CN108365171A - Lithium ion secondary battery cathode and its manufacturing method and lithium rechargeable battery - Google Patents
Lithium ion secondary battery cathode and its manufacturing method and lithium rechargeable battery Download PDFInfo
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- CN108365171A CN108365171A CN201810067959.5A CN201810067959A CN108365171A CN 108365171 A CN108365171 A CN 108365171A CN 201810067959 A CN201810067959 A CN 201810067959A CN 108365171 A CN108365171 A CN 108365171A
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- current
- collector
- ion secondary
- lithium ion
- 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
Abstract
The present invention provides lithium ion secondary battery cathode and its manufacturing method and lithium rechargeable battery, can inhibit charge and discharge cycles reduced performance and can ensure required energy capacity.Lithium ion secondary battery cathode (1) has at least one stepped construction, which is constituted by two current-collectors (21,22) and by the negative electrode active material layer (31) of this two current-collector (21,22) clamping.
Description
Technical field
The present invention relates to lithium ion secondary battery cathode and its manufacturing method and lithium rechargeable batteries.
Background technology
In the past, the secondary cell as the power supply for being used in 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 have by current collector surface formed 10~300 μm of thickness tin film layer obtained from material for the lithium from
The cathode of sub- secondary cell (referring for example to patent document 1).
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2001-68094 bulletins
Invention content
The subject that the invention solves
It can be from however, volume expansion of the tin film layer after receiving lithium ion is very big, when being repeated discharge and recharge reaction
The sur-face peeling of the current collector layer, thus there are problems that the charge-discharge performance of the lithium rechargeable battery reduces.
It is an object of the invention to eliminate the above problem, even if while provide one kind when discharge and recharge reaction is repeated
The tin overlay film formed on the surface of current-collector will not reduction that is peeling-off and can inhibiting charge and discharge cycles performance and can
Ensure the lithium ion secondary battery cathode and its manufacturing method of required energy capacity.
In addition, the present invention also aims to provide a kind of lithium ion two having the lithium ion secondary battery cathode
Primary cell.
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, is had at least one
Stepped construction, the stepped construction are made of two current-collectors and the negative electrode active material layer being clamped by this two current-collector.
The present invention lithium ion secondary battery cathode in, negative electrode active material layer by two current-collectors be clamped and by two
Current-collector constrains, thus, even if the negative electrode active material can be prevented if charge and discharge are repeated in a lithium ion secondary battery
Layer is removed from the current-collector, so as to inhibit charge and discharge cycles the reduction of performance.
The present invention lithium ion secondary battery cathode in, the negative electrode active material layer can by be selected from tin overlay film,
A kind of material composition of aluminium film, the group of aluminium alloy film composition.At this moment, the tin overlay film is preferably made of tin plated film.
In addition, in the lithium ion secondary battery cathode of the present invention, the current-collector can be by metal film coated or surface
Metal powder with tin plated film is constituted.At this moment, it is described it is metal film coated can be made of metal foil, can also be by metal coating structure
At.In addition, it can also be plate that film, which can be foil, it can also be that particle arranges and formed the state of film-form.
The lithium ion secondary battery cathode of the present invention can effectively be manufactured by following manufacturing methods.The lithium
The manufacturing method of ion secondary battery cathode has：It is formed on by the metal film coated current-collector constituted and to be made of tin plated film
1st step of negative electrode active material layer；And on the negative electrode active material layer formed by the 1st step formed by
The second step for the current-collector that metal coating with 1000nm or less thickness ranges is constituted, also, at least carry out the 1st step
The rapid and second step is each primary.
In addition, the lithium ion secondary battery cathode of the present invention can also be carried out effectively by manufacturing method below
Manufacture.The manufacturing method of the lithium ion secondary battery cathode has：Tin plated film is formed to obtain on the surface of metal powder
1st step of the metal powder with tin plated film on surface；Prepare the second step of slurry, wherein the slurry includes by described
1st step and the metal powder with tin plated film on the surface that is formed, and, the slurry prepared by the second step is coated with
By the third step on the metal film coated current-collector constituted.The manufacturing method can also by have the method for following step come
Effectively manufactured：It is formed by metal-plated on the tow sides for the negative electrode active material layer being made of aluminium film or aluminium alloy film
The step of current-collector that film is constituted.
In addition, the lithium rechargeable battery of the present invention is configured to have：The lithium ion secondary battery cathode；With
The anode that the negative electrode active material layer of the cathode configures in opposite directions；With, configuration the cathode and it is described anode between
Electrolyte layer.
Description of the drawings
Fig. 1 is the schematic sectional view for a configuration example for indicating the lithium ion secondary battery cathode of the present invention.
Fig. 2A is that the schematic of the 1st step in the manufacturing method for indicate lithium ion secondary battery cathode shown in FIG. 1 cuts
Face figure.
Fig. 2 B are that the schematic of second step in the manufacturing method for indicate lithium ion secondary battery cathode shown in FIG. 1 cuts
Face figure.
Fig. 2 C are the 2nd the 1st steps of progress in the manufacturing method for indicate lithium ion secondary battery cathode shown in FIG. 1
Schematic sectional view.
Fig. 2 D are the 2nd progress second steps in the manufacturing method for indicate lithium ion secondary battery cathode shown in FIG. 1
Schematic sectional view.
Fig. 3 is to indicate showing for the composition for having the lithium rechargeable battery of lithium ion secondary battery cathode shown in FIG. 1
Meaning property sectional view.
Fig. 4 A are the schematic sectional views for other configuration examples for indicating the lithium ion secondary battery cathode of the present invention.
Fig. 4 B are the enlarged views of Fig. 4 A.
Fig. 5 is the lithium rechargeable battery for the present invention for indicating to have lithium ion secondary battery cathode shown in Fig. 4 A
The schematic sectional view of composition.
Fig. 6 is to indicate to have in the lithium rechargeable battery of the present invention that tin overlay film is used as the negative of negative electrode active material layer
The chart of charge-discharge characteristic when pole.
Fig. 7 is to indicate to have in the lithium rechargeable battery of the present invention that aluminium film or aluminium alloy film are used as negative electrode active material
The chart of charge-discharge characteristic when the cathode of matter layer.
Symbol description
1 lithium ion secondary battery cathode
21,22 current-collectors
24 metal powders
31,32,33 tin overlay films
4 lithium rechargeable batteries are used
C1,C2Current-collector
A1,A2Negative electrode active material layer
Specific implementation mode
Then, with reference to attached drawing, the embodiment that present invention be described in more detail.
As shown in Figure 1, the lithium ion secondary battery cathode 1 of the 1st form of present embodiment has interlaced with each other three
Layer 21,22,23 and two layers tin overlay film 31,32 of current-collector.Tin overlay film 31,32 forms negative electrode active material layer.
At this moment, the lithium ion secondary battery cathode 1 of the 1st form specifically has：The 1st current-collector being made of metal foil
21；The 1st tin overlay film 31 formed on the 1st current-collector 21；The 2nd be made of metal coating formed on the 1st tin overlay film 31
Current-collector 22；The 2nd tin overlay film 32 formed on the 2nd current-collector 22；What is formed on the 2nd tin overlay film 32 is made of metal coating
The 3rd current-collector 23.Here, as the 1st tin plated film 31 of negative electrode active material layer by the 1st current-collector 21 and the 2nd current-collector 22
Clamping, the 2nd tin plated film 32 as negative electrode active material layer are clamped by the 2nd current-collector 22 and the 3rd current-collector 23.
The lithium ion secondary battery cathode 1 of 1st form shown in FIG. 1 has two tin overlay films as described above by two
The stepped construction of current-collector clamping.But lithium ion secondary battery cathode 1 can also be further equipped with it is more, be, for example, 20
A following range of stepped construction.
As long as the conductive metal foil of the 1st current-collector 21, does not make it special restriction.Such as it can be with
The 1st current-collector is formed using foils such as aluminium, copper, steel, titaniums.In order to improve the energy density of battery, the thickness of the 1st current-collector 21 with
It is thin to be preferred.But if excessively thin, then it is difficult to be handled, productivity reduces.Therefore, which is preferably 1~50 μm.This
Outside, the 1st current-collector 21 can cut surface or be dissolved to form bumps.
2nd current-collector 22 and the 3rd current-collector 23 are for example by being that 1000nm plated copper films below are constituted with thickness range.It can
To utilize coating method on the 1st tin overlay film 31 formed in preceding step respectively in the later-described manufacturing method or the 2nd tin overlay film 32
Form the 2nd current-collector 22 and the 3rd current-collector 23.Galvanoplastic and electroless plating method may be used in above-mentioned coating method.But from can
It is made from the point of view of more porous porous material, electroless plating method may be used to form the 2nd current-collector 22 and the 3rd current collection
Device 23.
In the later-described manufacturing method, on the 1st current-collector 21 and the 2nd current-collector 22 the 1st is formed using coating method respectively
Tin overlay film 31 and the 2nd tin overlay film 32.Although galvanoplastic or electroless plating method may be used in above-mentioned coating method, but from relative to collection
Electric appliance 21,22 simply, can be formed inexpensively from the point of view of adaptation is good and the overlay film of large area, it is preferred to use galvanoplastic shape
At the 1st tin overlay film 31 and the 2nd tin overlay film 32.
1st tin overlay film 31 and the 2nd tin overlay film 32 preferably form the thickness of 100nm~100 μm by above-mentioned coating method.When
When the less than 100nm of the thickness of 1 tin overlay film 31 and the 2nd tin overlay film 32, receive the lithium ion as negative electrode active material make it is used
It is small, therefore preferably 100nm or more.On the other hand, when above-mentioned thickness is more than 100 μm, the infiltration of electrolyte is more time-consuming and difficult
To be manufactured, therefore preferably 100 μm or less.
Then, the 1st manufacturing method of lithium ion secondary battery cathode 1 is illustrated with reference to Fig. 2A~Fig. 2 D.
When manufacturing lithium ion secondary battery cathode 1, first, as shown in Figure 2 A, in the 1st current-collector being made of copper foil
On 21 the 1st tin overlay film 31 is formed using galvanoplastic.Wherein, above-mentioned copper foil is covered as the metal of the thickness with 1~50 μ m
Film.
When forming the 1st tin overlay film 31 by plating, the 1st current-collector 21 is impregnated in the acid such as nitric acid, hydrochloric acid, sulfuric acid,
Or after dirt, oxidation film for by washing removing surface etc., epoxy glue band is utilized to cover a side surface of the 1st current-collector 21
Whole surface and another party surface a part of surface.Then, the 1st shielded current-collector 21 is impregnated into plating bath,
It is powered at an established temperature, thus forms the 1st tin overlay film 31 in the not shielded surface portion of the 1st current-collector 21.Its
In, above-mentioned plating bath is by the way that the pink salts such as stannic chloride are dissolved into the acid such as sulfuric acid, methanesulfonic acid (methanesulfonic acid)
In and formed.In addition, the thickness of the 1st tin overlay film 31 can be managed by conduction time.
In addition, above-mentioned plating bath can be that the pink salts such as stannic chloride are dissolved into instead of aqueous slkalis such as the sodium hydroxides of sulfuric acid
In plating bath.
Then, as shown in Figure 2 B, plated by copper using electroless plating method formation on the 1st tin overlay film 31 formed in preceding step
The 2nd current-collector 22 that film is constituted.
When forming 2 current-collector 22 using the electroless plating method of copper, the 1st current-collector of the 1st tin overlay film 31 will be formed with
21 are impregnated into plating bath, are heated up to set point of temperature.Wherein, the bath of above-mentioned plating is by by copper sulphate and being used as the secondary phosphorus of reducing agent
Sour sodium is dissolved into sulfuric acid and is formed.In this way, the 1st tin overlay film 31 and do not covered by the 1st tin overlay film 21 the 1st
On current-collector 21, the 2nd current-collector 22 with 1000nm following range of thickness is formed.The thickness of 2nd current-collector 22 can lead to
The mild dip time of liquid for crossing above-mentioned plating bath is managed.It should be noted that can before forming the 2nd current-collector 22,
The surface for being formed with the 1st current-collector 21 of the 1st tin overlay film 31 is cleaned with water etc..In addition, above-mentioned plating bath can also lead to
Cross in sodium hydroxide, potassium hydroxide dissolve copper cyanider and dissolve Rochelle salt, ammonia and formed.
It can alternatively, it is also possible to the configuration on the 1st tin overlay film 31 and the 1st current-collector 21 not covered by the 1st tin overlay film 31
The curtain-shaped cover member (not shown) for forming diameter 1mm micropores below, is handled by above-mentioned electroless plating method.Above-mentioned shielding portion
Part is removed after the formation of the 2nd current-collector 22.In this way, the 2nd current-collector 22 can be arranged to lithium ion to be easy thoroughly
The form crossed.
Then, as shown in Figure 2 C, on the 2nd current-collector 22 the 2nd tin overlay film 32 is formed using galvanoplastic.2nd tin overlay film 32
Formed can on the 1st current-collector 21 formed the 1st tin overlay film situation exact same way carry out.At this moment, in addition to tin
It in addition, can also be with the co-precipitation plated film such as copper, nickel, silver.
Then, as shown in Figure 2 D, the 3rd current-collector 23 is formed on the 2nd tin overlay film 32 formed by preceding step, thus shape
At lithium ion secondary battery cathode 1 shown in FIG. 1.The formation of 3rd current-collector 23 can be the same as forming on the 1st tin overlay film 31
The situation exact same way of 2 current-collectors 22 carries out.
Furthermore, it is also possible to the processing that punches be imposed to the lithium ion secondary battery cathode 1 formed through the above way, to carry
High electrolyte is impregnated with.
It should be noted that on the lithium ion secondary battery cathode 1 formed through the above way, in the 1st current-collector
At 21 end (being right part in Fig. 2 D), the 1st current-collector 21, the 2nd current-collector 22 and the 3rd current-collector 23 are connected with each other.
In addition, in Fig. 2A~Fig. 2 D, the tin that is constituted by forming tin plated film on the current-collector 21 being made of metal foil
Overlay film 31, and the current-collector 22 being made of metal coating is formed on tin overlay film 31, form the tin as negative electrode active material layer
The stepped construction that overlay film 31 is clamped by two current-collectors 21,22.But it is also possible to above-mentioned tin overlay film is substituted using aluminium overlay film,
To substitute above-mentioned stepped construction.It is made of metal coating alternatively, can also be formed in the tow sides of aluminium film or aluminium alloy film
Current-collector.The stacking knot being clamped by two current-collectors as the aluminium film or aluminium alloy film of negative electrode active material layer can also be formed
Structure.
As above-mentioned aluminium alloy film, 2000 systems (kind platform/Japanese Industrial Specifications (JIS)) comprising Cu or Du can be included
Draw aluminium (duralumin), 3000 systems (kind platform/Japanese Industrial Specifications (JIS)) comprising Mn, 4000 systems (kind platform/day comprising Si
This commercial size (JIS)), 5000 systems (kind platform/Japanese Industrial Specifications (JIS)) comprising Mg, 6000 systems comprising Mg and Si (kind
Platform/Japanese Industrial Specifications (JIS)), 7000 systems (kind platform/Japanese Industrial Specifications (JIS)) etc. comprising Zn, Mg.In addition to this,
The Alloy Foil comprising other elements can be used.Alternatively, it is also possible to using aluminum bronze, Aluminum tin alloy foils, lithium-aluminium alloy foil.Moreover,
It can also utilize and be coated with the slurry being made of binders (binder) such as the auxiliary agents such as alumina particles, carbon, polyvinylidene fluoride (PVDF)
The aluminium alloy film of material, the aluminium alloy film that aluminium paste can also be coated on current-collector.
As the metal for forming the metal coating, nickel, tin, silver, gold, copper etc. can be included.
The lithium ion secondary battery cathode 1 of 1st form of present embodiment can be used in lithium ion two shown in Fig. 3
In primary cell 4.
Lithium rechargeable battery 4 is by configuring lithium ion secondary battery cathode 1 in the inside of battery unit 5, being impregnated with
Electrolyte layer 6 and anode 7 that the isolation film of electrolyte is constituted and constitute.In lithium rechargeable battery 4, lithium rechargeable battery
With cathode 1 by the 3rd current-collector 23 via isolation film 6 with anode 7 it is opposite in a manner of configure.Anode 7 has 71 He of anode current collector
Positive-electrode mixture layer 72 configures in such a way that positive-electrode mixture layer 72 and isolation film 6 are opposite.In addition, lithium rechargeable battery is used
It is connected with negative wire 8 on 1st current-collector 21 of cathode 1, positive wire 9 is connected in the anode current collector 71 of anode 7.
In lithium rechargeable battery 4, isolation film can use the material such as made of the synthetic resin polyethylene.This
Outside, as the electrolyte infiltrated in isolation film, the phosphate stated using the following general formula (1) can be used as solvent and
Dissolved with lithium salts as electrolyte obtained from support salt in the solvent.
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, can be the same or different each other.In addition, if the straight-chain alkyl carbon atom number increases, viscosity becomes
Must be excessively high, then 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.Alternatively, it is also possible on the basis of having lithium salts or
Person replaces above-mentioned lithium salts and uses sodium salt.
The concentration range of the support salt in the electrolyte be preferably 0.1~3mol/L, further preferably 0.6~
1.5mol/L.At this moment, the pH of electrolyte is preferably 4~10.It should be noted that as long as the pH of electrolyte is in 4~10 ranges
It is interior, then it can add the additive relative to the 50% of electrolyte whole quality amount below.As additive, carbon can be enumerated
Sour vinylene (VC), vinylethylene carbonate (VEC), ethylene carbonate (EC), dimethyl carbonate (DMC), carbonic acid diethyl
Ester (DEC), methyl ethyl carbonate (EMC), propylene carbonate (PC), the dimethoxy-ethane with ether, diethylene glycol dimethyl
Ether, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, succinic acid (acid anhydride), maleic acid (acid anhydride), gamma-butyrolacton, in γ-penta
Object obtained by ester, thiirane, sulfolane, ionic liquid, borate, acetonitrile, phosphonitrile etc. or the part hydrogen in them are fluorinated
Matter etc..
In addition, electrolyte layer 6 can also be by gel rubber material be added to the material formed in above-mentioned electrolyte be infiltrated up to every
From the electrolyte layer for making its gelation in film and by heating.As above-mentioned gel rubber material, such as poly- inclined difluoro can be included
The polymerization initiators such as ethylene hexafluoropropene (PVDF-HFP), (poly-) acrylonitrile, (poly-) acrylic acid, polymethyl methacrylate or
Polymer.
In addition it is possible to use solid electrolyte is as electrolyte layer 6.As above-mentioned solid electrolyte, can use
Li3PO4、Li7La3Zr2O12、La2/3-xLixTiO3、Li0.33La0.55TiO3、Li1.3Al0.7Ti1.3(PO 4)3Equal oxide solids electricity
Xie Zhi；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 electrolyte of halogens；Polyethylene oxide (PEO) is gathered
Ethylene oxide-LiTFSI, lithium phosphate nitrogen oxides (LiPON) etc..Since these materials are non-volatile, it can be considered that these materials
Material can also be contributed compared with liquid electrolyte improving safety.
As long as the conductive material of current-collector 71 in anode 7, does not make special restriction.For example, may be used also
To use such as the current-collector constituted by aluminium, copper, steel, titanium.In order to improve the energy density of battery, the thickness of current-collector 71 with
It is thin to be preferred, but if excessively thin, then it is difficult to be handled, productivity reduces.Therefore, the thickness range of current-collector 71 preferably 5~50 μ
m。
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, thus will utilize blade coating by manufactured slurry
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 it is higher, 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, also includes conductive auxiliary agent.
As the positive active material, LiMnO can be included2、LixMn2O4(0 ＜ x ＜ 2), Li2MnO3、
LixMn1.5Ni0.5O4(0 ＜ x ＜ 2) etc. has the LiMn2O4 of layer structure or has the LiMn2O4 of spinel structure；LiCo2O2、
LiNiO2Or the compound obtained from other metal replacements of the part in its transition metal；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 displacements 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 >=0.4, γ≤0.2) or LiαNiβCoγMnδO2(1≤α≤
1.2 ,+δ=1 β+γ, β >=0.4, γ≤0.2).
The positive active material can be used alone any one in the compound, can also combine 2 kinds of chemical combination
It more than object is used.
Iron sulfide, ferrous disulfide, sulphur, copper, polythiaether, Li can be used3VO4Deng as a positive electrode active material.In addition,
It can also use and form the free sills such as the nitroxyl compound of nitroxyl free radical part-structure as a positive electrode active material.
When using these materials as a positive electrode active material, 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.
According to the lithium rechargeable battery 4 for having lithium ion secondary battery cathode 1, even if in a lithium ion secondary battery
Charge and discharge are repeated, can also prevent tin overlay film 31,32 from being removed from current-collector 21,22,23, to inhibit charge and discharge cycles
It the reduction of performance and is expected to ensure required energy capacity.
Then, as schematically indicated in Fig. 4 A, in the lithium ion secondary battery cathode of the 2nd form of present embodiment
In 1, has the layer for including metal powder 24 in metal foil 21, metal powder 24 has tin plated film 31 on the surface thereof.
Herein, as shown in Fig. 4 B shown in being amplified a part of figure to Fig. 4 A, in the lithium ion secondary of the 2nd form
In negative electrode battery 1, the 1st current-collector C is formed by metal foil 211While, form the 2nd current-collector C2.2nd current-collector C2By gold
The tin plated film 31 for belonging to powder 24 and being formed in 24 side of metal powder is constituted.In addition, the tin plated film 31 by being formed in 24 lower section of metal powder
Form negative electrode active material layer A1While, the tin plated film 31 by being formed in 24 top of metal powder forms negative electrode active material layer A2。
As a result, in the lithium ion secondary battery cathode 1 of the 2nd form, negative electrode active material layer A is formed1By current collection
Device C1、C2The stepped construction of clamping.
The metal foil 21 of lithium ion secondary battery cathode 1 as the 2nd form, can use with the lithium of the 1st form from
The 21 identical material of the 1st current-collector of sub- secondary battery cathode 1.In addition, as long as metal powder 24 has the metal of electric conductivity
Powder, because without making particular determination to it.The powder such as may be used aluminium, copper, steel and titanium of metal powder 24.Metal powder 24 is excellent
Choosing has the average grain diameter of 100 μm of ranges below.
In addition, the tin plated film 31 on 24 surface of metal powder can utilize and the lithium ion secondary battery cathode 1 of the 1st form
The identical mode of generation type of tin overlay film 31,32 is formed.
The lithium ion secondary battery cathode 1 of 2nd form shown in Fig. 4 A can for example be manufactured by following manner：
Surface is had into the metal powder 24 of tin overlay film 31 and binder and conductive auxiliary agent are mixed into slurry, and the slurry is applied to metal
On foil 21.In addition it is also possible to further form collector film by plated film gimmick after coating.
The lithium ion secondary battery cathode 1 of 2nd form of present embodiment can be used in lithium ion two shown in fig. 5
Primary cell 4.Lithium rechargeable battery 4 shown in fig. 5 is in addition to using the lithium ion secondary battery cathode 1 of the 2nd form as negative
Except pole 1, the composition that remaining constitutes lithium rechargeable battery 4 as shown in figure 3 is identical.Therefore, to identical part
Mark identical symbol, and detailed description will be omitted.
Then, the embodiment of the present invention and comparative example are shown.
Embodiment
(embodiment 1)
In the present embodiment, the copper foil for being first 10 μm using thickness utilizes electricity as the 1st current-collector 21 on current-collector 21
Plating forms the tin plated film that thickness is 2 μm, to which tin overlay film 31 be made.Then, forming thickness using plating on tin overlay film 31 is
The plated copper film of 200nm forms tin overlay film 31 and is clamped by the 1st current-collector 21 and the 2nd current-collector 22 to which the 2nd current-collector 22 be made
Stepped construction.Then, above-mentioned laminate structure is punched into the material of diameter 15mm sizes, to which lithium ion secondary electricity be made
Pond cathode 1.
Then, by LiNi as a positive electrode active material0.5Mn0.3Co0.2O2, as the acetylene black of conductive auxiliary agent
(acetylene black), as binder polyvinylidene fluoride (PVDF) with 94:3:3 mass ratio mixes to prepare
Slurry, it is to form positive-electrode mixture layer 72 on 20 μm of aluminium foil that obtained slurry, which is coated on thickness,.Then, it will form
The anode current collector 71 of positive-electrode mixture layer 72 is punched into the material of diameter 14mm sizes, to which anode 7 be made.
Then, the polythene material that arranging thickness is 20 μm between cathode 1 and anode 4 is as isolation film (diameter
20mm), electrolyte layer 6 obtained from electrolyte is infiltrated in the isolation film.And using the electrolyte layer 6 be made coin shape lithium from
Sub- secondary cell 4.During making above-mentioned electrolyte layer 6, following electrolyte are used：With 80:20 volume ratio mixes phosphorus
Triethylenetetraminehexaacetic acid ester (TEP) and fluoroethylene carbonate (FEC), are made mixed solvent, in the in the mixed solvent with the dense of 1.0mol/L
Degree dissolving LiPF6。
Then, use lithium rechargeable battery 4 obtained in the present embodiment, under the voltage of 2.5~3.85V ranges with
1C electric currents carry out repeated charge to lithium rechargeable battery 4.Change by charge/discharge capacity relative to charge and discharge cycles number is turned into
It is shown in Figure 6 for charge-discharge characteristic at this time.
(embodiment 2)
In the present embodiment, in grain size it is first on 15 μm of 24 surface of copper powder, forming thickness using electroless plating method is
The copper powder 24 for having tin plated film 31 on surface is made in 0.2 μm of tin plated film 31.Then, will there is tin plated film 31 on the surface
Copper powder 24, the acetylene black as conductive auxiliary agent, the polyvinylidene fluoride as binder (PVDF) are with 90:4:6 mass ratio is mixed
It closes to prepare slurry, and it is to be punched into diameter after making it dry on 10 μm of copper foil 21 that slurry obtained, which is coated on thickness,
The material of 15mm sizes, to which lithium ion secondary battery cathode 1 be made.
Then, in addition to use in the present embodiment made of other than lithium ion secondary battery cathode 1, other with implementation
Lithium rechargeable battery 4 is made in 1 exact same way of example.
Then, other than using manufactured lithium rechargeable battery 4 in the present embodiment, other are with complete with embodiment 1
Exactly the same mode implements charge and discharge repeatedly to lithium rechargeable battery 4.By charge/discharge capacity relative to charge and discharge cycles number
It is shown in Figure 6 to become the charge-discharge characteristic being turned at this time.
(embodiment 3)
In the present embodiment, with 70:20:10 volume ratio mixed phosphate triethyl (TEP), fluoroethylene carbonate
(FEC) and dimethyl carbonate (DMC) mixed solvent, is made, LiPF is dissolved with the concentration of 1.2mol/L in the in the mixed solvent6,
And by the mixed solvent and polyvinylidene fluoride hexafluoropropene (PVDF-HFP) as gel rubber material with 90:10 mass ratio
Mixing, is prepared into electrolyte.
Then, in addition to use include above-mentioned gel rubber material electrolyte other than, remaining and 2 exact same way of embodiment
Coin shape lithium rechargeable battery 4 is made, 1 hour at a temperature of which is maintained at 60 DEG C, makes the electrolysis
Pension gelation, to form electrolyte layer 6.
Then, other than using manufactured lithium rechargeable battery 4 in the present embodiment, other are with complete with embodiment 1
Exactly the same mode implements charge and discharge repeatedly to lithium rechargeable battery 4.By charge/discharge capacity relative to charge and discharge cycles number
Become and is turned to charge-discharge characteristic at this time and shown in Figure 6.
(comparative example 1)
In this comparative example, the copper foil for being first 10 μm using thickness utilizes plating as current-collector 21 on current-collector 21
The tin plated film that thickness is 2 μm is formed, to which tin overlay film 31 be made.Then, the stacking that will be made of current-collector 21 and tin overlay film 31
Structure is punched into the material of diameter 15mm sizes, and cathode is made.
Then, in addition to use in this comparative example made of other than cathode 1, other with 1 identical side of embodiment
Lithium rechargeable battery 4 is made in formula.
Then, other than using manufactured lithium rechargeable battery 4 in this comparative example, other are with complete with embodiment 1
Exactly the same mode implements charge and discharge repeatedly to lithium rechargeable battery 4.By charge/discharge capacity relative to charge and discharge cycles number
It is shown in Figure 6 to become the charge-discharge characteristic being turned at this time.
(embodiment 4)
In the present embodiment, the tow sides for the aluminium foil for being first 15 μm in the thickness as negative electrode active material layer utilize
Electroless plating method forms the nickel plated film that thickness is 0.3 μm, current-collector is made, and form negative electrode active material layer by two current-collectors
The laminate structure of clamping.Then, above-mentioned laminate structure is punched into diameter 15mm sizes lithium rechargeable battery is made
With cathode 1.
Then, in addition to use in the present embodiment made of other than lithium ion secondary battery cathode 1, other with implementation
Lithium rechargeable battery 4 is made in 1 exact same way of example.
Then, use in the present embodiment made of lithium rechargeable battery 4, under the voltage of 2.5~4.15V ranges with
1C electric currents carry out repeated charge to lithium rechargeable battery 4.Change by charge/discharge capacity relative to charge and discharge cycles number is turned into
It is shown in Figure 7 for charge-discharge characteristic at this time.
(embodiment 5)
In the present embodiment, other than using lithium-aluminium alloy foil to substitute aluminium foil, other are with identical with embodiment 4
Lithium rechargeable battery 4 is made in mode.
Then, other than using manufactured lithium rechargeable battery 4 in the present embodiment, other are with complete with embodiment 4
Exactly the same mode carries out repeated charge to lithium rechargeable battery 4.By charge/discharge capacity relative to charge and discharge cycles number
It is shown in Figure 7 to become the charge-discharge characteristic being turned at this time.
(comparative example 2)
In this comparative example, first, the aluminium foil that thickness is 15 μm is punched into the material that diameter is 15mm sizes, be made negative
Pole 1.
Then, with 80:20 volume ratio mixed phosphate triethyl (TEP) and fluoroethylene carbonate (FEC), is made mixing
Solvent dissolves LiPF in the in the mixed solvent with the concentration of 1.2mol/L6, it is prepared into electrolyte.
Then, other than using manufactured cathode 1 in this comparative example and electrolyte, other are with complete with embodiment 4
Lithium rechargeable battery 4 is made in identical mode.
Then, other than using manufactured lithium rechargeable battery 4 in this comparative example, other are with complete with embodiment 4
Exactly the same mode carries out repeated charge to lithium rechargeable battery 4.By charge/discharge capacity relative to charge and discharge cycles number
It is shown in Figure 7 to become the charge-discharge characteristic being turned at this time.
From Fig. 6 it will be apparent that, according to the lithium rechargeable battery for using tin overlay film 31 to be clamped by two current-collectors 21,22
With the lithium rechargeable battery 4 of the embodiment 1 of cathode 1, tin overlay film 31 will not be removed from current-collector 21,22, therefore, even if
The deterioration of capacity can also be inhibited by being repeated after charge and discharge cycles.And on the other hand, it is made only according to tin overlay film 31 is used
Do not have on current-collector 21 but on tin overlay film 31 current-collector 22 thus tin overlay film 31 cathode that is not clamped by current-collector 21,22
The lithium rechargeable battery 4 of comparative example 1, tin overlay film 31 can be removed from current-collector 21, therefore, charge and discharge cycles be repeated
Afterwards, the deterioration of capacity can not be inhibited.
In addition, it is therefore evident that, according to the embodiment for having used the lithium ion secondary battery cathode 1 for having following copper powders 24
2 lithium rechargeable battery 4, can inhibit the deterioration of capacity even if being repeated after charge and discharge cycles, and with implementation
The lithium rechargeable battery 4 of example 1 is compared and improves capacity.Wherein, above-mentioned copper powder 24 has tin plated film 31 on the surface thereof.
In addition, it is therefore evident that, according to the lithium rechargeable battery 4 for the embodiment 3 for having following electrolyte layers 6, even if
The deterioration of capacity can also be inhibited by being repeated after charge and discharge cycles, and compared with the lithium rechargeable battery of embodiment 24 into
One step improves capacity.Wherein, the electrolyte comprising gel rubber material of above-mentioned electrolyte layer 6 is gelled.Include by having
Electrolyte layer 6 that the electrolyte of gel rubber material is gelled and the reasons why capacity is improved, may be considered following reasons：Through
The barrier that the electrolyte of gelation plays the role of the micronized of inhibitory activity substance, active material is spread to electrolyte.
In addition, it will be apparent that, according to the lithium rechargeable battery 4 of embodiment 4, aluminium foil will not be from by nickel plated film from Fig. 7
It is removed on the current-collector of composition, therefore, the deterioration of capacity can be inhibited even if being repeated after charge and discharge cycles.Wherein,
The lithium rechargeable battery 4 of above-described embodiment 4 uses following lithium ion secondary battery cathodes 1：As negative electrode active material
There is the current-collector being made of nickel plated film, negative electrode active material layer to be clamped by two current-collectors on the tow sides of the aluminium foil of layer.
In addition, according to the lithium rechargeable battery 4 for applying example 4, it is formed with nickel plated film using electroless plating method on the tow sides of aluminium foil,
Therefore the oxidation overlay film of aluminium foil surface is removed, so can inhibit side reaction, so as to improve capacity.
On the other hand, it is therefore evident that, according to using aluminium foil as the lithium rechargeable battery 4 of the comparative example 2 of cathode, aluminium foil surface
Oxidation overlay film be not removed, thus side reaction cannot be inhibited, so, the capacity compared with the lithium rechargeable battery 4 of embodiment 4
It tails off.
In addition, it is therefore evident that, according to the lithium rechargeable battery 4 of embodiment 5, even if after charge and discharge cycles are repeated
Also it can inhibit the deterioration of capacity, also, capacity is improved compared with the lithium rechargeable battery of embodiment 44.Wherein,
The lithium rechargeable battery 4 of above-described embodiment 5 uses following lithium ion secondary battery cathodes 1：As negative electrode active material
There is the current-collector being made of nickel plated film, negative electrode active material layer is by two current collections on the tow sides of the alumel foil of matter layer
Device is clamped.
It may be considered by the reasons why making capacity improve using alumel foil as negative electrode active material layer following
Reason：Other than the lithium in aluminium alloy is taken out as capacity, the anti-of the less following formula of volume expansion (2) mainly has occurred
It answers, so that the burden that lithium ion secondary battery cathode 1 is born is mitigated.
2LiAl+Li→Li3Al2···(2)。
Claims (15)
1. a kind of lithium ion secondary battery cathode, which is characterized in that have at least one stepped construction, the stepped construction by
Two current-collectors and the negative electrode active material layer composition being clamped by this two current-collector.
2. lithium ion secondary battery cathode according to claim 1, which is characterized in that
The negative electrode active material layer is made of a kind of material of the group formed selected from tin overlay film, aluminium foil, alloy foil.
3. lithium ion secondary battery cathode according to claim 2, which is characterized in that
The tin overlay film is made of tin plated film.
4. lithium ion secondary battery cathode according to any one of claim 1 to 3, which is characterized in that
The current-collector by metal film coated or surface there is the metal powder of tin plated film to constitute.
5. lithium ion secondary battery cathode according to claim 4, which is characterized in that
It is described metal film coated to be made of metal foil or metal coating.
6. lithium ion secondary battery cathode according to claim 5, which is characterized in that
The metal foil is made of a kind of metal of the group formed selected from aluminium, copper, steel, titanium.
7. lithium ion secondary battery cathode according to claim 5, which is characterized in that
The metal coating is made of tin or nickel.
8. lithium ion secondary battery cathode according to claim 4, which is characterized in that
The metal powder is made of a kind of metal of the group formed selected from aluminium, copper, steel, titanium.
9. lithium ion secondary battery cathode according to claim 1, which is characterized in that
Have at least one laminate structure in the following manner on the 1st current-collector being made of copper foil, the laminate structure by
The negative electrode active material layer being made up of tin plated film and the 2nd current-collector composition being made up of plated copper film, aforesaid way refer to：Make
The 2nd current-collector phase of the negative electrode active material layer and the 1st current-collector or other adjacent laminate structures
To.
10. lithium ion secondary battery cathode according to claim 1, which is characterized in that
Has the layer being made of copper powder on the current-collector being made of copper foil, the copper powder has tin plated film on its surface.
11. lithium ion secondary battery cathode according to claim 1, which is characterized in that
There is nickel plated film in the tow sides for the negative electrode active material layer being made of aluminium foil or alloy foil.
12. a kind of manufacturing method of lithium ion secondary battery cathode, which is characterized in that have：
The 1st step of the negative electrode active material layer being made of tin plated film is formed on by the metal film coated current-collector constituted；With
It is formed by the gold with 1000nm or less thickness ranges on the negative electrode active material layer formed by the 1st step
Belong to the second step for the current-collector that plated film is constituted,
Also, it at least carries out the 1st step and the second step is each primary.
13. a kind of manufacturing method of lithium ion secondary battery cathode, which is characterized in that have：
Tin plated film is formed to obtain the 1st step of the metal powder with tin plated film on the surface on the surface of metal powder；
Prepare the second step of slurry, wherein the slurry includes by having tin plating on the surface that the 1st step is formed
The metal powder of film, and
The slurry prepared by the second step is coated on by the third step on the metal film coated current-collector constituted.
14. a kind of manufacturing method of lithium ion secondary battery cathode, which is characterized in that have：
The collection being made of metal coating is formed on the tow sides for the negative electrode active material layer being made of aluminium foil or alloy foil
The step of electric appliance.
15. a kind of lithium rechargeable battery, which is characterized in that have：
Cathode, anode and electrolyte layer,
The cathode has at least one stepped construction, and the stepped construction is by two current-collectors and by the clamping of this two current-collector
Negative electrode active material layer is constituted；
The negative electrode active material layer of the anode and the cathode configures in opposite directions；
The electrolyte layer configuration is between the cathode and the anode.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2017012582 | 2017-01-26 | ||
| JP2017-012582 | 2017-01-26 | ||
| JP2017236444A JP2018120849A (en) | 2017-01-26 | 2017-12-08 | Negative electrode for lithium ion secondary battery, manufacturing method of the same, and lithium ion secondary battery |
| JP2017-236444 | 2017-12-08 |
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|---|---|
| CN108365171A true CN108365171A (en) | 2018-08-03 |
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| CN201810067959.5A Pending CN108365171A (en) | 2017-01-26 | 2018-01-24 | Lithium ion secondary battery cathode and its manufacturing method and lithium rechargeable battery |
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| CN111916815A (en) * | 2019-05-08 | 2020-11-10 | 宁德时代新能源科技股份有限公司 | Lithium metal battery |
| CN114730888A (en) * | 2020-05-08 | 2022-07-08 | 株式会社Lg新能源 | Negative electrode current collector for lithium-free battery, electrode assembly comprising same, and lithium-free battery |
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| CN204315663U (en) * | 2014-11-12 | 2015-05-06 | 南京中储新能源有限公司 | A kind of aluminium-sulfur battery Graphene coating negative pole |
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| JP2004362809A (en) * | 2003-06-02 | 2004-12-24 | Nissan Motor Co Ltd | Negative electrode for nonaqueous battery, nonaqueous battery using it, and method of manufacturing negative active material |
| JP2011003383A (en) * | 2009-06-18 | 2011-01-06 | Furukawa Battery Co Ltd:The | Manufacturing method of negative electrode for lithium secondary battery, and lithium secondary battery |
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| CN109244599A (en) * | 2018-10-30 | 2019-01-18 | 江苏塔菲尔新能源科技股份有限公司 | A kind of composite negative pole pole piece with rapid heating function and the battery core and battery using it |
| CN111916815A (en) * | 2019-05-08 | 2020-11-10 | 宁德时代新能源科技股份有限公司 | Lithium metal battery |
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