CN108365170A - Lithium ion secondary battery cathode and lithium rechargeable battery - Google Patents
Lithium ion secondary battery cathode and lithium rechargeable battery Download PDFInfo
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- CN108365170A CN108365170A CN201810067791.8A CN201810067791A CN108365170A CN 108365170 A CN108365170 A CN 108365170A CN 201810067791 A CN201810067791 A CN 201810067791A CN 108365170 A CN108365170 A CN 108365170A
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- anode member
- overlay film
- lithium ion
- ion secondary
- secondary battery
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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
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or 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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- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
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Abstract
The present invention provides lithium ion secondary battery cathode and lithium rechargeable battery, can inhibit charge and discharge cycles the reduction of performance and can ensure required energy capacity.Lithium ion secondary battery cathode (1) has the first anode member (2) and the second anode member (3), the first anode member (2) have tabular current-collector (21) and cover its surface and thickness be 100~1200nm ranges the first tin overlay film (22)；Second anode member (3) have conductive mesh current collector (32) and cover its mesh current collector (32) surface and thickness be 100~1200nm ranges the second tin overlay film (33), which has the space (34) that is surrounded by the second tin overlay film (33).It is laminated with the second anode member of at least one (3) on first tin overlay film (22).
Description
Technical field
The present invention relates to lithium ion secondary battery cathodes and lithium rechargeable battery.
Background technology
In the past, as the secondary cell used in the power supply of mancarried electronic aid etc., there is known lithium rechargeable batteries.
Existing research is more than carbon material in the negative electrode active material of the lithium rechargeable battery using theoretical capacity
Tin, for example, as it is known that by the surface of current-collector formed 10~300 μ m thicks tin overlay film obtained from substance for the lithium from
The cathode of sub- secondary cell (referring for example to patent document 1).
It can be from however, volume expansion of the tin overlay film when receiving lithium ion is very big, when being repeated discharge and recharge reaction
The sur-face peeling of the current-collector, thus the problem of reduced there are the charge-discharge performance of the lithium rechargeable battery.
Therefore, in order to solve described problem, it is known that it is a kind of using the staggered net formed by fine copper wire as current-collector and to the current-collector
Implement it is tin plating obtained from lithium ion secondary battery cathode (referring for example to patent document 2).
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2001-68094 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2008-91035 bulletins
Invention content
The subject that the invention solves
However, even if using the staggered net formed by fine copper wire as current-collector, due to the tin overlay film receive lithium from
The large volume of the period of the day from 11 p.m. to 1 a.m expands, and is also phase in terms of the sur-face peeling of the current-collector when discharge and recharge reaction is repeated
With, thus be desirable to be improved.
The present invention is in view of the situation, it is therefore intended that, even if providing one kind when discharge and recharge reaction is repeated in current collection
The tin overlay film formed on the surface of device is not also removed and can inhibit charge and discharge cycles the reduction of performance and can ensure required energy
Measure the lithium ion secondary battery cathode of capacity.
In addition, the present invention also aims to provide the lithium ion secondary for having the lithium ion secondary battery cathode
Battery.
The means used to solve the problem
In order to realize the purpose, lithium ion secondary battery cathode of the invention is characterized in that having：
First anode member, the thickness for having tabular current-collector and covering the surface of the tabular current-collector is 100
First tin overlay film of~1200nm ranges；With
Second anode member, has：Conductive mesh current collector and the surface that covers the mesh current collector
Thickness is the second tin overlay film of 100~1200nm ranges, which has the space surrounded by the second tin overlay film；
At least one second anode member is laminated on first tin overlay film of first anode member.
In the lithium ion secondary battery cathode of the present invention, first anode member has tabular current-collector and covers
Cover the first tin overlay film on the surface of the tabular current-collector.Here, thickness of the first tin film-coating tool for 100~1200nm ranges
Degree, therefore, can inhibit volume expansion when receiving lithium ion, when charge and discharge being repeated in lithium ion battery, also can
It prevents from removing to inhibit charge and discharge cycles the reduction of performance from the current-collector.
When the thickness of the first tin overlay film is less than 100nm, as negative electrode active material, the effect of lithium ion is received to become
It is small, and when the thickness of the first tin overlay film is more than 1200nm, then it can not inhibit volume expansion when receiving lithium ion.
On the other hand, lithium ion secondary battery cathode of the invention is only by having the first tin of the thickness of the range
Overlay film, it is difficult to ensure required energy capacity.Therefore, lithium ion secondary battery cathode of the invention is in first cathode portion
It is laminated with the second anode member described at least one on first tin overlay film of part.
Second anode member has：Conductive mesh current collector and the surface for covering the mesh current collector
Thickness be 100~1200nm ranges the second tin overlay film.In addition, second anode member is covered by the second tin overlay film
The surface for covering the mesh current collector, to have the space surrounded by the second tin overlay film.
As a result, when being laminated with second anode member on the first tin overlay film of first anode member, in lithium
In ion battery, electrolyte is full of the space surrounded by the second tin overlay film.Therefore, the first tin overlay film and described second
Both tin overlay films can well be contacted by the electrolyte with lithium ion, it can be ensured that required energy capacity.
In the lithium ion secondary battery cathode of the present invention, as long as being at least laminated 1 on first anode member
Second anode member can adjust the energy capacity of the lithium ion secondary battery cathode according to its quantity.
It should be noted that the reasons why thickness of the second tin overlay film is set as the range of 100~1200nm with it is described
The case where first tin overlay film, is identical.
In the lithium ion secondary battery cathode of the present invention, the first tin overlay film and the second tin overlay film can pass through no electricity
Solution plating is formed, but is preferably formed by being electroplated.By using plating, tin overlay film is good to the adaptation of current-collector, can be easy and
Inexpensively form the tin overlay film of large area.
In addition, the lithium rechargeable battery of the present invention can have：The lithium ion secondary battery cathode, with described the
The anode and electrolyte that two anode members configure in opposite directions.
Description of the drawings
Fig. 1 is the schematic sectional view for a configuration example for showing the lithium ion secondary battery cathode of the present invention.
Fig. 2 is the plan view of the second anode member shown in Fig. 1.
Fig. 3 is the schematic sectional view for a configuration example for showing the lithium rechargeable battery of the present invention.
Fig. 4 is the relationship shown between the thickness and charge-discharge performance of the first tin overlay film in the first anode member
Figure.
Fig. 5 is the plan view that the key position for the metal otter board for showing to use in mesh current collector is constituted.
Fig. 6 is the assembling figure for another configuration example for showing the lithium rechargeable battery of the present invention.
Fig. 7 is the figure for the charge-discharge performance for showing the lithium rechargeable battery of the present invention.
Symbol description
1 lithium ion secondary battery cathode
2 first anode members
3 second anode members
4,16 lithium rechargeable battery
21 tabular current-collectors
22 first tin overlay films
31 filaments
32,34 mesh current collector
33 second tin overlay films.
Specific implementation mode
Then, with reference to attached drawing, further detailed description of embodiments of the present invention.
As shown in Figure 1, the lithium ion secondary battery cathode 1 of present embodiment has the first anode member 2 and
Two anode members 3.First anode member 2 has tabular current-collector 21 and covers at least one table of tabular current-collector 21
The first tin overlay film 22 in face.In addition, the second anode member 3 is laminated on the first tin overlay film 22, have：It is conductive by thin
The second tin overlay film 33 on the surface of mesh current collector 32 and covering filament 31 that line 31 is formed.
As long as the conductive material of tabular current-collector 21, there is no particular limitation, can use for example
By the tabular current-collector of the formation such as aluminium, copper, steel, titanium.In addition, the material as tabular current-collector 21, can also use tin.
At this point, tabular current-collector 21 doubles as the first tin overlay film 22.The thickness of tabular current-collector 21 is close for the energy for improving battery
Degree and be preferred with thin, but if excessively thin, then be difficult to handle, productivity reduces, therefore preferably 5~50 μm of range.In addition, flat
Plate current-collector 21 can cut surface or dissolve to form bumps.
First tin overlay film 22 has the thickness of 100~1200nm ranges.First tin overlay film 22 can be by plating or without electricity
Solution plating is formed, since the adaptation to tabular current-collector 21 is good, can easily and inexpensively form the overlay film of large area, thus
It is preferred that being formed by being electroplated.
When forming the first tin overlay film 22 by plating, it can be carried out by following manner：Tabular current-collector 21 is impregnated
In the acid such as nitric acid, hydrochloric acid, sulfuric acid or after washing is to remove the dirt on surface, aoxidize overlay film etc., it is impregnated in sulfuric acid etc.
In plating bath dissolved with pink salts such as stannic chlorides in acid, it is powered at an established temperature.At this point, in order to form first evenly
Tin overlay film 22 can dissolve Beta Naphthol 99MIN, gelatin, cresol sulfonic acid in right amount.The plating bath can be for replacement sulfur acid and in sodium hydroxide
Plating bath dissolved with pink salts such as stannic chlorides in equal aqueous slkalis.The thickness of first tin overlay film 22 can be by conduction time come pipe
Reason.
As long as the filament 31 for forming mesh current collector 32 is conductive material, there is no particular limitation, can
To use such as the line of the formation by aluminium, copper, steel, titanium.In addition, the material as filament 31, can also use tin.At this point, thin
Line 31 doubles as the second tin overlay film 33.The material of filament 31 can be identical as tabular current-collector 21, can also be different.
In order to improve the energy density of battery, the thickness of mesh current collector 32 is preferred with thin, but if excessively thin, then is difficult to locate
Reason, productivity reduces, therefore the thickness of preferably 3~500 μ ms.
Second tin overlay film 33 has the thickness of 100~1200nm ranges, can pass through side identical with the first tin overlay film 22
Method is formed.At this point, as shown in Figure 2, the second tin overlay film 33 is formed in the surface of filament 31, therefore the second anode member 3 has
The standby space 34 surrounded by the second tin overlay film 33.
It should be noted that in the second anode member 3, mesh current collector 32 can be made of 31 track and column braiding of filament
Object, or on the foil formed by conductive material as punch metal, be formed uniformly the object in hole.
In addition, mesh current collector 32 can be to be cut with the introducing of stagger arrangement shape on the tablet that metallic plate etc. is formed by conductive material
Mouth is simultaneously expanded to be shaped to the metal otter board of diamond shape, tortoise-shell shaped.In the case of net staggered obtained from woven wire,
In bending or stretching, gap between filament is opened or is closed, and because of the interval of this gap and non-constant, is manufacturing the second cathode
It can be deformed applying minimum power when component 3, it is difficult to manufacture the second anode member 3.On the other hand, it is obtained with woven wire
To staggered net compare, punch metal, metal otter board bending when, due to a degree of hardness, shape
It is easy to be fixed, stretch relative to a degree of, gap will not open or close.Therefore, such as cylinder battery unit, winding
In the such battery unit that the second anode member 3 bends in battery unit of type, interlock with obtained from woven wire
The net of shape is compared, more preferably punch metal, metal otter board.In addition, punch metal, metal otter board can also be bent, therefore also
It can be applied to the battery of flexible shape.
Made of mesh current collector 32 is 31 track and column braiding of filament when object, the interval (sieve pore) of filament 31 reaches for example
1~50 μm of range.In addition, when mesh current collector 32 is formed by metal otter board, for example, reach line width be 0.001~10mm,
The range that opening short side dimension is 0.01~10mm, opening long edge size is 0.05~50mm.
For the diameter in the space 34 in the second anode member 3, electrolyte when stating lithium rechargeable battery 4 after its formation
It is easy infiltration and does not lead to the increased mode of resistance, it is excellent when mesh current collector 32 is object made of 31 track and column braiding of filament
It is selected as 0.001~48 μm of range, further preferably 1~40 μm of range.In addition, being by metal mesh in mesh current collector 32
When plate formation, the diameter in the space 34 in the second anode member 3 is preferably the range of 0.001 μm~10mm, further preferably 1
~500 μm of range.In addition, when mesh current collector 32 is formed or formed by metal otter board by 31 track and column braiding of filament,
The voidage of second anode member 3 is both preferably 1% or more.
In present embodiment, as the example of lithium ion secondary battery cathode 1, show on the first anode member 2
It is laminated with 1 the second anode member 3.But as long as lithium ion secondary battery cathode 1 is laminated on the first anode member 2
Multiple second anode members 3 can be further laminated in the second anode member of at least one 3.The quantity of second anode member 3
There is no particular limitation, in order to make manufacture be easy, preferably 1~5 range.
In addition, the first anode member 2 is conductive, the function as current-collector is also played, therefore can be negative first
Between pole component 2 and the second anode member 3, the mixture layer for including negative electrode active material is arranged.As the negative electrode active material
Matter, it can be cited for example that artificial graphite, natural graphite, hard carbon, soft carbon, silicon, silica, tin, silver, aluminium, zinc, lead, germanium, lithium etc.,
Or their alloy.The mixture layer comprising negative electrode active material can add bonding into the negative electrode active material
Agent, conductive auxiliary agent etc. can also will be born to make slurry and the slurry is coated on the first anode member 2 by described
The foil that pole active material is formed is configured on the first anode member 2.Thereafter, the second cathode portion is configured on said mixture layer
Part 3.
The lithium rechargeable battery 4 that the lithium ion secondary battery cathode 1 of present embodiment can for example be shown in FIG. 3
Middle use.
Lithium rechargeable battery 4 is in the inside of battery unit 5 by configuring lithium ion secondary battery cathode 1, being impregnated with
The isolation film 6 of electrolyte and anode 7 and constitute.In lithium rechargeable battery 4, lithium ion secondary battery cathode 1 is negative with second
Pole component 2 is configured across isolation film 6 with positive 7 opposite modes.Anode 7 has anode current collector 71 and positive-electrode mixture layer
72, it is configured in such a way that positive-electrode mixture layer 72 and isolation film 6 are opposite.In addition, the tabular of lithium ion secondary battery cathode 1
Current-collector 21 and mesh current collector 32 are connect with negative wire 8, and the anode current collector 71 of anode 7 is connect with positive wire 9.
In lithium rechargeable battery 4, as isolation film 6, it can use such as made of the synthetic resin polyethylene
Isolation film.In addition, as the electrolyte infiltrated in isolation film 6, can use using phosphate shown in the following general formula (1) as
Solvent and in the solvent dissolved with lithium salts as support salt obtained from electrolyte.
In general formula (1), R1、R2、R3For the straight-chains such as alkyl, alkenyl, alkynyl alkyl, or part thereof hydrogen replaced by fluorine and obtain
The group arrived, each other can it is identical, can also be different.In addition, if the straight-chain alkyl carbon atom number increases, viscosity becomes
It obtains excessively high, it is difficult to handle, therefore preferably carbon atom number is 7 hereinafter, further preferably carbon atom number is 3 or less.
As the phosphate, have appropriate viscosity and to the high-dissolvability as the lithium salts for supporting salt in terms of, it is excellent
It is selected as such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate (trifluoroethyl) ester.
As the lithium salts, LiPF can be enumerated6、LiAsF6、LiAlCl4、LiClO4、LiBF4、LiSbF6、Li2SO4、
Li3PO4、Li2HPO4、LiH2PO4、LiCF3SO3、LiC4F9SO3, include the LiN (FSO of imines compound anion2)2、LiN
(CF3SO2)2、LiN(C2F5SO2)2、LiN(CF3SO2)(C2F5SO2)、LiN(CF3SO2)(C4F9SO2), with five-membered ring structure
LiN(CF2SO2)2(CF2), the LiN (CF with six-membered ring structure2SO2)2(CF2)2Deng.It, can be in addition, as the lithium salts
Enumerate LiPF6In at least one fluorine atom replaced by fluoro-alkyl obtained from LiPF5(CF3)、LiPF5(C2F5)、LiPF5
(C3F7)、LiPF4(CF3)2、LiPF4(CF3)(C2F5)、LiPF3(CF3)3Deng.At this point, the pH of electrolyte is preferably 4~10 model
It encloses.
It should be noted that as long as the pH of electrolyte is 4~10, then the addition of 60 volume % amounts below can be added
Agent.As additive, can enumerate vinylene carbonate (VC), vinylethylene carbonate (VEC), ethylene carbonate (EC),
Dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), propylene carbonate (PC), the diformazan with ether
Oxygroup ethane, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, succinic acid (acid anhydride), maleic acid
(acid anhydride), gamma-butyrolacton, gamma-valerolactone, thiirane, sulfolane, ionic liquid, borate, acetonitrile, phosphonitrile etc. or they in
Part hydrogen group be fluorinated obtained from substance etc..
In addition, by being repeated charge and discharge, tin dilation repeatedly, micronized from current-collector to remove, in order to make
It does not spread in a liquid, can be added into above-mentioned electrolyte polymerization initiator, polymer and make its gelation.As described
Polymerization initiator, polymer can use polyvinylidene fluoride hexafluoropropene (PVDF-HFP), (poly-) acrylonitrile, (poly-) third
Olefin(e) acid, polymethyl methacrylate etc., but it is not limited to these.Furthermore, it is possible to add crosslinking agent into these.It is described in order to make
Electrolyte Gel can heat up each battery after making battery, so that the electrolyte thermal polymerization is used, but also may be used
After carrying out initial several cycle charge-discharges, to heat up to make its gelation.
In addition, as the method for preventing tin particle from spreading in a liquid, solid electrolyte can also be used.As described solid
Body electrolyte can use Li3PO4、Li7La3Zr2O12、La2/3-xLixTiO3、Li0.33La0.55TiO3、Li1.3Al0.7Ti1.3
(PO4)3Equal solid oxide electrolytes；LiaGexPySz(a, x, y are arbitrary value), LiSiPSCl, LSPPS (Lil0.35
[Sn0.27Si1.08]P1.65S12(Li3.45[Sn0.09Si0.36]P0.55S4Deng or they are added to the sulphur system solid electricity of halogens
Xie Zhi；Polyethylene oxide (PEO), polyethylene oxide-LiTFSI, lithium phosphate nitrogen oxides (LiPON) etc..These materials are not waved
Hair, it is understood that compared with liquid electrolyte, also contributes the raising of safety.
The concentration of the support salt in the electrolyte is preferably the range of 0.1~3mol/L, further preferably 0.6
The range of~1.5mol/L.
As long as the conductive material of current-collector 71 in anode 7, there is no particular limitation, can be with use example
Such as by aluminium, copper, steel, titanium formation current-collector.The thickness of current-collector 71 is preferred to improve the energy density of battery with thin,
But if excessively thin, then it is difficult to handle, productivity reduces, therefore preferably 5~50 μm of range.
Positive-electrode mixture layer 72 in anode 7 can be formed by following manner：By positive active material and poly- inclined difluoro
The binders such as ethylene (PVDF) mix in right amount, are diluted with N-Methyl pyrrolidone, and the slurry thus made is utilized blade coating
Method etc. is coated on current-collector 71, is formed by coating.72 preferred positive active material of positive-electrode mixture layer is relative to total amount
Containing ratio be height, for example, the containing ratio is preferably 85 mass % or more.In addition, positive-electrode mixture layer 72 can include institute
It states except positive active material and the binder, including conductive auxiliary agent.
As the positive active material, LiMnO can be enumerated2、LixMn2O4(0<x<2)、Li2MnO3、
LixMn1.5Ni0.5O4(0<x<Etc. 2) have the LiMn2O4 of layer structure or have the LiMn2O4 of spinel structure；LiCo2O2、
LiNiO2Or the part in its transition metal replaced by other metals obtained from compound；LiNi1/3Co1/3Mn1/3O2Equal spies
Fixed transition metal is no more than the lithium transition-metal oxide of whole half；Make Li in these lithium transition-metal oxides and changes
Metering composition is learned compared to the compound for reaching surplus；LiFePO4Etc. the compound etc. for having olivine structural.
In addition, as the positive active material, a part of quilt of the metal in these metal oxides can also be used
Material obtained from the substitutions such as Al, Fe, P, Ti, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La.Especially
Ground, preferably LiαNiβCoγAlδO2(1≤α≤2 ,+δ=1 β+γ, β >=0.7, γ≤0.2) or LiαNiβCoγMnδO2(1≤α≤
1.2 ,+δ=1 β+γ, β >=0.1, γ≤0.2).
The positive active material can be used alone any one of described compound, can also be applied in combination 2 kinds with
On.
In anode 7, positive-electrode mixture layer 72 is substituted, iron sulfide, ferrous disulfide, sulphur, polythiaether, Li can be used3VO4Deng
As a positive electrode active material.Further, it is also possible to freely using nitroxyl compound for forming nitroxyl free radical part-structure etc.
Sill.In the case of these positive active materials, without lithium source in battery, it is therefore desirable for by with lithium source short circuit, vapor deposition
Deng, in advance in cathode adulterate (dope) lithium.
Embodiment
Then, examples and comparative examples of the present invention are shown.
(reference example 1~4, comparison reference example 1)
In this reference example, the copper foil (50mm × 50mm) that thickness is 20 μm is regard as tabular current-collector 21 first, to it
Another surface epoxy glue band is covered in surface sulfuric acid scrubbing, is impregnated in the electroless plating bath for being warming up to 50 DEG C,
The first tin overlay film 22 is formed on not shielded surface.Then, the tabular current-collector 21 for foring the first tin overlay film 22 is cut out
It is cut to the size of 26mm × 44mm, to which the first anode member 2 be made.At this point, adjustment dip time, makes have respectively
5 kind of first anode member 2 of the first tin overlay film 22 of the thickness of 230nm, 440nm, 770nm, 1200nm, 2000nm.
Then, by LiCoO as a positive electrode active material2, conductive auxiliary agent, the poly- inclined difluoro as bonding agent (binder)
Ethylene (PVDF) is with 92:4:4 mass ratio mixes to prepare slurry, and obtained slurry is coated on by scraper for coating method
On the aluminium foil (50mm × 50mm) that thickness is 15 μm, positive-electrode mixture layer is formed.The aluminium of the positive-electrode mixture layer will be formd
Foil is cut into the size of 25mm × 44mm, to which anode be made.
Then, the polyethylene separators that thickness is 25 μm are arranged between each first anode member 2 and the anode
(30mm × 50mm) and object vacuum sealing obtained from infiltration electrolyte is laminated cell list in the polyethylene separators
Member makes 5 kinds of lithium rechargeable batteries using the first anode member 2 as cathode shown in Fig. 1.The electrolyte is in phosphoric acid
LiPF is included with the concentration of 1.0mol/L in triethyl solvent6。
Then, by the lithium rechargeable battery in the environment of 25 DEG C with the charging current for charging of 0.1mA until the upper limit
Current potential 4.05V stops after ten minutes, and aforesaid operations are denoted as 1 cycle, carry out the behaviour of 10 cycles by electric discharge until 2.5V
Make, measure the discharge capacity (mAh) after each cycle, evaluates the charge-discharge performance of the first anode member 2.
The thickness of first tin overlay film 22 is denoted as reference example 1 for the case where 230nm, the case where 440nm is denoted as reference example
2, the case where 770nm, is denoted as reference example 3, the case where 1200nm is denoted as reference example 4, the case where 2000nm is denoted as to compare ginseng
Example 1 is examined, Fig. 4 is as a result shown in.
As shown in Figure 4, the thickness of the first tin overlay film 22 be 2000nm comparison reference example 1 in the case of, with repeatedly into
Row recycles and discharge capacity reduces, and in contrast, the thickness of the first tin overlay film 22 is the reference example 1~4 of 230~1200nm
In the case of, discharge capacity originally is maintained if even if cycle is repeated, and has excellent charge-discharge performance.
It is possible thereby to expect, according to the first cathode used in the first tin overlay film 22 of the thickness for having 100~1200nm
The lithium rechargeable battery of lithium ion secondary battery cathode 1 obtained from the second anode member 3 is laminated on component 2, can press down
The reduction of charge-discharge performance processed, and also can ensure that required energy capacity.
(embodiment 1)
In the present embodiment, first, tabular current-collector 21 is made in 10 μm of copper foil of thickness, in addition to this, with it is described
1~4 identical mode of reference example forms the first tin overlay film of the thickness of 400nm in one surface by electroless plating
22.Then, it is the discoid of a diameter of 14mm by the punching of tabular current-collector 21 of the first tin overlay film 22 is formd, to be made
First anode member 2.
Then, to positive and negative the two of an end of copper metal otter board shown in Fig. 5 (COSMO CO., LTD. system) 34
Face with epoxy glue band cover, in addition to this, in a manner of identical with the first anode member 2, by not shielded part into
Row electroless plating, to formed 400nm thickness the second tin overlay film (not shown).Metal otter board 34 has 26 μm of thickness
Degree, as shown in Figure 5, is formed line width W be 0.14mm, opening short side dimension SW be 0.64mm, be open long edge size LW be
The mesh current collector of 1.3mm.
Then, the part punching that will form the second tin overlay film of metal otter board 34 is the discoid of a diameter of 14mm, from
And the second anode member 3 is made, and on the other hand, do not form metal otter board 34 second being connected with the second anode member 3
The semicircle plate-like that part (shielded part) punching of tin overlay film is a diameter of 14mm, forms leading part 35.
Then, as shown in Figure 6, on a diameter of 20mm, the stainless steel lower cover 11 that thickness is 2mm, stacking is straight
It is the separator 12 for the stainless steel that diameter is 15mm and thickness is 1mm, the first anode member 2, the second anode member 3, a diameter of
Polyethylene isolation film 13 that 19mm and thickness are 20 μm, the lithium foil for being 100 μm as a diameter of 16mm and thickness to electrode
14, infiltrate electrolyte in isolation film 13, by gained object with by outer diameter be 1.8mm, internal depth is 2mm round-ended cylinder
Stainless steel upper cover 15 sealing that shape body is formed, to make the button cell (half-cell) 16 as lithium rechargeable battery.
At this point, the first anode member 2 is arranged in such a way that the first tin overlay film 22 is 3 side of the second anode member.In addition, lead member 35 is such as
It bends to be inserted between lower cover 11 and separator 12 like that shown in single-point dotted line in Fig. 6, thus has promotion negative by second
The function of 3 afflux of pole component.
The electrolyte is in triethyl phosphate/dimethyl carbonate (DEC)/fluoroethylene carbonate (FEC) (8/1/1=
Vol% include) LiPF with the concentration of 1.0mol/L in solvent6.In addition, electrode of the button cell 15 using lower cover 11 as side
On the other hand plate and using upper cover 14 as to electrode plate between lower cover 11 and upper cover 15, is equipped and is formed by insulator
It seals (not shown).It should be noted that separator 12 has the first cathode for being sealed at and being clamped by lower cover 11 and upper cover 15
Component 2, the second anode member 3, isolation film 13, as the function of distinguishing the lithium foil 14 of pole adjacent component.
Then, to the button cell 16 obtained in the present embodiment, 15 cycles are carried out under the voltage of the range of 0.1~2V
The magnitude of current based on 1C charge and discharge when, relative to initial charge capacity 0.4mAh, 15 cycle after sustainment rate be
111%.As a result it is shown in Fig. 7.
In the button cell 16 obtained in the present embodiment, it is believed that charging capacity during cycle is repeated
The reasons why rising, is that the electrolyte gradually infiltrates by the hole portion (opening) of the metal otter board 34 as mesh current collector
The inside of two anode members 3, response area increase.
(embodiment 2)
In the present embodiment, on the first anode member 2 be laminated 2 second anode members 3, in addition to this, with embodiment 1
Exact same way makes the button cell 16 as lithium rechargeable battery.
Then, to the button cell 16 obtained in the present embodiment, 15 cycles of progress under the voltage of 0.1~2V ranges
When the charge and discharge of the magnitude of current based on 1C, relative to initial charge capacity 0.63mAh, the sustainment rate after 15 cycles is 100%.
As a result it is shown in Fig. 7.
(embodiment 3)
In the present embodiment, electrolyte use is in triethyl phosphate/dimethyl carbonate (DMC)/FEC (80/1/1=vol%)
The PVDF-HFP of middle mixing 8wt% simultaneously further dissolves LiPF with 1.0mol/L6Obtained from electrolyte, in addition to this, with
1 exact same way of embodiment makes button cell 16.
Then, the button cell 16 obtained in the present embodiment is heated up to 1 hour in the state of 60 DEG C to make the electricity
After solving pension gelation, when carrying out the charge and discharge of the magnitude of current based on 1C of 15 cycles under the voltage of the range of 0.1~2V, phase
For initial charge capacity 0.36mAh, the sustainment rate after 15 cycles is 99%.As a result it is shown in Fig. 7.
Make the button for the embodiment 1 that the button cell 16 of the present embodiment of Electrolyte Gel is shown with electrolyte is liquid
The capacity maintenance rate of 16 almost the same degree of battery, constant capacity maintenance rate is shown from initial stage, is properly termed as reliability height
Battery.
(comparative example 1)
In this comparative example, the second anode member 3 is not laminated completely on the first anode member 2, in addition to this, with implementation
1 exact same way of example makes the button cell 16 as lithium rechargeable battery.
Then, to the button cell 16 obtained in this comparative example, 15 cycles are carried out under the voltage of the range of 0.1~2V
The magnitude of current based on 1C charge and discharge when, relative to initial charge capacity 0.14mAh, 15 cycle after sustainment rate be
91%.As a result it is shown in Fig. 7.
As shown in Figure 7, according to the lithium rechargeable battery (button cell for the embodiment 1,2 for having the second anode member 3
16) reduction of performance, can be inhibited charge and discharge cycles, and can ensure required energy capacity.In addition, according to embodiment
2 lithium rechargeable battery can by making the quantity of the second anode member 3 be more than the lithium rechargeable battery of embodiment 1
Further ensure that energy-capacity.
On the other hand it is found that according to the lithium rechargeable battery for the comparative example 1 for not having the second anode member 3 completely, with
The lithium rechargeable battery of embodiment 1,2 is compared, and not only cannot ensure sufficient energy capacity, but also in charge-discharge performance
Reduction in terms of, also the lithium rechargeable battery than embodiment 1,2 is poor.
Claims (12)
1. a kind of lithium ion secondary battery cathode, which is characterized in that have：
First anode member, have tabular current-collector and cover the tabular current collector surface and thickness be 100~
First tin overlay film of 1200nm ranges；With
Second anode member, has：It conductive mesh current collector and covers the mesh current collector surface and thickness and is
Second tin overlay film of 100~1200nm ranges, second anode member have the space surrounded by the second tin overlay film；
At least one second anode member is laminated on first tin overlay film of first anode member.
2. lithium ion secondary battery cathode according to claim 1, which is characterized in that
The tabular current-collector is made of a kind of metal selected from the group being made of following metal：Aluminium, copper, steel, titanium.
3. lithium ion secondary battery cathode according to claim 1, which is characterized in that
The tabular current-collector has the thickness of 5~50 μ ms.
4. lithium ion secondary battery cathode according to claim 1, which is characterized in that
The mesh current collector is made of a kind of material selected from the group being made of llowing group of materials：Net made of filament track and column braiding
Shape body, punch metal, metal otter board.
5. lithium ion secondary battery cathode according to claim 4, which is characterized in that
Reticulate body made of the filament track and column braiding is made of a kind of metal fine selected from the group being made of following metal：
Aluminium, copper, steel, titanium, tin.
6. lithium ion secondary battery cathode according to claim 4, which is characterized in that
Reticulate body made of the filament track and column braiding has the sieve pore of 1~50 μ m.
7. lithium ion secondary battery cathode according to claim 4, which is characterized in that
The metal otter board have the line width of 0.001~10mm ranges, the opening short side dimension of 0.01~10mm ranges, 0.05~
The opening long edge size of 50mm ranges.
8. lithium ion secondary battery cathode according to claim 1, which is characterized in that
The mesh current collector has the thickness of 3~500 μ ms.
9. lithium ion secondary battery cathode according to claim 1, which is characterized in that
The first tin overlay film or the second tin overlay film are electroplating films.
10. lithium ion secondary battery cathode according to claim 1, which is characterized in that
Between first anode member and second anode member, has the mixture layer comprising negative electrode active material.
11. lithium ion secondary battery cathode according to claim 10, which is characterized in that
The negative electrode active material being contained in the mixture layer is at least one material selected from the group being made of llowing group of materials：
Artificial graphite, natural graphite, hard carbon, soft carbon, silicon, silica, tin, silver, aluminium, zinc, lead, germanium, lithium etc. or these above-mentioned materials
Alloy.
12. a kind of lithium rechargeable battery, which is characterized in that have：
Cathode, anode and electrolyte,
The cathode has：First anode member has tabular current-collector and covers a table of the tabular current-collector
Face and thickness are the first tin overlay films of 100~1200nm ranges；And second anode member, have：Conductive net
Shape current-collector and cover the mesh current collector surface and thickness be 100~1200nm ranges the second tin overlay film；Described second is negative
Pole component has the space surrounded by the second tin overlay film；It is laminated on first tin overlay film of first anode member described
Second anode member；
The anode configures in opposite directions with second anode member.
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| JP2017-012581 | 2017-01-26 | ||
| JP2017012581 | 2017-01-26 | ||
| JP2017-198321 | 2017-10-12 | ||
| JP2017198321 | 2017-10-12 | ||
| JP2017-226668 | 2017-11-27 | ||
| JP2017226668A JP6745782B2 (en) | 2017-01-26 | 2017-11-27 | Negative electrode for lithium-ion secondary battery and lithium-ion secondary battery |
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| CN108365170B CN108365170B (en) | 2021-03-30 |
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