CN105190955B - The manufacture method of electrode for nonaqueous electrolyte secondary battery and electrode for nonaqueous electrolyte secondary battery - Google Patents
The manufacture method of electrode for nonaqueous electrolyte secondary battery and electrode for nonaqueous electrolyte secondary battery Download PDFInfo
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- CN105190955B CN105190955B CN201480025451.9A CN201480025451A CN105190955B CN 105190955 B CN105190955 B CN 105190955B CN 201480025451 A CN201480025451 A CN 201480025451A CN 105190955 B CN105190955 B CN 105190955B
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
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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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Abstract
A kind of electrode for nonaqueous electrolyte secondary battery, has：Collector is with metal foil (110), and it possesses the multiple protruding portion (111) prominent at least one side side；Active material layer (120), it is to bury the surface that the collector is formed at the collector metal foil in the way of metal foil, opening portion (112) is formed with the front end of the protuberance, in the active material layer, groove (121) is formed with around the protuberance.
Description
Technical field
The present invention relates to the electrode for nonaqueous electrolyte secondary battery using lithium rechargeable battery as representative and its manufacturer
Method.
Background technology
Now, lithium rechargeable battery be widely used as mobile phone, notebook computer, DV, digital acousticses,
Or electronics, the power supply of electrical equipment such as portable music player.In recent years, the vapour as referred to as economy car is also being promoted
The power of the vehicles such as car (that is, electric automobile (EV), hybrid electric vehicle (HEV), plug-in hybrid vehicle (P-HEV))
The practical application in source.Therewith, the further high capacity of lithium rechargeable battery is not required nothing more than, and because requiring cell resistance
Reduce the raising for the large current density electrical characteristics brought.Required in order to this, Patent Document 1 discloses following lithium ion two
Primary cell, i.e. to form multiple through holes in the collector foil for negative or positive electrode, while making around the through hole to current collection
The mode that at least one side side of paper tinsel is protruded is processed, thereby, it is possible to be carried while the high capacity of lithium rechargeable battery
High large current density electrical characteristics.
In addition, in patent document 1, disclosing following purport, i.e. processed by carrying out three-dimensional shape to collector foil
And prevent that active material layer from peeling off from collector foil, while improving electronics conducting networks by the way that there is hole in collector foil, reduce electricity
Electrode resistance, can carry out high current charge-discharge.In other words, in patent document 1, following technology is disclosed, i.e. by changing
The relation of kind collector foil and active material layer, can carry out high current charge-discharge.
Prior art literature
Patent document
Patent document 1:(Japan) JP 2008-311171 publications
Invent problem to be solved
But, use the situation of lithium rechargeable battery in the power source of the vehicles such as economy car as described above
Under, it is desirable to the further raising of high capacity and large current density electrical characteristics, therefore, only improve current collection as described above
The relation of paper tinsel and active material layer, it is difficult to fully realize the raising of required characteristic.
The content of the invention
The present invention be in view of this problem and develop, its object is to can realize high capacity and big there is provided one kind
The electrode for nonaqueous electrolyte secondary battery of the raising of current charge-discharge electrical characteristics and the system of electrode for nonaqueous electrolyte secondary battery
Make method.
In order to reach above-mentioned purpose, electrode for nonaqueous electrolyte secondary battery of the invention is characterised by having：Current collection
Body metal foil, it possesses the multiple protruding portion prominent at least one side side；Active material layer, it is used with the embedded collector
The mode of metal foil is formed at the surface of the collector metal foil, opening portion is formed in the front end of the protuberance, in institute
Active material layer is stated, groove is formed with around the protuberance.
So, in the electrode for nonaqueous electrolyte secondary battery of the present invention, due to from the surface of active material layer, the back side
The groove extended towards collector with the surface of metal foil is formed at around protuberance, therefore compared with prior art, can be subtracted
The specific insulation of small electrode for nonaqueous electrolyte secondary battery.
If in addition, manufacture using the present invention electrode for nonaqueous electrolyte secondary battery rechargeable nonaqueous electrolytic battery,
Then by forming the groove, it is possible to increase constitute the diffusivity of the electrolyte of rechargeable nonaqueous electrolytic battery, it is ensured that the movement of ion
Path, can realize the reduction of the internal resistance of rechargeable nonaqueous electrolytic battery.
In above-mentioned electrode for nonaqueous electrolyte secondary battery, at least a portion of preferably described groove reaches the current collection
Body metal foil.In addition, in above-mentioned any electrode for nonaqueous electrolyte secondary battery, preferably described protuberance is to the collection
The two sides side of electric body metal foil is protruded.
In these electrode for nonaqueous electrolyte secondary battery, the sheet for bringing the formation of groove can be played more well
The effect of invention.That is, in these electrode for nonaqueous electrolyte secondary battery, rechargeable nonaqueous electrolytic battery electricity consumption can be reduced
The specific insulation of pole and further realization use the rechargeable nonaqueous electrolytic battery of electrode for nonaqueous electrolyte secondary battery
Internal resistance reduction.
In order to reach above-mentioned purpose, its feature of the manufacture method of electrode for nonaqueous electrolyte secondary battery of the invention exists
In having：Paper tinsel manufacturing procedure, forms prominent at least one side side of collector metal foil, and have opening portion in front end
Multiple protruding portion；Working procedure of coating, the mode that the collector is buried with metal foil, in the table of the collector metal foil
Face applies the cream containing active material and solvent, forms active material layer；Dry, groove formation process, makes the solvent seasoning, and
Active material layer formation groove around the protuberance.
So, in the manufacture method of the electrode for nonaqueous electrolyte secondary battery of the present invention, due to the week in protuberance
Enclose to form the groove that surface, the back side from active material layer extend towards the surface of collector metal foil, therefore and prior art
Compare, the specific insulation of electrode for nonaqueous electrolyte secondary battery can be reduced.
If in addition, using non-aqueous manufactured by the manufacture method of the electrode for nonaqueous electrolyte secondary battery by the present invention
Electrolyte secondary battery electrode, manufactures rechargeable nonaqueous electrolytic battery, then by being formed with the groove, it is possible to increase constitute non-aqueous
The diffusivity of the electrolyte of electrolyte secondary battery, it is ensured that the mobile route of ion, can realize rechargeable nonaqueous electrolytic battery
The reduction of internal resistance.
In the manufacture method of above-mentioned electrode for nonaqueous electrolyte secondary battery, preferably in the drying, groove formation work
In sequence, at least a portion of the groove is set to reach the collector metal foil.In this rechargeable nonaqueous electrolytic battery electricity consumption
In the manufacture method of pole, the effect of the invention for bringing the formation of groove can be played more well.That is, in this non-water power
Solve electrolitc secondary cell electrode manufacture method in, can reduce electrode for nonaqueous electrolyte secondary battery specific insulation,
And further realize that the internal resistance of rechargeable nonaqueous electrolytic battery using electrode for nonaqueous electrolyte secondary battery subtracts
It is small.
In addition, in the manufacture method of any of the above-described electrode for nonaqueous electrolyte secondary battery, preferably in the coating work
In sequence, make not formed the thickness of the active material layer in the region of the protuberance, than the area for being formed with the protuberance
The thickness of the active material layer in domain, in the drying, groove formation process, not form the region of the protuberance
In the active material layer for starting point formation groove.By this manufacturing process, (protrusion can not be formed around protuberance
In the region in portion) active material layer, to easily and reliably form groove.
According to the present invention, the nonaqueous electrolyte for the raising that can realize high capacity and large current density electrical characteristics can be provided
The manufacture method of electrode for secondary battery and electrode for nonaqueous electrolyte secondary battery.
Brief description of the drawings
Fig. 1 is the schematic diagram on the surface for the lithium ion secondary battery anode for representing one embodiment of the present invention；
Fig. 2 is the profile of the lithium ion secondary battery anode along Fig. 1 line II-II；
Fig. 3 is the profile of the lithium ion secondary battery anode along Fig. 1 line III-III；
Fig. 4 is the schematic diagram for the variation for representing the lithium ion secondary battery anode of the present invention；
Fig. 5 is the schematic diagram for the variation for representing the lithium ion secondary battery anode of the present invention；
Fig. 6 is to represent] present invention electrode manufacturing process flow chart；
Fig. 7 is the schematic diagram for representing the paper tinsel processing unit (plant) of the present invention；
Fig. 8 is the SEM image on the surface of the lithium ion secondary battery anode of embodiment 2.
Symbol description
100：Lithium ion secondary battery anode (electrode for nonaqueous electrolyte secondary battery)
110：Collector metal foil
111：Protuberance
111a：Face side protuberance
111b：Rear side protuberance
112：Opening portion
120：Active material layer
120a：Face side active material layer
120b：Rear side active material layer
121：Groove
121a：Surface side channel
121b：Back side side channel
200：Paper tinsel processing unit (plant)
202：Paper tinsel conveying roller
203：Model
204：Base station
Embodiment
Hereinafter, referring to the drawings, as the present invention electrode for nonaqueous electrolyte secondary battery optimal embodiment it
One, entered in detail exemplified by being formed with the lithium ion secondary battery anode of active material layer with the two sides of metal foil in collector
Row explanation.In addition, the present invention is not limited to the content of following explanation, can arbitrarily it be changed and real in the scope for not changing its main idea
Apply.In addition, accompanying drawing used in the explanation of embodiment, is all the rechargeable nonaqueous electrolytic battery for schematically showing the present invention
With the figure of electrode, emphasizing, amplify, reduce or omitting for locality is carried out sometimes for sharpening understanding, is not correctly
Represent the figure of the ratio or shape of each composition part etc..In addition, the various numerical value used in embodiment and embodiment, are all represented
One example, can carry out various changes as needed.
(construction of lithium ion secondary battery anode)
First, 1~Fig. 3 of reference picture, to the construction of the lithium ion secondary battery anode 100 of one embodiment of the present invention
Illustrate.Here, Fig. 1 is showing for the surface for the lithium ion secondary battery anode 100 for representing one embodiment of the present invention
It is intended to.In addition, Fig. 2 is the profile of the lithium ion secondary battery anode 100 along the line II-II in Fig. 1, Fig. 3 be along
The profile of the lithium ion secondary battery anode 100 of line III-III in Fig. 1.
From Fig. 1~Fig. 3, collector metal foil is embedded with the inside of lithium ion secondary battery anode 100
110.As collector metal foil 110, for example, it is adapted to use aluminium foil.In addition, it is following, for lithium ion secondary battery anode
The convenience of 100 construction explanation, by one side of the collector in lithium ion secondary battery anode 100 with metal foil 110
Side is expressed as surface, another surface side is expressed as into the back side, but strictly speaking, this it is merely meant that it is upper the problem of, can not also define
Surface, the back side of lithium ion secondary battery anode 100.
In addition, from Fig. 1~Fig. 3, in collector metal foil 110, front end has the multiple protruding portion of opening portion 112
111 are formed as rectangular.Specifically, face side protuberance 111a is formed with the surface of metal foil 110 in collector, in collection
Electric body is formed with rear side protuberance 111b, face side protuberance 111a and rear side protuberance with the back side of metal foil 110
111b is alternately arranged.In addition, protuberance 111 to the collector mode prominent with the two sides of metal foil 110 to form, but not necessarily
It is prominent to two sides, as long as to be formed to the prominent mode of at least one side.In addition, as shown in figure 3, face side protuberance 111a
And rear side protuberance 111b is alternately arranged, but the configuration of protuberance 111 is not limited to this configuration.
In addition, being formed with active material layer 120 with the two sides of metal foil 110 in collector.Specifically, used in collector
The face side of metal foil 110 is formed with face side active material layer 120a, and the back of the body is formed with the back side of metal foil 110 in collector
Surface side active material layer 120b, collector is with metal foil 110 by face side active material layer 120a and rear side active material layer
120b is clamped.In other words, collector metal foil 110 is embedded in active material layer 120.Active material layer 120 for
Suction and the active material for releasing lithium ion are main material, the conductive auxiliary agent of the movement containing auxiliary electron and for making activity
Material and the adhesive of conductive auxiliary agent bonding.As active material, for example, it can use containing lithium metal oxide, phosphorus containing lithium metal
Acid compound or compound containing lithium ion etc..
As shown in Figures 1 and 2, it is formed with groove 121 in active material layer 120.In more detail, in face side active material
Layer 120a, is formed with surface side channel 121a, overleaf side active matter in the way of surrounding face side protuberance 111a around it
Matter layer 120b, is formed with back side side channel 121b in the way of surrounding rear side protuberance 111b around it.Moreover, in visual lithium
When ion secondary battery is with the face side of positive pole 100, face side protuberance 111a is located at what is be made up of four surface side channel 121a
The center in generally square region, in the rear side of visual lithium ion secondary battery anode 100, rear side protuberance
111b is located at by the center in four back side side channel 121b generally square regions constituted.
In addition, in the present embodiment, groove is formed with the way of surrounding is configured at centered on protuberance 111
121, but the forming position of groove 121 is not limited to such position.As long as groove 121 is formed at around protuberance 111, example
, or can also as groove 121 for example can also be as shown in figure 4, be formed as polygon (octagon) shape surrounding protuberance 111
As shown in figure 5, being formed as semicircle shape along a direction of protuberance 111.
In addition, groove 121 is from the respective surface of active material layer 120, (that is, face side active material layer 120a and rear side are lived
Property material layer 120b surface) extend towards collector metal foil 110, reach collector metal foil 110.In addition, groove 121
Width, depth etc. can arbitrarily be selected according to conditions such as the configuration of groove 121 or the species of active material for constituting active material layer 120
Select, but preferably at least one part reaches collector metal foil 110.
(manufacture method of lithium ion secondary battery anode)
Then, reference picture 6 and Fig. 7 are illustrated to the manufacture method of above-mentioned lithium ion secondary battery anode 100.
This, Fig. 6 is the flow chart of the manufacturing process of the lithium ion secondary battery anode 100 of the present invention.In addition, Fig. 7 is to represent this hair
The schematic diagram of paper tinsel processing unit (plant) 200 used in the manufacture of bright lithium ion secondary battery anode 100.
First, in paper tinsel manufacturing procedure, being formed with multiple front ends in collector metal foil 110 has opening portion 112
(the Fig. 6 of protuberance 111：Step S1).For example, as shown in fig. 7, the collector gold that will be conveyed by paper tinsel conveying roller 202 to L directions
Belong to paper tinsel 110 and be arranged on base station 204, and be formed rectangular multiple small convex portions (for example, its be shaped as coniform)
Model 203 is clamped.More specifically, by making base station 204 be lifted along M directions desired at the time of, configuration up and down is passed through
Model 203 clamps collector metal foil 110.Here, the convex portion of the model 203 configured up and down is not contacted each other, the convex portion that
This is located at the position intermeshed at grade.Thus, it is possible in collector with metal foil 110, while before will be multiple
Protuberance 111 of the end with opening portion 112 forms rectangular.
In addition, so-called punching processing as described above is only an example of paper tinsel processing method, it can also replace with logical
Crossing makes paper tinsel be formed with surface between a pair of rolls of multiple small convex portions by and forming front end has the protuberance of opening portion 112
111, the other method such as so-called roller punch process.
Then, in working procedure of coating, the collector after the processing of paper tinsel manufacturing procedure applies activity with the two sides of metal foil 110
Material layer formation cream, forms (the Fig. 6 of active material layer 120：Step S2).Here, active material layer formation is by activity with cream
The cream that material, conductive auxiliary agent and adhesive are mixed in appropriate solvent (water solvent or non-water solvent).As
The method that collector applies active material layer formation cream with the two sides of metal foil 110, can suitably be used and existing known
The same technological means of method.For example, suitable using flat painting machine, metal mold coating machine, gravure coater, comma coater etc.
When applying device method.
In addition, in drying, groove formation process in subsequent processing, in order to efficiently form groove (i.e. it is easy to and reliably)
121, preferably active material formation produces the part applied thicker with metal foil 110 relative to collector with cream and applied compared with unfertile land
Deposited part.Specifically, in working procedure of coating, preferably make not formed active material layer 120 in the region of protuberance 111
Thickness, than the thickness for the active material layer 120 being formed with the region of protuberance 111.
Then, in drying, groove formation process, the current collection of active material layer formation cream is coated with from working procedure of coating
Body metal foil 110 makes solvent seasoning, also, the work around the protuberance 111 being formed in collector metal foil 110
Property the formation of material layer 120 groove 121 (Fig. 6：Step S3).As making the method for solvent seasoning, it is considered to be used alone spontaneously dry, heat
The existing known method such as wind, low warm wind, vacuum, infrared ray, far infrared and electric wire is applied in combination they are multiple
Method, can be suitably using the conduct different with internal drying progress of active material layer formation cream surface in order to form groove 121
The method of condition.Here, why selecting the active material layer formation cream surface condition different with internal drying progress, examine
Worry is to form groove with the stress produced inside cream using active material layer formation.In more detail, by limiting to collection
The active material layer formation cream that electric body is applied with metal foil 110 (is received to the Volume Changes of thickness direction caused by drying
Contracting), active material layer formation is easily produced the Volume Changes to in-plane with cream, simultaneously as in protuberance 111
Front end is formed with opening portion 112, so that inside active material layer formation cream, the stress that Volume Changes are produced is uniform, or
Do not produce irregular, but centered on opening portion 112 (anchoring effect of opening portion 112), forcefully produce relative to opening
The tensile stress in the direction of oral area 112.As a result, be not the active material layer 120 near protuberance 111, but prominent
The active material layer 120 gone out around portion 111 regularly forms groove 121.And then, in the working procedure of coating of preceding process, due to phase
Produced for collector metal foil 110 and be coated with active material layer formation thicker and be coated with work with the part of cream and compared with unfertile land
The part of property material layer formation cream, therefore, it is possible to using the part applied compared with unfertile land as starting point, more effectively form groove.
In addition, in above-mentioned working procedure of coating and drying, groove formation process, after applying cream simultaneously on paper tinsel two sides, carrying out molten
The drying of agent and to active material layer formation groove, but it is also possible to after the one side coating cream of paper tinsel, carry out the drying of solvent and to work
Property material layer formation groove, then same process is carried out to another side.Additionally, it is preferred that continuously carrying out paper tinsel manufacturing procedure, coating work
Sequence and drying, groove formation process.
Then, stamping procedure (Fig. 6 is carried out：Step S4).In stamping procedure, by drying, groove formation process, solvent is done
It is dry, the space produced between active material, conductive auxiliary agent and adhesive is reduced, therefore, pressurization compression is carried out, forms active matter
Matter layer 120., can be using skill and technique such as existing known roller pressing, flat board pressings as the method for pressurization compression.
By the process of step S1~step S4 as previously discussed, the lithium ion two of one embodiment of the present invention is completed
Primary cell positive pole 100.
(effect of electrode for nonaqueous electrolyte secondary battery)
Hereinafter, by embodiments of the invention and comparative example (existing electrode for nonaqueous electrolyte secondary battery), to this hair
The effect of bright electrode for nonaqueous electrolyte secondary battery is illustrated.
(embodiment 1)
As the lithium ion secondary battery anode of embodiments of the invention, first, the phosphorus of positive active material will be used as
Sour iron lithium (LFP), conductive auxiliary agent and adhesive are blended in solvent, and active material formation cream is made.Afterwards, in 20 μm of thickness
The two sides processing front end of aluminium foil has after the protuberance of opening portion, and above-mentioned active material formation is applied on the two sides of the aluminium foil and is used
Cream, so that one side reaches 140g/m2Coating amount.And then, by making solvent seasoning, the protuberance formed on the aluminium foil
Around active material layer on form groove.Then, the part progress punching press of above-mentioned coating, drying, groove formation will be completed, is improved
After the density of active material layer, 50mm × 50mm square shape is cut to, lithium ion secondary battery anode is made.
(comparative example 1)
It is different from the lithium ion secondary battery anode of embodiment as comparative example 1, it is produced on the table of active material layer
Face, the back side do not form the structure of groove.Therefore, as the preparation method of comparative example 1, in the way of not forming groove in active material layer
Make solvent seasoning, other processes are used and the same preparation method of above-described embodiment.In addition, the viewpoint from the generation for preventing groove goes out
Hair, active material formation reduces the part that collector is applied thicker with metal foil relatively with cream and compared with unfertile land coating as far as possible
Partial film thickness difference.That is, in collector metal foil, be adjusted to the coating amount of active material formation cream tends to one as far as possible
Cause.
(comparative example 2)
Different from the lithium ion secondary battery anode of embodiment as comparative example 2, generation has flat aluminium foil conduct
Collector does not form with metal foil and the structure of groove at the surface of active material layer, the back side.That is, the lithium ion secondary of comparative example 2
The collector metal foil of positive electrode for battery is different from the aluminium foil of the lithium ion secondary battery anode of embodiment, does not form protrusion
Portion.Therefore, as the preparation method of comparative example 2, using the flat aluminium foil for not implementing paper tinsel manufacturing procedure, and with active material
The mode that layer does not form groove makes solvent seasoning, and other processes are just acted on and the same preparation method of above-described embodiment.In addition, than
In lithium ion secondary battery anode compared with example 2, due to be with the aluminium foil of metal foil as collector it is flat, therefore, as long as
It is formed flatly the active material formation cream at the surface for being coated on aluminium foil, the back side, you can form the active material on aluminium foil
It is consistent with the coating amount of cream, in the drying process after, groove is not formed in active material.
(measurement 1 of specific insulation)
As the evaluation of embodiment, comparative example 1 and comparative example 2, to what is obtained in embodiment, comparative example 1 and comparative example 2
Lithium ion secondary battery anode, uses low-resistivity tester (Mitsubishi Chemical ア Na リ テ ッ Network society system, ProductName：ロレス
タ ー GP, model：MCP-T610 the measurement of respective specific insulation) is carried out.Following table 1 represents its result.
[table 1]
Table 1：The difference and evaluation result of embodiment, comparative example 1 and comparative example 2
| Processing to aluminium foil | The formation of the groove of active material layer | Specific insulation (Ω cm) | |
| Embodiment 1 | Have | Have | 144.48 |
| Comparative example 1 | Have | Nothing | 329.84 |
| Comparative example 2 | Nothing | Nothing | 253.73 |
As shown in table 1, the specific insulation of the lithium ion secondary battery anode of embodiment 1, is the lithium ion of comparative example 1
About the 44% of the specific insulation of anode of secondary cell, is the volume resistance of the lithium ion secondary battery anode of comparative example 2
About the 57% of rate.That is, the specific insulation of the lithium ion secondary battery anode of embodiment 1 is used with existing lithium rechargeable battery
Positive pole compares, and is about 1/2, distinguishes it is the low electrode of the existing electrode of resistance ratio.
(embodiment 2)
LiFePO4 (LFP), conductive auxiliary agent and adhesive are mixed in a solvent with the ratio of components different from embodiment 1,
Make active material formation cream.Afterwards, by making lithium ion secondary battery anode with the same process of embodiment 1
(50mm × 50mm square shape).
The surface of the lithium ion secondary battery anode made in embodiment 2 is observed with scanning electron microscope (SEM)
Figure be Fig. 8 (A), (B).Particularly Fig. 8 (A) represents that coating, dry, groove form the state of rear (before punching press), and Fig. 8 (B) is represented
State after punching press.Such as Fig. 8 (A), shown in (B), it is understood that in the state of before stamping and after punching press, all regular landform
Into there is groove.
(comparative example 3)
As comparative example 3, made cream in addition, passes through as active material formation cream using in embodiment 2
The same process with comparative example 1, is produced on the lithium ion secondary battery anode that the surface of active material layer, the back side do not form groove
(50mm × 50mm square shape).
(comparative example 4)
As comparative example 4, made cream in addition, passes through as active material formation cream using in embodiment 2
The same process with comparative example 2, making has flat aluminium foil as collector with metal foil and in the table of active material layer
Face, the back side do not form the lithium ion secondary battery anode (50mm × 50mm square shape) of groove.
(measurement 2 of specific insulation)
Similarly enter as the evaluation of embodiment 2, comparative example 3 and comparative example 4, and embodiment 1, comparative example 1 and comparative example 2
The measurement of the respective specific insulation of row.Its result is represented in following table 2.
[table 2]
Table 2：The difference and evaluation result of embodiment 2, comparative example 3 and comparative example 4
| Processing to aluminium foil | The formation of the groove of active material layer | Specific insulation (Ω cm) | |
| Embodiment 2 | Have | Have | 12.98 |
| Comparative example 3 | Have | Nothing | 80.65 |
| Comparative example 4 | Nothing | Nothing | 24.65 |
As shown in table 2, the specific insulation of the lithium ion secondary battery anode of embodiment 2, is the lithium ion of comparative example 3
About the 16% of the specific insulation of anode of secondary cell, is the volume resistance of the lithium ion secondary battery anode of comparative example 4
About the 52% of rate.That is, the specific insulation of the lithium ion secondary battery anode of the present embodiment 2 and existing lithium rechargeable battery
Compared with positive pole, be about less than 1/2, distinguish it is the low electrode of the existing electrode of resistance ratio.
In addition, the value shown in value and table 2 shown in table 1 be the reason for differing 1 digit because, active material formation cream
Ratio of components is different, i.e. with cream, the volume intrinsic resistance rate of itself is different for active material formation.
(embodiment 3)
With with embodiment 1 and the different ratio of components of embodiment 2 by LiFePO4 (LFP), conductive auxiliary agent and adhesive molten
Mixed in agent, make active material formation cream.Afterwards, it is one side 120g/m with the coating amount of cream to make active material formation2, remove
Beyond this, by with the same process of embodiment 1 and embodiment 2 make lithium ion secondary battery anode (50mm × 50mm's
Square shape).
(comparative example 5)
As comparative example 5, using in embodiment 3 made cream as active material formation cream, make active material shape
Into being one side 120g/m with the coating amount of cream2, in addition, by with comparative example 2 and the same process of comparative example 4, make tool
There is flat aluminium foil as collector with metal foil and do not form the lithium ion secondary of groove at the surface of active material layer, the back side
Positive electrode for battery (50mm × 50mm square shape).
(measurement 3 and the measurement of reaction resistance of specific insulation)
As the evaluation of embodiment 3 and comparative example 5, and embodiment 1 and embodiment 2 and 1~comparative example of comparative example 4 it is same
Ground carries out the measurement of respective specific insulation.In addition, also carrying out the measurement of reaction resistance using AC impedence method.Following table
Its result is represented in 3.
[table 3]
Table 3：The difference and evaluation result of embodiment 3 and comparative example 5
As shown in table 3, the specific insulation of the lithium ion secondary battery anode of embodiment 3, is the lithium ion of comparative example 5
About the 87% of the specific insulation of anode of secondary cell, in addition, the reaction electricity of the lithium ion secondary battery anode of embodiment 3
About the 63% of the reaction resistance of lithium ion secondary battery anode for comparative example 5 is hindered, no matter which key element, with existing lithium ion
Anode of secondary cell more shows low value, therefore, and the lithium ion secondary battery anode of embodiment 3 is existing for resistance ratio
The low electrode of electrode, in addition, distinguishing the electrode of the reduction for the internal resistance that can further realize lithium rechargeable battery.
The reasons why as the above results are obtained, it is contemplated that the groove formed on active material layer has an impact.In more detail,
Think in active material layer, produce (the density change of active material that the active material of the part of formed groove becomes closeer
Get Geng Gao) part, closeer part is become in active material, and electronics is easily moved, it is contemplated that, as a result, lithium ion secondary is electric
The specific insulation step-down of pond positive pole.
So, if made using resistance for the lithium ion secondary battery anode of about 1/2 embodiment of existing product
Make lithium rechargeable battery, then can provide can fully realize high capacity, improve large current density electrical characteristics lithium from
Sub- secondary cell.
In addition, by forming groove as described above in active material layer, adding the electrolysis for constituting lithium rechargeable battery
The contact area of liquid and active material layer, shortens the distance of the electrolyte and collector metal foil, so as to improve this
The diffusivity of electrolyte.Thus, the diffusivity for constituting the electrolyte of lithium rechargeable battery is improved, it is ensured that the mobile road of ion
Footpath, can realize the reduction of the internal resistance of lithium rechargeable battery.
In addition, in the lithium ion secondary battery anode 100 of above-mentioned embodiment and embodiment, at least one of groove 121
Part reaches collector metal foil 110.In addition, protuberance 111 is prominent with the two sides side of metal foil 110 to collector.According to
The composition of this groove 121, can reduce the specific insulation of lithium ion secondary battery anode 100, and can further realize
Use the reduction of the internal resistance of the lithium rechargeable battery of lithium ion secondary battery anode 100.
In addition, in above-mentioned embodiment and embodiment, as the electrode of rechargeable nonaqueous electrolytic battery, with just extremely
One example is illustrated, but for negative pole, can also be set as same composition.In this case, structure sometimes
It is also different from positive pole into the active material layer of negative pole and the material of collector metal foil, but the effect with positive pole equally can be obtained
Really.
Industrial applicability
The electrode particularly internal resistance of the present invention is relatively low, therefore, it can be suitably applied to such as economy car
Power source etc. needs the secondary cell of high current charge-discharge.
Claims (7)
1. a kind of electrode for nonaqueous electrolyte secondary battery, it is characterised in that have：
Collector metal foil, it possesses the multiple protruding portion prominent at least one side side；
Active material layer, it is to bury the table that the collector is formed at the collector metal foil in the way of metal foil
Face,
Opening portion is formed in the front end of the protuberance,
In the active material layer, the groove formation produced using the stress produced in the active material layer is in the protuberance
Around.
2. electrode for nonaqueous electrolyte secondary battery as claimed in claim 1, it is characterised in that at least a portion of the groove
Reach the collector metal foil.
3. electrode for nonaqueous electrolyte secondary battery as claimed in claim 1 or 2, it is characterised in that the groove is each to surround
The mode of the individual protuberance is formed.
4. electrode for nonaqueous electrolyte secondary battery as claimed in claim 1 or 2, it is characterised in that the protuberance is to institute
The two sides side for stating collector metal foil is protruded.
5. a kind of manufacture method of electrode for nonaqueous electrolyte secondary battery, it is characterised in that have：
Paper tinsel manufacturing procedure, forms prominent at least one side side of collector metal foil, and has in front end the multiple of opening portion
Protuberance；
Working procedure of coating, the mode that the collector is buried with metal foil is applied on the surface of the collector metal foil
Cream containing active material and solvent, forms active material layer；
Dry, groove formation process, makes the solvent seasoning, stress is produced in the active material layer, so that in the protrusion
Active material layer formation groove around portion.
6. the manufacture method of electrode for nonaqueous electrolyte secondary battery as claimed in claim 5, it is characterised in that described dry
In dry, groove formation process, at least a portion of the groove is set to reach the collector metal foil.
7. the manufacture method of the electrode for nonaqueous electrolyte secondary battery as described in claim 5 or 6, it is characterised in that
In the working procedure of coating, make not formed the thickness of the active material layer in the region of the protuberance, than being formed
There is the thickness of the active material layer in the region of the protuberance,
In the drying, groove formation process, the active material layer in region not form the protuberance is starting point
Form groove.
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| JP2013-115156 | 2013-05-31 | ||
| JP2013115156 | 2013-05-31 | ||
| PCT/JP2014/063608 WO2014192637A1 (en) | 2013-05-31 | 2014-05-22 | Electrode for non-aqueous electrolyte secondary battery, and manufacturing method of electrode for non-aqueous electrolyte secondary battery |
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| CN105190955B true CN105190955B (en) | 2017-09-26 |
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| KR (1) | KR102212144B1 (en) |
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| JP6819531B2 (en) | 2017-09-28 | 2021-01-27 | トヨタ自動車株式会社 | Metal film forming method and metal film forming device |
| CN114430026A (en) * | 2022-03-08 | 2022-05-03 | 国网浙江省电力有限公司电力科学研究院 | Electrode, alkaline storage battery using same and preparation method of electrode |
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| JPH09161785A (en) * | 1995-12-13 | 1997-06-20 | Matsushita Electric Ind Co Ltd | Electrode for storage battery |
| JP2003017040A (en) * | 2001-06-28 | 2003-01-17 | Sanyo Electric Co Ltd | Electrode for lithium secondary battery, and manufacturing method thereof |
| CN102598368A (en) * | 2009-10-23 | 2012-07-18 | Sei株式会社 | Methods for manufacturing lithium secondary battery and current-collecting foil for lithium secondary battery, and current-collecting foil for lithium secondary battery |
| CN103022504A (en) * | 2012-12-21 | 2013-04-03 | 中银（宁波）电池有限公司 | Current collector for battery |
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| JP3016769B1 (en) * | 1998-12-02 | 2000-03-06 | 片山特殊工業株式会社 | Method of manufacturing electrode plate for battery, electrode plate manufactured by the method, and battery provided with the electrode plate |
| JP4475722B2 (en) * | 2000-02-21 | 2010-06-09 | 古河電池株式会社 | ELECTRODE FOR LITHIUM BATTERY, METHOD FOR PRODUCING THE SAME, AND BATTERY USING THE SAME |
| JP4774232B2 (en) * | 2005-04-13 | 2011-09-14 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery electrode and method for producing the same |
| KR100901048B1 (en) * | 2005-12-28 | 2009-06-04 | 파나소닉 주식회사 | Nonaqueous electrolyte secondary battery |
| CN101099251A (en) * | 2005-12-28 | 2008-01-02 | 松下电器产业株式会社 | Nonaqueous electrolyte secondary battery |
| JP2008277242A (en) * | 2007-03-30 | 2008-11-13 | Sanyo Electric Co Ltd | Electrode for lithium secondary battery and lithium secondary battery |
| JP5224020B2 (en) | 2007-06-18 | 2013-07-03 | エス・イー・アイ株式会社 | Lithium secondary battery |
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- 2014-05-22 WO PCT/JP2014/063608 patent/WO2014192637A1/en active Application Filing
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Patent Citations (4)
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| JPH09161785A (en) * | 1995-12-13 | 1997-06-20 | Matsushita Electric Ind Co Ltd | Electrode for storage battery |
| JP2003017040A (en) * | 2001-06-28 | 2003-01-17 | Sanyo Electric Co Ltd | Electrode for lithium secondary battery, and manufacturing method thereof |
| CN102598368A (en) * | 2009-10-23 | 2012-07-18 | Sei株式会社 | Methods for manufacturing lithium secondary battery and current-collecting foil for lithium secondary battery, and current-collecting foil for lithium secondary battery |
| CN103022504A (en) * | 2012-12-21 | 2013-04-03 | 中银（宁波）电池有限公司 | Current collector for battery |
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| KR102212144B1 (en) | 2021-02-04 |
| CN105190955A (en) | 2015-12-23 |
| TW201511394A (en) | 2015-03-16 |
| TWI622209B (en) | 2018-04-21 |
| WO2014192637A1 (en) | 2014-12-04 |
| JPWO2014192637A1 (en) | 2017-02-23 |
| KR20160014621A (en) | 2016-02-11 |
| JP6393681B2 (en) | 2018-09-19 |
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