of embodiment 1.
Fig. 2 is the cross-sectional view for indicating the formation process of negative electrode tab.
Fig. 3 is the electron micrograph (figure) of spherical silicon dioxide.
Fig. 4 is the electron micrograph (figure) of unsetting silica.
Fig. 5 is the figure (chart) for the measurement result for indicating partition film thickness.
Fig. 6 is the figure (chart) for the measurement result of resistance value for indicating partition.
Fig. 7 is the figure (chart) for the measurement result of film-strength for indicating partition.
Fig. 8 is the figure (chart) for indicating to have used the measurement result of the film-strength of the partition of polypropylene or heat-resistant sheet.
Fig. 9 is the figure (chart) for the measurement result of speed characteristic for indicating lithium ion battery.
Figure 10 is the flow chart for indicating an example of manufacturing sequence for the lithium ion battery of embodiment 2.
Figure 11 is the cross-sectional view for indicating an example of manufacturing process for the lithium ion battery of embodiment 2.
Figure 12 is the cross-sectional view for indicating an example of manufacturing process for the lithium ion battery of embodiment 2.
Figure 13 is the cross-sectional view for indicating an example of manufacturing process for the lithium ion battery of embodiment 2.
Figure 14 is the top view for indicating an example of manufacturing process for the lithium ion battery of embodiment 2.
Figure 15 is the cross-sectional view for indicating an example of manufacturing process for the lithium ion battery of embodiment 2.
Figure 16 is the cross-sectional view for indicating an example of manufacturing process for the lithium ion battery of embodiment 2.
Figure 17 is the cross-sectional view for indicating an example of manufacturing process for the lithium ion battery of embodiment 2.
Figure 18 is the top view for indicating an example of manufacturing process for the lithium ion battery of embodiment 2.
Figure 19 is the perspective view for indicating an example of manufacturing process for the lithium ion battery of embodiment 2.
Figure 20 is the cross-sectional view for indicating an example of manufacturing process for the lithium ion battery of embodiment 2.
Figure 21 is the figure for indicating an example of structure for the lithium ion battery of laminated-type.
Figure 22 is the concept map for indicating an example of manufacturing device for the lithium ion battery of embodiment 3.
Specific embodiment
In the following embodiments, if not it is especially necessary, do not repeat the explanation of same or same part in principle.
Further, in the following embodiments for convenience when necessary, be divided into multiple portions or
Embodiment is illustrated, but the case where in addition to especially clearly stating, above-mentioned multiple portions or embodiment not milli each other
It is irrelevant, but in relationships such as some or all variations, detailed description, the supplementary explanations that a side is another party.
In addition, in the following embodiments, in quantity for referring to element etc. (including number, numerical value, amount, range etc.)
In the case of, the case where being limited to the case where in addition to especially clearly stating and clearly specific quantity in principle etc., and it is unlimited
It is set to the specific quantity.Further, it is possible to be set as specific quantity above and below.
In addition, in the following embodiments, the case where in addition to especially clearly stating and it is considered necessary in principle
Clear situation etc., it is self-evident that this composition element (also comprising element step etc.), which is not necessarily necessary this point,.
In addition, in the following embodiments, " being made of A ", " being formed by A ", " tool are being referred to as constituent element etc.
When having A ", " comprising A ", the case where in addition to especially explicitly indicating that the purport for only limiting the element etc., and non-excluded wanting in addition to this
Element is self-evident.Equally, in the following embodiments, it in shape, the positional relationship etc. for referring to constituent element etc., removes
The case where especially explicitly indicating that and it is considered situation about not knowing in principle etc., actually comprising with the shape etc. approximate
Or similar shape etc..The situation is also identical for above-mentioned numerical value and range etc..
In addition, in the following embodiments, in the case where indicating range as A~B, in addition to especially explicitly indicating that
The case where, indicate A or more B range below.
Hereinafter, embodiment is described in detail based on attached drawing.In addition, for illustrating whole attached drawings of embodiment
In, identical appended drawing reference is marked for component with the same function, omits its repeated explanation.In addition, in order to facilitate understanding
Attached drawing also marks shade in a top view sometimes.
(embodiment 1)
< construction illustrates >
Fig. 1 is the synoptic diagram for indicating a part of the structure of lithium ion battery of present embodiment.Lithium ion battery (lithium from
Sub- battery) have as described above by positive plate, negative plate and the insulating properties for preventing contact of the positive plate with negative plate
Constituting portion made of partition stacking.In the present embodiment, as shown in Figure 1, have negative electrode tab NS and positive plate PS are laminated and
At constituting portion.
[negative electrode tab]
Negative electrode tab NS has negative plate NE and partition SPn.Negative plate NE has metal foil Na and negative electrode layer, and (electrode layer is born
Pole film) Nb.Metal foil (also referred to as collector foil, electrode foil) Na is, for example, Cu foil.Negative electrode layer Nb at least has occlusion and release
The negative electrode active material of lithium ion.Negative electrode layer Nb also has binder, dispersing agent, other additions except negative electrode active material
Agent etc..
Negative plate NE can for example be added by the mixture (negative electrode material) to above-mentioned negative electrode active material, binder etc.
Dispersion solvent is kneaded and makes slurry, and the negative paste is carried out heat coated on metal foil (Cu foil) Na later
Air-dry dry formed.
Partition SPn is the component for preventing positive plate PE with the insulating properties of the contact of negative plate NE.Here, matching as one layer
It sets on negative plate NE.Partition SPn has spherical silicon dioxide, unsetting silica and makes in their mixture
Particle bonding binder.In addition to this, partition SPn also can have dispersing agent etc..
Partition SPn can for example pass through the mixing to above-mentioned spherical silicon dioxide, unsetting silica and binder etc.
Object (separator material) adds dispersion solvent, is kneaded and makes partition slurry, and by the slurry coating on negative plate NE,
Carry out heated-air drying later to be formed.
In addition, as shown in Fig. 2, the negative plate NE and partition SPn that constitute negative electrode tab NS also can be by metal foil (Cu
Foil) apply negative paste on Na, then apply partition slurry on the negative paste of coating after, carry out heated-air drying
To be formed.
[positive plate]
Positive plate PS has positive plate PE and partition SPp.Positive plate PE has metal foil Pa and anode layer (electrode layer, just
Pole film) Pb.Metal foil (also referred to as collector foil, electrode foil) Pa.E.g. Al foil.Anode layer Pb at least has occlusion and release
The positive active material of lithium ion.Anode layer Pb also has binder, dispersing agent, other additions except positive active material
Agent etc..
Positive plate PE can for example be added by the mixture (positive electrode) to above-mentioned positive active material, binder etc.
Dispersion solvent is kneaded and makes slurry, and by the anode slurry coating on metal foil (Al foil) Pa, carries out heat later
Air-dry dry formed.
Partition SPp is the component for preventing positive plate PE with the insulating properties of the contact of negative plate NE.Here, matching as one layer
It sets on positive plate PE.Partition SPp has spherical silicon dioxide, unsetting silica and makes in their mixture
Particle bonding binder.In addition to this, partition SPp also can have dispersing agent etc..
Partition SPp can for example pass through the mixing to above-mentioned spherical silicon dioxide, unsetting silica and binder etc.
Object (separator material) adds dispersion solvent, is kneaded and makes partition slurry, and by the slurry coating on positive plate PE,
Carry out heated-air drying later to be formed.
In addition, the positive plate PE and partition SPp for constituting positive plate PS also can in the same manner as negative electrode tab NS shown in Fig. 2
By applied on metal foil (Al foil) Pa positive slurry, then on the positive slurry of coating coating partition with slurry it
Afterwards, heated-air drying is carried out to be formed.
The constituting portion that above-mentioned negative electrode tab NS and positive plate PS are laminated immerses electrolyte (not shown).
In addition, being both equipped with the partition as insulating materials in negative electrode tab NS and positive plate PS, but can also in Fig. 1
With the only setting partition either in negative electrode tab NS and positive plate PS.
< preparation method illustrates >
Fig. 2 is the cross-sectional view for indicating the formation process of negative electrode tab.
As shown in Fig. 2, applying the negative paste S (Nb) sprayed from nozzle NZ1 on metal foil (Cu foil) Na, connect down
Come, the partition that sprays from nozzle NZ2 is applied on negative paste S (Nb) with slurry S (SPn).In this way, continuously coating liquid
Slurry.In addition it is also possible to which the boundary in double-deck overlay generates negative paste S (Nb) and partition with slurry S's (SPn)
Mixed layer.
Next, being thermally dried to double-deck overlay on metal foil (Cu foil) Na, evaporate solvent composition.By
This, can form the laminated section of negative electrode layer Nb Yu partition SPn on metal foil (Cu foil) Na.Other sayings are exchanged with, are capable of forming
The laminate component (negative electrode tab NS) of negative plate NE and partition SPn.In addition, in Fig. 2, though the boundary of each layer is specifically called out,
After heat drying, mixed layer can also be remained in the boundary of negative electrode layer Nb and partition SPn.
Alternatively, it is also possible to which the laminated section of negative electrode layer Nb and partition SPn to be coated on to the two sides (reference of metal foil (Cu foil) Na
The circle portion of Figure 20).In this case, the back side of metal foil (Cu foil) Na is set as upside, in the same manner as above-mentioned operation successively
Coating negative paste S (Nb) and partition slurry S (SPn) are simultaneously thermally dried.
It in Fig. 2, is illustrated by taking negative electrode tab NS as an example, but positive plate PS can be also identically formed.For example, in gold
Belong to and apply the anode that sprays from nozzle NZ1 on foil (Al foil) Pa with slurry S (Pb), is next applied positive on slurry S (Pb)
The partition that sprays from nozzle NZ2 is applied with slurry S (SPp).In this way, the slurry of continuously coating liquid.Next, to metal foil (Al
Foil) double-deck overlay on Pa is thermally dried, and evaporate solvent composition.Thereby, it is possible on metal foil (Al foil) Pa
Form the laminated section of anode layer Pb and partition SPp.It changes other sayings into, is capable of forming the stacking structure of positive plate PE Yu partition SPp
Part (positive plate PS).In addition it is also possible to which the laminated section of anode layer Pb and partition SPp to be coated in the two sides of metal foil (Al foil) Pa
(referring to the circle portion of Figure 20).In this case, the back side of metal foil (Al foil) Pa is set as upside, in the same manner as above-mentioned operation
Successively coating anode slurry S (Pb) and partition slurry S (SPp), and be thermally dried.
Later, after overlapping negative electrode tab NS and positive plate PS, the laminates is wound and form rolled electrode group.It connects down
Come, after being inserted into battery can by rolled electrode group and inject electrolyte, battery cover be installed on battery can top and is sealed,
Thus it is fabricated to lithium ion battery.About the manufacturing process of lithium ion battery, it is described in detail in embodiment 2.
< operating principle >
The operating principle of lithium ion battery is illustrated.When connecting charger between positive plate PE and negative plate NE
When, the lithium ion being inserted into positive active material is detached from, and is discharged into electrolyte.At this point, since lithium ion is from positive-active
Substance is detached from, and electronics flows to charger from anode.Then, the lithium ion being discharged into electrolyte moves in the electrolytic solution, passes through
Partition and reach cathode.The lithium ion for reaching cathode is inserted into the negative electrode active material for constituting cathode.At this point, due to lithium from
Son is inserted into negative electrode active material, and thus electronics flows into cathode.So, electronics is moved via charger from positive to cathode
Dynamic, thus charging terminates.
On the other hand, when connecting external loading between positive plate PE and negative plate NE, it is inserted into negative electrode active material
Interior lithium ion is detached from and discharges into electrolyte.At this point, discharging electronics from cathode.Then, be discharged into lithium in electrolyte from
Son moves in the electrolytic solution, reaches anode by partition.The lithium ion for reaching anode, which is inserted into, constitutes the positive living of anode
In property substance.At this point, electronics flows into anode.So, anode is moved to from cathode due to electronics, thus discharged.This
Sample, in lithium ion battery, can by be inserted into lithium ion between positive active material and negative electrode active material, be detached from come
Carry out charging and discharging.
Here, by the clear mechanism of the charging and discharging of above-mentioned lithium ion battery it is found that partition (SPn, SPp) is in the battery
It isolation positive electrode and negative electrode and keeps electrolyte and ensures the important component of the ionic conductivity between positive electrode and negative electrode.
Here, there is silica dioxide granule and make in order to improve insulating properties in the partition (SPn, SPp) of present embodiment
The binder of particle bonding.As silica dioxide granule, the mixture of spherical silicon dioxide and unsetting silica is used.
Spherical silicon dioxide refers to that shape is spherical silica.For example, can be by making powder in the flame of high temperature
Broken silica melts and forms its spheroidizing by surface tension.The commercially available product of spherical silicon dioxide is more, such as
Spherical silicon dioxide with TOKUYAMA corporation, DENKA corporation.Particle diameter also has a variety of, and commercial type has 2
μm~30 μm of spherical silicon dioxide.The electron micrograph of spherical silicon dioxide is shown in FIG. 3.It is shown in Fig. 3 spherical
The average grain diameter of silica is 4 μm, and is non-porous.
Unsetting silica refers to, shape and non-spherical and have angular silica.Also referred to as have angle silica,
Non- amorphous silicon dioxide, crushing silica etc..For example, can be formed by crushing silica.Unsetting titanium dioxide
The commercially available product of silicon is also more, such as the unsetting silica with ball east corporation, Seishin Enterprise corporation.
Particle diameter also has a variety of, and commercial type has 1 μm~100 μm of unsetting silica.It is shown in FIG. 4 unsetting two
The electron micrograph of silica.The average grain diameter of unsetting silica shown in Fig. 4 is 7 μm, and is non-porous
's.
Embodiment
Silica dioxide granule, binder, dispersing agent and dispersion solvent are kneaded and are fabricated to partition slurry.As
Silica dioxide granule has used spherical silicon dioxide and unsetting silica.As spherical silicon dioxide and unsetting dioxy
SiClx uses the silica being illustrated referring to Fig. 3, Fig. 4.It is used respectively with 100 weight %:0 weight %, 75 weight %:
The silica dioxide granule that mixes of ratio of 25 weight %, 50 weight %:50 weight %, 25 weight %:75 weight %.It will system
The slurry made is set as sample S1 (100%), sample S2 (75%), sample S3 (50%), sample S4 (25%).
1 > of < embodiment
Use the titanium dioxide for mixing spherical silicon dioxide and unsetting silica by ratio below
Silicon particle.Vingon (PVDF) is used as binder, and polyvinyl pyrrole network alkanone is used as dispersing agent
(PVP), N- methyl pyrrole network alkanone (NMP) is used as dispersion solvent.It makes spherical silicon dioxide and unsetting titanium dioxide
The slurry that silicon is mixed respectively with the ratio of 100%:0%, 75%:25%, 25%:75%, and it is set as sample S1
(100%), sample S2 (75%), sample S4 (25%).By silica dioxide granule (spherical silicon dioxide and unsetting titanium dioxide
Silicon), binder (PVDF), dispersion solvent (NMP), the weight ratio of dispersing agent (PVP) respectively 40~45 weight %, about 5%,
It is adjusted in the range of 50~55 weight %, 0~0.1 weight %.
(partition film thickness)
For slurry and the drying for applying above-mentioned sample S1 (100%), sample S2 (75%) and sample S4 (25%)
At film, measure its film thickness.The measurement result of partition film thickness is shown in FIG. 5.In Fig. 5, the pump for being used to spray slurry is turned
Fast (rpm) is set as horizontal axis, and the film thickness (μm) after the coating of slurry, drying is set as the longitudinal axis.Revolution speed is corresponding with spray volume, therefore
If revolution speed increases, film thickness becomes larger.When being compared under identical revolution speed, the film thickness of sample S4 (25%) compares sample
S1 (100%) is big.Since the volume of spherical silicon dioxide and the per unit weight of unsetting silica is not significantly different, recognize
It is bigger than sample S1 (100%) for the hole rate of sample S4 (25%).In the case where hole rate is big, it is believed that be easy to immerse electrolysis
The degree of excursion of liquid, lithium ion increases.On the other hand, compared with sample S4 (25%), titanium dioxide of the sample S1 (100%) in same amount
Film thickness under silicon is small, can reduce by stacking or wound film come using battery size, can be improved every battery volume
Discharge capacity.In addition, the film thickness of sample S1 (100%) and sample S2 (75%) is same degree.
In addition, sample S4 (25%) -2 makes the weight ratio of dispersion solvent increase by 5% relative to sample S4 (25%), dioxy
The total weight of SiClx is than reducing 5%.As illustrated, it was found that the trend that film thickness becomes smaller when the amount of dispersion solvent increases.
(insulation characterisitic)
For the above-mentioned sample S1 (100%) of coating, sample S2 (75%), sample S3 (50%) and sample S4 (25%)
Slurry and film made of drying, measure its resistance value.In Fig. 6, the index (insulated electro that the value of S1 (100%) is set as to 1 is utilized
Resistance index) come indicate partition insulating resistance value measurement result.In Fig. 6, by the ratio (mixing ratio of spherical silicon dioxide
Example) it is set as horizontal axis (%), the insulation resistance index of the film after the coating of slurry, drying is set as the longitudinal axis.As shown in fig. 6, sample
The resistance value of S2 (75%), sample S3 (50%) and sample S4 (25%) are greater than sample S1 (100%).In particular, resistance value
It increased dramatically from sample S2 (75%), it is believed that just cause the rising of resistance value to be imitated by slightly adding unsetting silica
Fruit.
(summary)
According to the research of above partition film thickness and insulation characterisitic, specify by mixing spherical silicon dioxide with it is indefinite
Shape silica to improve the insulation characterisitic between the positive electrode and negative electrode of partition, and improves the holding of the electrolyte of partition
Characteristic.Relative to the mixed weight of spherical silicon dioxide and unsetting silica, the ratio of unsetting silica is preferably
75% or less 25 weight % or more.
2 > of < embodiment
(air permeance resistance degree)
Production silica dioxide granule, binder, dispersing agent and dispersion solvent are kneaded made of partition slurry and
It is that the slurry of spherical silicon dioxide is used only as above-mentioned silica dioxide granule, is set to sample S1 (100%), production is only
Using the slurry of unsetting silica, it is set to sample S5 (0%).
For the slurry for applying above-mentioned sample S1 (100%) and sample S5 (0%) and film made of drying, it is measured thoroughly
Vapour lock dynamics (Ge Erlai value).For the slurry for applying above-mentioned sample S1 (100%) and sample S5 (0%) and made of drying
Film is able to confirm that the high-permeability of liquid compared with non-woven fabrics partition.The Ge Erlai of the case where being only spherical silicon dioxide (S1)
The Ge Erlai value of the case where value is 7~10, is only unsetting silica (S5) is 20, and the Ge Erlai value of non-woven fabrics partition is
100~130.
Thus, it is believed that for having used silica dioxide granule made of mixing spherical silicon dioxide and unsetting silica
Partition, be also able to maintain that the high-permeability of liquid.
In addition, being realised that the Ge Erlai value of the case where being only unsetting silica (S5) than being only spherical silicon dioxide
Situation (S1) is slightly higher, and the permeability of liquid is low.In this regard, in the case where having used unsetting silica tortuosity ratio increase by
It is considered key factor.In the case where tortuosity ratio height, it is able to suppress the dendritic growth bring anode by undesirable metal
Short circuit between plate and negative plate.
The height of liquid is able to maintain that by mixing spherical silicon dioxide and unsetting silica according to above investigation
Permeability simultaneously improves tortuosity ratio, is able to suppress by the short circuit between dendritic growth bring positive plate and negative plate.
(film-strength)
Production silica dioxide granule, binder, dispersing agent and dispersion solvent are kneaded made of partition slurry and
It is the slurry that unsetting silica is used only as above-mentioned silica dioxide granule, is set to sample S5 (0%).Prepare
5 stacked films made of applying negative paste on Cu foil, then applying the slurry of sample S5 (0%) and dry, measurement film are strong
Degree (perforation intensity).The measurement result of the film-strength of partition is shown in FIG. 7.In Fig. 7, by the weight of the weight loaded on film
Amount (thrust (N)) is set as horizontal axis, and resistance (Ohm) is set as the longitudinal axis.Resistance is the resistance between the electrode on negative plate and film, should
The reduction of resistance means the short circuit as caused by the destruction of film.The film-strength of film shown in Fig. 7 is about 200N.Common poly-
In the case where carrying out identical test on the partition of propylene, film-strength is about 50N (referring to (a) of Fig. 8).In addition, using resistance to
Hot material is about 200N (referring to figure to the film-strength for the partition that polypropylene carries out so-called heat-resistant sheet made of coating
8 (b)).Fig. 8 is the figure for indicating to have used the measurement result of the film-strength of the partition of polypropylene or heat-resistant sheet.
In this way, realizing the simplification of the production of partition by the way that partition is set as coated film, and further by applying together
(continuously coating) can be such that film-strength improves.The raising of such film-strength is using spherical silicon dioxide and unsetting two
It also can be realized in the case where the mixture of silica.
(summary)
According to the research of above air permeance resistance degree and film-strength, with spherical silicon dioxide and unsetting titanium dioxide
Also it can be realized the raising of air permeance resistance degree, film-strength in the partition of silicon.In addition, by being mixed with unsetting silica, energy
Tortuosity ratio is enough improved, is able to suppress by the short circuit between dendritic growth bring positive plate and negative plate.
3 > of < embodiment
(speed characteristic)
Production mixes spherical silicon dioxide and unsetting silica respectively with the ratio of 100%:0%, 25%:75%
Made of slurry, and be set to sample S1 (100%), sample S4 (25%).Using on Cu foil apply negative paste, connect
The slurry of coating sample S1 (100%) or sample S4 (25%) and stacked film made of drying, make the lithium of laminated-type from
Sub- battery (referring to embodiment 2), and measure respective speed characteristic.The speed characteristic of lithium ion battery is shown in FIG. 9
Measurement result.In Fig. 9, c rate is set as horizontal axis, capacity ratio (%) is set as the longitudinal axis.The numerical value A of horizontal axis refers in 1/A
Make its electric discharge in time.For example, the case where 10 c rate refers to, its electric discharge is made within (1/10) time, each chart it is corresponding
The numerical value of the longitudinal axis refers to, the ratio of the initial discharge capacity relative to the discharge capacity within (1/10) time in the case where electric discharge
Example.
In chart, L24_sc1, L24_sc2 are figures the case where having used sample S4 (25%).L23_sc1,L23_sc2,
L23_sc3 is figure the case where having used sample S1 (100%).In addition, the difference of L23_sc1, L23_sc2, L23_sc3 exist
In the coating amount of the slurry of sample S1 (100%).For spraying the revolution speed of the slurry of L23_sc1, L23_sc2, L23_sc3
It (rpm) is 20rpm, 15rpm, 10rpm.It is clear that by each chart of L23_sc1, L23_sc2, L23_sc3, for spraying slurry
The revolution speed of material is smaller, i.e. the coating amount of slurry is fewer, and the film thickness of partition is thinner, inhibits the reduction of capacity ratio.This is
Because the film thickness of partition is relatively thin, therefore interelectrode resistance becomes smaller.
In contrast, the revolution speed (rpm) for spraying the slurry of L24_sc1, L24_sc2 is 25rpm.In this way, although
The coating amount of slurry is serial more than L23, but the reduction of capacity ratio is inhibited compared with L23 series.
It is clear that in this way, by mixing spherical silicon dioxide and unsetting silica, is able to suppress capacity ratio
It reduces, realizes the raising of flash-over characteristic.
According to the above embodiments as a result, following concentration illustrates preferred partition powder and partition slurry.
< is about partition powder >
The partition of present embodiment is in the partition slurry used in the production of lithium ion battery with powder
Powder (powder).
In the present embodiment, aforementioned barriers use in powder comprising as silica dioxide granule spherical silicon dioxide and
The mixture of unsetting silica and the binder (adhesive) for bonding each particle in the mixture.Relative to ball
The mixed weight of shape silica and unsetting silica, the ratio of unsetting silica are preferably 25 weight % or more 75
Weight % or less.
In addition, as described in Example 1 above, being able to use Vingon (PVDF) as binder.In addition,
Also butadiene-styrene rubber (SBR) can be used.
In the case where using water solvent (such as water, ethyl alcohol etc.) as dispersion solvent, it is preferable to use butadiene-styrene rubber
(SBR), organic solvent (also referred to as solvent series solvent, organic solvent are being used as dispersion solvent.For example, N- methyl pyrrole
Network alkanone (NMP) etc.) in the case where, it is preferable to use Vingon (PVDF).
Here, in the present embodiment, as partition powder, having used silica dioxide granule, but oxygen also can be used
Change other inorganic oxide particles such as alumina particles.That is, can also be used as partition powder with replacement of silicon dioxide particle
Spherical alumina particle and unsetting alumina particle.Wherein, from the density of silica dioxide granule compared with alumina particle
From the perspective of weight small, that battery can be reduced, silica dioxide granule is more preferably used.In addition, as described above, relative to ball
The mixed weight of shape particle and unsetting particle, the ratio of unsetting particle are preferably 25 weight % or more, 75 weight % or less.
In addition, the particle diameter (average diameter of particle) of the spherical particle in inorganic oxide particles is preferably 0.1 μm~10 μm.Separately
Outside, the particle diameter of unsetting particle (average diameter of particle) is preferably set as 0.1 μm~10 μm.Further, preferably by nothing
The ratio of machine oxide particle (total weight of spherical particle and unsetting particle) is set as 20 weight of weight %~60 % of slurry.
In addition, having used spherical particle and unsetting particle, but it also can be used as above-mentioned inorganic oxide particles
The particle of its shape.That is, by making variform particle mixing, especially keeping spherical particle and the particle of simultaneously non-spherical mixed
It closes, said effect can be played.
In addition, having used non-porous particle as Fig. 3, silica dioxide granule shown in Fig. 4, but also can be used more
Hole silica dioxide granule.For example, it is also possible to use the porous irregular spherical silica dioxide granule of Corefront corporation
(3 μm~500 μm of particle diameter).In addition, in porous silica silicon particle, also can be used with nano-pores (such as hole
Diameter 5nm~50nm) particle with two kinds of pores in micron pore (such as 0.1 μm~20 μm of aperture).Such porous silica
Silicon can be formed by special synthetic method (such as sol-gel method).Certainly, as the inorganic oxygen other than silica
Above-mentioned porous structure also can be used in compound particle.
In addition, dispersing agent can also be added as partition powder.Dispersing agent have make inorganic oxide in the slurry
The function of grain dispersion.As dispersing agent, it is able to use polyvinyl pyrrole network alkanone (PVP) etc..
If only passing through addition dispersion solvent etc., it will be able to be readily formed slurry using such partition powder.
< is about partition slurry >
The partition of present embodiment is the partition slurry to form the partition of lithium ion battery with slurry.
In the present embodiment, aforementioned barriers use in slurry comprising as silica dioxide granule spherical silicon dioxide and
The mixture of unsetting silica, the binder (adhesive) for bonding each particle in the mixture and dispersion solvent.
As binder and dispersion solvent, it is able to use Vingon (PVDF) and organic solvent (for example, N- methyl pyrrole
Network alkanone (NMP) etc.).Alternatively, it is also possible to use butadiene-styrene rubber (SBR) and water solvent (such as water, ethyl alcohol etc.).
In addition, dispersing agent (dispersant particle) can also be added as partition slurry.Dispersing agent have make in the slurry
The function of inorganic oxide particles dispersion.As dispersing agent, it is able to use polyvinyl pyrrole network alkanone (PVP) etc..
(embodiment 2)
In the present embodiment, for having used the partition being described in detail in the embodiment 1 powder, partition slurry
The manufacturing method of lithium ion battery be illustrated, and be clearly the lithium for having used aforementioned barriers powder, partition slurry
One example of the structure of ion battery.
Figure 10 is the flow chart for indicating an example of manufacturing sequence for the lithium ion battery of embodiments of the present invention.Figure
11~Figure 20 is the figure for indicating an example of manufacturing process for the lithium ion battery of present embodiment.Figure 14 and Figure 18 is to bow
View, Figure 19 are perspective views, and other figures are cross-sectional views.Along process shown in Fig. 10, to the manufacturing method of lithium ion battery into
Row illustrates.
1. positive plate manufactures
< is kneaded, deploys process >
Firstly, addition dispersion is molten in positive electrode (positive active material, binder, dispersing agent, other additives etc.)
Agent is kneaded and makes anode with slurry S (Pb).
The first working procedure of coating of < (electrode material) >
Next, as shown in figure 11, anode is relatively thin with slurry S (Pb) and be evenly coated at laminar metal foil
On the surface of (Al foil) Pa.For example, using slit die coating machine, from opening portion is sprayed in the nozzle NZ1 of slit-shaped to metal
Anode is sprayed on foil (Al foil) Pa uses slurry S (Pb).
The second working procedure of coating of < (insulating materials) >
It is partition slurry S (SPp) is relatively thin and be evenly coated at anode with slurry S (Pb) next, as shown in figure 12
Surface on.For example, using slurry S to positive in the nozzle NZ2 of slit-shaped from opening portion is sprayed using slit die coating machine
(Pb) partition is sprayed on slurry S (SPp).
Here, partition slurry S (SPp) includes inorganic oxide particles (spherical dioxy as illustrated by embodiment 1
The mixture of SiClx and unsetting silica), the binder that bonds inorganic oxide particles, make inorganic oxide particles point
The dispersion solvent (solvent) of scattered dispersing agent and dissolution binder.As binder and dispersion solvent, using gathering inclined chloroethene
Alkene (PVDF) and organic solvent (for example, N- methyl pyrrole network alkanone (NMP) etc.).Alternatively, it is also possible to use butadiene-styrene rubber
(SBR) and water solvent (such as water, ethyl alcohol etc.).As dispersing agent, polyvinyl pyrrole network alkanone (PVP) etc. is used.
In addition, the first working procedure of coating is preferably carried out by a coated portion with the second working procedure of coating.Further, to just
Pole on slurry S (Pb) apply partition slurry S (SPp) above-mentioned second working procedure of coating in, it is (not dry not being dried
Dry) anode coating partition slurry S (SPp) on slurry S (Pb).
< drying process >
Next, to successively coated with the anode metal foil (Al foil) of slurry S (Pb) and partition slurry S (SPp)
Pa carries out heated-air drying.Solvent composition evaporation of the anode in slurry S (Pb) and partition slurry S (SPp) as a result, forms
The stacked film (Figure 13) of anode layer (cathode film) Pb and partition.That is, formed by metal foil (Al foil) Pa, anode layer Pb thereon,
And the positive plate PS that partition SPp thereon is constituted.It changes other sayings into, is formed in by metal foil (Al foil) Pa and anode layer Pb
Positive plate PS made of partition SPp is configured on the positive plate PE of composition.
< film thickness measuring step >
Later, for example, carrying out the measurement of total film thickness of the anode layer Pb and partition SPp of positive plate PS.
In addition, it is formed with anode layer Pb and partition SPp on the surface of metal foil (Al foil) Pa in above-mentioned operation, but
The stacked film of anode layer Pb and partition SPp can also be formed on the two sides of metal foil (Al foil) Pa (referring to the circle of Figure 20
Portion).For example, by the way that positive plate PS is wound in take-up roll, invert positive plate PS, by the back side of metal foil (Al foil) Pa (with
The face of applicator surface opposite side) it is set as upper surface, carrying out identical process, (< is kneaded, deploys the first working procedure of coating of process >, <
(electrode material) >, < the second working procedure of coating (insulating materials) >, < drying process >), at the back side of metal foil (Al foil) Pa
On be also capable of forming the stacked film of anode layer Pb Yu partition SPp.Next, carrying out the < film thickness measuring of the stacked film on the back side
Process >.
< manufacturing procedure >
Next, the processing such as being compressed and being cut off relative to positive plate PS.For example, positive plate PS is cut into battery
Size needed for monomer.For example, as shown in figure 14, positive plate PS is cut into it is substantially rectangular, further along positive plate PS
Long side region and be uncoated anode slurry S (Pb), partition slurry S (SPp) region multiple notch are being set (just
Pole collector plate PTAB).
2. negative plate manufactures
< is kneaded, deploys process >
Firstly, addition dispersion is molten in negative electrode material (negative electrode active material, binder, dispersing agent, other additives etc.)
Agent is kneaded and makes negative paste S (Nb).
The first working procedure of coating of < (electrode material) >
Next, as shown in figure 15, it is negative paste S (Nb) is relatively thin and be evenly coated at laminar metal foil
On the surface of (Cu foil) Na.For example, using slit die coating machine, from opening portion is sprayed in the nozzle NZ1 of slit-shaped to metal
Negative paste S (Nb) is sprayed on foil (Cu foil) Na.
The second working procedure of coating of < (insulating materials) >
Next, as shown in figure 16, it is partition slurry S (SPn) is relatively thin and be evenly coated at negative paste S (Nb)
Surface on.For example, using slit die coating machine, from opening portion is sprayed in the nozzle NZ2 of slit-shaped to negative paste S
(Nb) partition is sprayed on slurry S (SPn).
Here, partition slurry S (SPn) includes inorganic oxide particles (spherical dioxy as illustrated by embodiment 1
The mixture of SiClx and unsetting silica), the binder that bonds inorganic oxide particles, make inorganic oxide particles point
The dispersion solvent (solvent) of scattered dispersing agent and dissolution binder.As binder and dispersion solvent, using gathering inclined chloroethene
Alkene (PVDF) and organic solvent (for example, N- methyl pyrrole network alkanone (NMP) etc.).Alternatively, it is also possible to use butadiene-styrene rubber
(SBR) and water solvent (such as water, ethyl alcohol etc.).As dispersing agent, polyvinyl pyrrole network alkanone (PVP) etc. is used.
In addition, the first working procedure of coating is preferably carried out by a coated portion with the second working procedure of coating.Further, to negative
Pole on slurry S (Nb) apply partition slurry S (SPn) above-mentioned second working procedure of coating in, it is (not dry not being dried
It is dry) on negative paste S (Nb) coating partition with slurry S (SPn).
< drying process >
Next, to the metal foil (Cu foil) for being successively coated with negative paste S (Nb) and partition slurry S (SPn)
Na carries out heated-air drying.The solvent composition of negative paste S (Nb) and partition in slurry S (SPn) evaporates as a result, is formed
The stacked film (Figure 17) of negative electrode layer (negative electrode film) Nb and partition.That is, formed by metal foil (Cu foil) Na, negative electrode layer Nb thereon,
The negative electrode tab NS that partition SPn thereon is constituted.It changes other sayings into, is formed in and is made of metal foil (Cu foil) Na and negative electrode layer Nb
Negative plate NE on configure partition SPn made of negative electrode tab NS.
< film thickness measuring step >
Later, for example, carrying out the measurement of total film thickness of the negative electrode layer Nb and partition SPn of negative electrode tab NS.
In addition, it is formed with negative electrode layer Nb and partition SPn on the surface of metal foil (Cu foil) Na in above-mentioned operation, but
The stacked film of negative electrode layer Nb and partition SPn can also be formed on the two sides of metal foil (Cu foil) Na (referring to the circle of Figure 20
Portion).For example, by the way that negative electrode tab NS is wound in take-up roll, invert negative electrode tab NS, by the back side of metal foil (Cu foil) Na (with
The face of applicator surface opposite side) it is set as upper surface, carrying out identical process, (< is kneaded, deploys the first working procedure of coating of process >, <
(electrode material) >, < the second working procedure of coating (insulating materials) >, < drying process >), at the back side of metal foil (Cu foil) Na
On be also capable of forming the stacked film of negative electrode layer Nb Yu partition SPn.Next, carrying out the < film thickness measuring of the stacked film on the back side
Process >.
< manufacturing procedure >
Next, the processing such as being compressed and being cut off relative to negative electrode tab NS.For example, negative electrode tab NS is cut into battery
Size needed for monomer.For example, as shown in figure 18, negative electrode tab NS is cut into it is substantially rectangular, further along negative electrode tab NS
Long side region and be uncoated negative paste S (Nb), partition slurry S (SPn) that multiple notch are arranged is (negative in region
Pole collector plate NTAB).
In addition, applying in positive plate PS and this two side of negative electrode tab NS and being used as the partition of insulating materials in above-mentioned operation
Slurry and form partition, but can also only either positive plate PS and negative electrode tab NS apply partition slurry.
3. battery cell assembles
< rolling step >
Next, as shown in figure 19, by positive plate PS it is Chong Die with negative electrode tab NS after, by the laminates using central spindle CR as axis
It is wound, forms rolled electrode group.In addition, from the end of a side of rolled electrode group, by the metal foil (Al of positive plate PS
Foil) the positive pole current collections piece PTAB that constitutes of Pa is prominent, from the end of another party, it is made of metal foil (Cu foil) Na of negative electrode tab NS
Cathode collector plate NTAB it is prominent.
< welding, assembling procedure >
Next, as shown in figure 20, using ultrasonic bonding to the positive pole current collections piece PTAB of a side side of rolled electrode group
It is attached with positive pole current collections ring PR.In addition, using ultrasonic bonding to the cathode collector plate of another party side of rolled electrode group
NTAB is attached with cathode collector ring NR.So, it is formed by rolled electrode group, positive pole current collections ring PR and cathode collector ring
The electrode unit that NR is constituted.
Next, being inserted into above-mentioned electrode unit in the inside of the columnar outer tinning CS with bottom, utilizing ultrasonic wave
The bottom and cathode collector ring NR for welding external tinning CS are attached.In addition, connecting battery cover by positive wire plate PT
CAP and positive pole current collections ring PR.For example, being led using ultrasonic bonding to anode of the ultrasonic bonding on the back side of battery cover CAP
Line plate PT is attached with positive pole current collections ring PR.
< drawing liquid process >
Next, injecting electrolyte (not shown) in outer tinning CS.As electrolyte, nonaqueous electrolytic solution is used.As above
It states like that, lithium ion battery is the battery for carrying out charging and discharging towards insertion, the disengaging of active material using lithium ion, lithium ion
It moves in the electrolytic solution.Lithium is strong reductant, generates hydrogen with water vigorous reaction.Therefore, in lithium ion battery, as electricity
It solves liquid and uses nonaqueous electrolytic solution.
< sealing process >
Next, it is caulking being carried out in the way of surrounding the periphery of battery cover CAP by the top of outer tinning CS, externally
Tinning CS is sealed.So, lithium ion battery can be manufactured.In addition, will winding positive electrode sheet PS and negative electrode tab like this
The laminates of NS and the battery for making the type of electrode group is referred to as winding-type lithium ion battery.
In contrast, the battery that the type of positive plate PS and negative electrode tab NS is laminated is referred to as to the lithium ion battery of laminated-type.
Figure 21 is the figure for indicating an example of structure for the lithium ion battery of laminated-type.(a) it is exploded perspective view, is (b) top view.
As illustrated, the lithium-ions battery of laminated-type is by clamping positive plate PS and negative electrode tab NS from upper and lower using exterior film F
Laminates and the inlet of hermetic electrolyte liquid other than periphery after inject electrolyte and seal inlet to be formed.This
Outside, positive pole current collections piece PTAB and cathode collector plate NTAB is sealed in such a way that from exterior film (battery exterior body), F is outstanding, anode
Collector plate PTAB and cathode collector plate NTAB respectively become positive terminal and negative terminal.In addition it is also possible to using by positive plate
PS and negative electrode tab NS are alternately laminated laminates made of multi-disc.
In this way, the partition of present embodiment other than winding-type lithium ion battery, can also be suitable for laminated-type
Lithium ion battery.
< charging and discharging process >
Next, lithium ion battery (battery cell) recharge to formation discharges.
< battery cell inspection operation >
Next, progress inspection relevant to the performance of above-mentioned lithium ion battery (battery cell) and reliability (such as
Electric current and the inspection of voltage when the capacity and voltage of battery cell, charge or discharge etc.).By above process,
Complete lithium ion battery.
4. module assembled
In module assembled process, combines multiple lithium ion batteries (battery cell) in series and constitute battery
Module further connects charge/discharge control controller and constitutes battery module (battery system) (module assembled).Later,
In module check process, carry out related to the performance of battery module and reliability assembled by module assembled process
Inspection (such as electric current, voltage etc. when checking the capacity of battery module, voltage, charge or discharge) (module check).
(embodiment 3)
In the present embodiment, the manufacturing device of lithium ion battery is illustrated.Figure 22 is to indicate implementation of the invention
The concept map of one example of the manufacturing device of the lithium ion battery of mode.
The manufacturing device of lithium ion battery shown in Figure 22 has the delivery section conveyed to metal foil 110, in metal
First coated portion 108 of coated electrode slurry (positive slurry or negative paste) and coating partition slurry on foil
Second coated portion 109 of material.It is applied in addition, the first coated portion 108 and the second coated portion 109 preferably carry out the first coating with second
A deposited coated portion.
Further, there is the manufacturing device of lithium ion battery the electrode slurry for making coating and partition slurry to dry
It drying oven 130 and is surveyed to by the dry electrode layer (anode layer or negative electrode layer) formed and total film thickness of partition
Fixed determination part 145.
In addition, the manufacturing device of lithium ion battery has the outlet roller 101, coiled metal foil 110 for sending out metal foil 110
Take-up roll 107.Metal foil 110 is between outlet roller 101 and take-up roll 107 by multiple rollers 102,103,104,105,106 as a result,
It supports and is conveyed along conveying direction S.Here, in order to use multiple rollers with constant speed to convey metal foil 110, it will be above-mentioned
Multiple rollers are referred to as delivery section.
On the landline of metal foil 110, the first coating is successively arranged from 101 side of outlet roller towards 107 side of take-up roll
Portion 108, the second coated portion 109, drying oven 130, determination part 145.
The first coated portion 108 be configured with to the electrode slurry of the electrode material as pulp-like (positive slurry or
Person's negative paste) 122 coating machine 121 (for example, slit die coating machine), the rollers opposed with coating machine 121 sprayed
102, transported metal foil 110 passes through between coating machine 121 and roller 102.Then, in the first coated portion 108, by specified amount
Electrode slurry 122 be coated in metal foil 110 from coating machine 121.
In addition, electrode slurry 122 is the active material to release, the occlusion for being able to carry out lithium ion by charging and discharging
Be kneaded with additives such as powder, the conductive agent of conductive agent etc., the binder for making these powder adhesions and solvent etc.,
The liquid of highly viscous pulp-like made of allotment.
On the other hand, configured with the partition slurry 124 to the insulating materials as pulp-like in the second coated portion 109
Coating machine (such as slit die coating machine) 123, the roller 103 opposed with coating machine 123 sprayed, transported metal foil
110 by between coating machine 123 and roller 103.Then, in the second coated portion 109, by the partition of specified amount with slurry 124 from
Coating machine 123 is coated on the electrode slurry 122 in metal foil 110.In other words, it in metal foil 110, is starched in electrode
Laminated clapboard slurry 124 on material 122.
In drying oven 130, electrode slurry 122 and partition in the metal foil 110 next to conveying are carried out with slurry 124
Hot-blast Heating simultaneously makes its solidification.That is, carrying out Hot-blast Heating to electrode slurry 122 and forming electrode layer (anode layer or cathode
Layer), partition is heated with slurry 124 and forms partition.It is laminated electrode layer and partition in metal foil 110 as a result, and shape
At electrode slice (positive plate or negative electrode tab) (1~Figure 18 referring to Fig.1).
In addition, being configured with micrometer caliper 142, the roller 106 opposed with micrometer caliper 142 on determination part 145.By
This, in determination part 145, by micrometer caliper 142, to complete including electrode layer and partition comprising transported electrode slice
Portion's film thickness is measured.
< has used the manufacturing method > of the lithium ion battery of above-mentioned manufacturing device
Next, being illustrated to the manufacturing method for the lithium ion battery for having used above-mentioned manufacturing device.Firstly, be kneaded,
Deploy electrode slurry (positive slurry or negative paste) 122.
The first working procedure of coating of < (electrode material) >
Next, the coating machine 121 being had using the first coated portion configured in the mode opposed with roller 102, it will be electric
Slurry (positive slurry or negative paste) 122 in pole is relatively thin and is evenly coated at the thin slice supplied from outlet roller 101
On the surface of the metal foil 110 of shape.
The second working procedure of coating of < (insulating materials) >
It, will be every next, the coating machine 123 being had using the second coated portion configured in the mode opposed with roller 103
Plate slurry 124 is relatively thin and is evenly coated on the surface of electrode slurry 122.
Here, partition slurry 124 includes inorganic oxide particles (spherical titanium dioxide as illustrated by embodiment 1
The mixture of silicon and unsetting silica), make inorganic oxide particles bond binder, disperse inorganic oxide particles
Dispersing agent and dissolve binder dispersion solvent (solvent).As binder and dispersion solvent, Vingon is used
(PVDF) and organic solvent (such as N- methyl pyrrole network alkanone (NMP) etc.).Alternatively, it is also possible to use butadiene-styrene rubber (SBR)
And water solvent (such as water, ethyl alcohol etc.).As dispersing agent, polyvinyl pyrrole network alkanone (PVP) etc. is used.
In this way, being able to carry out electrode slurry 122 and partition slurry by using the manufacturing device of present embodiment
124 coating together (continuously coating).
< drying process >
Next, conveying metal foil 110 in the drying oven 130 as hot-air drying stove.In drying oven 130, pass through
To in electrode slurry 122 and partition with the solvent composition in slurry 124 carry out heating make its evaporation, make electrode slurry
122 and partition it is dry with slurry 124, electrode film and partition are formed in together in metal foil 110.As a result, in metal foil
On 110, it is formed with the electrode slice (positive plate or negative electrode tab) comprising electrode film and partition.That is, if using negative paste
It is capable of forming negative electrode tab, is capable of forming positive plate if using anode slurry.
< film thickness measuring step >
In determination part 145, using micrometer caliper 142, electrode layer and partition comprising transported electrode slice are carried out
The measurement of whole film thickness inside.Later, electrode slice is wound in take-up roll 107.
Later, metal foil 110 can also be made to invert, the back side (face with applicator surface opposite side) of metal foil 110 is set
For upper surface, carrying out same processes, (< is kneaded, allotment the first working procedure of coating of process >, < (electrode material) >, < second is applied
Process (insulating materials) >, < drying process >, < film thickness measuring step >).
According to the manufacturing device of above-mentioned lithium ion battery, electrode film, partition can be set as coated film, it can be by above-mentioned layer
Folded film applies (continuously coating) together.In addition, according to above-mentioned coating machine 121 (such as slit die coating machine), can it is relatively thin and
Positive slurry, negative paste and partition slurry is uniformly coated.In this way, manufacturing device illustrated by present embodiment
Can ideal application in the manufacture for the lithium ion battery for having used partition illustrated by embodiment 1,2.
More than, the invention carried out by the present inventor is specifically illustrated based on the embodiment, but the present invention is not limited to upper
Embodiment, embodiment are stated, it is self-evident for capable of making various changes within the scope of its spirit.
In addition, to be not limited to above-mentioned digital camera, notebook computer, mobile phone etc. portable for above-mentioned lithium ion battery
Formula electronic equipment can also be suitable for battery for electric automobile, electric power storage battery.As such electric car electricity consumption
Pond, electric power storage battery etc. can be realized the large-scale battery of high capacity, high output and high-energy density, above-mentioned lithium ion
Battery is useful.
Description of symbols
101, outlet roller；102, roller；103, roller；104, roller；105, roller；106, roller；107, take-up roll；108, the first coating
Portion；109, the second coated portion；110, metal foil；121, coating machine；122, electrode slurry；123, coating machine；124, partition is used
Slurry；130, drying oven；142, micrometer caliper；145, determination part；CAP, battery cover；CR, central spindle；CS, outer tinning；F, exterior
Film；Na, metal foil (Cu foil)；Nb, negative electrode layer；NE, negative plate；NR, cathode collector ring；NS, negative electrode tab；NTAB, cathode current collection
Piece；NZ1, nozzle；NZ2, nozzle；Pa, metal foil (Al foil)；Pb, anode layer；PE, positive plate；PR, positive pole current collections ring；PS, just
Pole piece；PT, positive wire plate；PTAB, positive pole current collections piece；S, conveying direction；S (Nb), negative paste；S (Pb), positive slurry
Material；SPn, partition；SPp, partition；S (SPn), partition slurry；S (SPp), partition slurry.
Claims (18)
1. a kind of partition powder is the partition powder of lithium ion battery, which is characterized in that
The partition is included with powder
First inorganic oxide particles；
Second inorganic oxide particles, shape are different from first inorganic oxide particles；And
Binder makes the particle in the mixture of first inorganic oxide particles and second inorganic oxide particles
Bonding.
2. partition powder according to claim 1, which is characterized in that
First inorganic oxide particles are spherical silicon dioxides,
Second inorganic oxide particles are unsetting silica.
3. partition powder according to claim 2, which is characterized in that
Relative to the mixed weight of the spherical silicon dioxide and the unsetting silica, the unsetting silica
Ratio is 25 weight % or more, 75 weight % or less.
4. partition powder according to claim 1, which is characterized in that
The partition has dispersant particle with powder.
5. partition powder according to claim 4, which is characterized in that
The dispersant particle is the particle of polyvinyl pyrrole network alkanone.
6. a kind of partition slurry is the partition slurry of lithium ion battery, which is characterized in that
The partition is included with slurry
First inorganic oxide particles；
Second inorganic oxide particles, shape are different from first inorganic oxide particles；
Binder makes the particle in the mixture of first inorganic oxide particles and second inorganic oxide particles
Bonding；And
Solvent dissolves the binder.
7. partition slurry according to claim 6, which is characterized in that
First inorganic oxide particles are spherical silicon dioxides,
Second inorganic oxide particles are unsetting silica.
8. partition slurry according to claim 7, which is characterized in that
Relative to the mixed weight of the spherical silicon dioxide and the unsetting silica, the unsetting silica
Ratio is 25 weight % or more, 75 weight % or less.
9. partition slurry according to claim 8, which is characterized in that
The binder is Vingon,
The solvent is organic solvent.
10. partition slurry according to claim 8, which is characterized in that
The binder is butadiene-styrene rubber,
The solvent is water solvent.
11. a kind of lithium ion battery, which is characterized in that
The lithium ion battery includes
Anode layer includes the positive active material for being occluded and being discharged to lithium ion；
Negative electrode layer includes the negative electrode active material that the lithium ion is occluded and discharged；
Partition, at least one party being laminated in the anode layer and the negative electrode layer；And
Electrolyte can be carried out movement for the lithium ion,
The partition includes
First inorganic oxide particles；
Second inorganic oxide particles, shape are different from first inorganic oxide particles；And
Binder makes the particle in the mixture of first inorganic oxide particles and second inorganic oxide particles
Bonding.
12. lithium ion battery according to claim 11, which is characterized in that
First inorganic oxide particles are spherical silicon dioxides,
Second inorganic oxide particles are unsetting silica.
13. lithium ion battery according to claim 12, which is characterized in that
Relative to the mixed weight of the spherical silicon dioxide and the unsetting silica, the unsetting silica
Ratio is 25 weight % or more, 75 weight % or less.
14. lithium ion battery according to claim 11, which is characterized in that
The partition has dispersant particle.
15. a kind of manufacturing method of lithium ion battery, which is characterized in that
The manufacturing method of the lithium ion battery includes:
(a) on the surface of metal foil coated electrode slurry process；
(b) process of partition slurry is applied on the electrode slurry；
(c) make the electrode slurry and the partition slurry dry and form the work of electrode slice in the metal foil
Sequence, the electrode slice have the electrode layer formed by the electrode slurry and on the electrode layer by the partition
The partition formed with slurry,
The partition used in (b) process is included with slurry
First inorganic oxide particles；
Second inorganic oxide particles, shape are different from first inorganic oxide particles；
Binder makes the particle in the mixture of first inorganic oxide particles and second inorganic oxide particles
Bonding；And
Solvent dissolves the binder.
16. the manufacturing method of lithium ion battery according to claim 15, which is characterized in that
In (b) process, the partition slurry is applied on the not withering electrode slurry.
17. the manufacturing method of lithium ion battery according to claim 15, which is characterized in that
First inorganic oxide particles are spherical silicon dioxides,
Second inorganic oxide particles are unsetting silica.
18. the manufacturing method of lithium ion battery according to claim 17, which is characterized in that
Relative to the mixed weight of the spherical silicon dioxide and the unsetting silica, the unsetting silica
Ratio is 25 weight % or more, 75 weight % or less.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-131043 | 2016-06-30 | ||
| JP2016131043A JP6779052B2 (en) | 2016-06-30 | 2016-06-30 | Separator powder, separator slurry, lithium-ion battery and its manufacturing method |
| PCT/JP2017/020009 WO2018003373A1 (en) | 2016-06-30 | 2017-05-30 | Powder for separators, slurry for separators, lithium ion battery and method for manufacturing same |
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| Publication Number | Publication Date |
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| CN109314208A true CN109314208A (en) | 2019-02-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201780035343.3A Pending CN109314208A (en) | 2016-06-30 | 2017-05-30 | Partition powder, partition slurry, lithium ion battery and its manufacturing method |
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| Country | Link |
|---|---|
| JP (1) | JP6779052B2 (en) |
| CN (1) | CN109314208A (en) |
| WO (1) | WO2018003373A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112151728A (en) * | 2019-06-28 | 2020-12-29 | 比亚迪股份有限公司 | Lithium ion battery composite diaphragm, preparation method thereof and lithium ion battery |
| CN112272893A (en) * | 2019-02-22 | 2021-01-26 | 株式会社Lg化学 | Separator for lithium secondary battery and method for manufacturing the same |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019244401A1 (en) * | 2018-06-19 | 2019-12-26 | 日立オートモティブシステムズ株式会社 | Lithium ion secondary battery and method for producing same |
| KR102421618B1 (en) * | 2019-03-25 | 2022-07-14 | 주식회사 엘지에너지솔루션 | Manufacturing method of separator for electrochemical device |
| KR102524662B1 (en) * | 2019-05-09 | 2023-04-20 | 주식회사 엘지에너지솔루션 | A binder resin composition and a separator for an electrochemical device including the same |
| KR102477643B1 (en) * | 2019-05-09 | 2022-12-13 | 주식회사 엘지에너지솔루션 | A separator for an electrochemical device and an electrochemical device comprising the same |
| JP7370808B2 (en) * | 2019-10-25 | 2023-10-30 | ニチコン株式会社 | Wound type secondary battery and its manufacturing method |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2018003373A1 (en) | 2018-01-04 |
| JP2018006146A (en) | 2018-01-11 |
| JP6779052B2 (en) | 2020-11-04 |
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