CN108365256A - Lithium rechargeable battery - Google Patents
Lithium rechargeable battery Download PDFInfo
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- CN108365256A CN108365256A CN201810071910.7A CN201810071910A CN108365256A CN 108365256 A CN108365256 A CN 108365256A CN 201810071910 A CN201810071910 A CN 201810071910A CN 108365256 A CN108365256 A CN 108365256A
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- Prior art keywords
- rechargeable battery
- lithium rechargeable
- electrolyte
- cathode
- tin
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
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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 a kind of lithium rechargeable battery.Lithium rechargeable battery according to the present invention carries out charge and discharge in the case of enabling to the overlay film being formed on collector surface not dissolve.Lithium rechargeable battery (1) has cathode (2), positive (3) and electrolyte.Cathode (3) has collector (31) and covers the overlay film (32) on collector (31) surface.The overlay film is the overlay film constituted selected from least one of the group being made of tin, lead, aluminum and zinc metal, and electrolyte includes phosphate ester solvent and supports salt, and pH ranges are 4~10.
Description
Technical field
The present invention relates to lithium rechargeable batteries.
Background technology
It is known in the art that there is a kind of lithium rechargeable battery to have cathode, anode and electrolyte, which has
The overlay film of collector and the negative electrode active material being formed on the collector surface.Theoretical capacity is more than carbon materials by existing research
The tin of material is used for the negative electrode active material of the lithium rechargeable battery.For example, as it is known that a kind of lithium rechargeable battery has
The tin overlay film that thickness is 10~300 μm is formed on the surface of collector using galvanoplastic (referring for example to patent document 1).
And, it is known to use lead (Pb), aluminium (Al), zinc (Zn) are as above-mentioned negative electrode active material (for example, referring to patent text
It offers 2).
In the lithium rechargeable battery of the above-mentioned prior art.It is above-mentioned positive by conducts such as cobalt acid lithium, lithium nickelate, LiMn2O4s
Positive active material, in above-mentioned electrolyte, dissolved with as the fluorine-containing lithium salts for supporting salt in carbonate-based solvent.As above-mentioned
Carbonate-based solvent can be used selected from by propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, γ-fourth
At least one of the group of lactone composition solvent.In addition, as above-mentioned fluorine-containing lithium salts, can use selected from by lithium hexafluoro phosphate, four
At least one of the group of lithium fluoroborate and trifluoromethyl sulfonic acid lithium composition compound.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2001-68094 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2004-95264 bulletins
Invention content
The subject that the invention solves
However, as cathode and using the electricity comprising carbonate-based solvent and support salt in the collector that will have tin overlay film
In the lithium rechargeable battery for solving liquid, have the following problems：Pass through one in the state that the tin overlay film is in contact with the electrolyte
After fixing time, charge and discharge can not be carried out or be equivalent to the durability decline of charge and discharge.
In addition, in the case where above-mentioned collector has any overlay film in lead overlay film, aluminium overlay film, zinc overlay film, there is also with
The identical problem of above-mentioned tin overlay film.
Present invention aims at the above problem is eliminated, it in cathode includes selected from being made of tin, lead, aluminum and zinc to provide a kind of
When at least one of group metal, charge and discharge and the lithium rechargeable battery with excellent charge-discharge characteristic can be also carried out.
The means used to solve the problem
The reason of present inventor is to following situations is studied repeatedly, the situation namely：Surface had into tin overlay film
Collector is as cathode and uses in the lithium rechargeable battery comprising carbonate-based solvent and the electrolyte for supporting salt, in the tin
In the state that overlay film is in contact with the electrolyte, by the case where charge and discharge can not be carried out after a certain period of time.
As a result, it has been found that including the pH of the above-mentioned electrolyte of carbonate-based solvent and support salt makees in 3.1~3.9 degree
For amphoteric metal tin in the state of being in contact with above-mentioned electrolyte, by that can dissolve after a certain period of time.
It is considered that it is because of following reason to generate the above situation：In the shape that above-mentioned tin overlay film is in contact with above-mentioned electrolyte
Under state, dissolving takes place by the boundary part after a certain period of time, being in contact from the electrolyte with the tin overlay film, and tin is molten
Solution gradually carries out, as a result, cause charge and discharge that can not carry out sometimes, or the durability relative to charge and discharge cycles declines.This
In, lead (Pb), aluminium (Al), zinc (Zn) and tin (Sn) equally, belong to amphoteric metal, it is therefore contemplated that by lead (Pb), aluminium
(Al), overlay film the case where being used as negative electrode active material that the mixture of zinc (Zn) or these metals is constituted is also and tin
Overlay film is identical, and when being in contact with above-mentioned electrolyte, above-mentioned overlay film can dissolve, and result may lead to not carry out charge and discharge
Electric or durability relative to charge and discharge cycles declines.Present inventor further studies above-mentioned discovery repeatedly, completes
The present invention.
Therefore, in order to achieve the above object, lithium rechargeable battery of the invention has cathode, anode and is located at cathode
Electrolyte layer between anode, the lithium rechargeable battery be characterized in that, the cathode include selected from by tin, lead, aluminium and
At least one of the group of zinc composition metal, the electrolyte layer include electrolyte, which includes solvent and support salt and pH
Ranging from 4~10.
The present invention lithium rechargeable battery in, the cathode include in the group being made of tin, lead, aluminum and zinc extremely
A kind of few meaning of metal includes following forms：The cathode has covering for collector and the metal that is formed on the collector surface
Film, the plated film is by the form that is constituted selected from least one of the group being made of tin, lead, aluminum and zinc metal；The overlay film is inherently
Selected from least one of the group being made of tin, lead, aluminum and zinc metal or by comprising selected from being made of tin, lead, aluminum and zinc
The form that the alloy of at least one of group metal is constituted.
In addition, above-mentioned cathode can be that have following overlay films above-mentioned metal film coated to substitute.The overlay film passes through following manner
It is formed：Metal powder, binder and carbon material etc. selected from least one of the group being made of tin, lead, aluminum and zinc metal are led
Electric auxiliary agent is distributed in solvent and forms slurry, and the slurry is applied on collector and forms overlay film.At this moment, above-mentioned metal
Powder is preferably provided with the average grain diameter of 10nm~100 μm.
In addition, in the lithium rechargeable battery of the present invention, above-mentioned electrolyte layer can also be that above-mentioned electrolyte is made to soak
Be seeped into the form for the isolation film being made of synthetic resin, can also be make the electrolyte comprising Gelling Materials be infiltrated up to this every
The form of gelation is implemented from film.It can for example be included as above-mentioned Gelling Materials：Polyvinylidene fluoride-hexafluoro third
Polymerization initiators or the polymer such as alkene (PVDF-HFP), (poly-) acrylonitrile, (poly-) acrylic acid, polymethyl methacrylate.In addition,
Including the above-mentioned electrolyte of above-mentioned Gelling Materials implements gelation by heating or using gel triggering agent.
In the lithium rechargeable battery of the present invention, by the pH ranges for the electrolyte for making to include in above-mentioned electrolyte layer
It is 4~10, the mixture as the tin of amphoteric metal, lead, aluminium, zinc or these metals does not dissolve substantially.
So lithium rechargeable battery according to the present invention, though electrolyte included in above-mentioned electrolyte layer with
Including when the cathode selected from least one of the group being made of above-mentioned tin, lead, aluminium, zinc metal is in contact, can also prevent above-mentioned
Any metal, its alloy or its metal powder dissolve.As a result, lithium rechargeable battery according to the present invention, even if
In the state that above-mentioned cathode and above-mentioned electrolyte are in contact and pass through certain time, can also carry out charge and discharge or acquisition
Excellent charge-discharge characteristic.
When the pH of above-mentioned electrolyte is less than 4 or more than 11, by the group formed as the tin, lead, aluminum and zinc of amphoteric metal
At least one of metal, its alloy or its metal powder can dissolve.
In the lithium rechargeable battery of the present invention, preferably above-mentioned solvent includes phosphate.By making above-mentioned solvent packet
Phosphate ester-containing, the electrolyte can be reliably by its pH controls in the range of 4~10.
In addition, in the lithium rechargeable battery of the present invention, above-mentioned phosphate has carbon atom number preferably on side chain
It is 3 alkyl below.It is 3 alkyl below by making above-mentioned phosphate that there is carbon atom number on side chain, appropriateness can be obtained
Viscosity and relative to support the higher solubility of salt.When the carbon atom number of above-mentioned alkyl is more than 3, viscosity then becomes excessively high,
It becomes difficult to be handled.
In the lithium rechargeable battery of the present invention, when above-mentioned cathode tin, lead, aluminum and zinc by comprising selected from being made of
It, can when charge and discharge are repeated to the lithium rechargeable battery in the case that the alloy of at least one of group metal is constituted
Inhibit the deterioration of capacity.This you can think of it because：Metal included in above-mentioned alloy other than tin, lead, aluminium or zinc
Can in cathode tin, lead, aluminium or zinc dilation play the role of buffer；Or included in above-mentioned alloy in addition to
When metal other than tin, lead, aluminium or zinc is the metal not reacted with lithium ion, the metal that does not react with the lithium ion
It can play the role of the skeleton as the electrode structure for keeping cathode.
In such a situation it is preferred to selected from least one of the group being made of tin, lead, aluminum and zinc metal in above-mentioned alloy
Content is 30% or more of the alloy total quality.When in above-mentioned alloy at least one in the group being made of tin, lead, aluminum and zinc
When the content of kind metal is less than the 30% of the alloy total quality, the energy density of lithium rechargeable battery can be caused to decline.
In addition, in the lithium rechargeable battery of the present invention, when above-mentioned electrolyte layer is by comprising Gelling Materials and quilt
When implementing the above-mentioned electrolyte composition of gelation, it is believed that the electrolyte after gelation plays the micro- of inhibitory activity substance
The effect for the barrier that granulation, active material are spread to electrolyte, can improve the capacity of lithium rechargeable battery.
The simple declaration of attached drawing
Fig. 1 is the schematic sectional view of an example for the structure for indicating the lithium rechargeable battery of the present invention.
Fig. 2 be indicate the present invention lithium rechargeable battery in by tinfoil paper or tin alloy foil itself as cathode when charge and discharge
The chart of electrical characteristics.
Fig. 3 be indicate the present invention lithium rechargeable battery in by aluminium foil or alloy foil itself as cathode when charge and discharge
The chart of electrical characteristics.
Fig. 4 is charge-discharge characteristic when having the cathode comprising aluminium powder in the lithium rechargeable battery for indicate the present invention
Chart.
Symbol description
1 lithium rechargeable battery
3 cathode
4 positive (to poles)
6 electrolyte layers
31 collectors
32 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 rechargeable battery 1 of present embodiment have the cathode 3 being disposed in inside battery unit 2,
Anode 4 and the isolation film (separator) 5 between cathode 3 and anode 4.Electrolyte is infiltrated in the isolation film 5 and is formed
Electrolyte layer 6.
Cathode 3 has collector 31 and covers the overlay film 32 of a side surface of collector 31, and overlay film 32 is configured to and is electrolysed
Matter layer 6 is opposite.In addition, being connected with negative wire 33 on collector 31.As long as overlay film 32 covers at least side of collector 31
Surface, overlay film 32 can also cover the tow sides of collector 31.
As long as the conductive material of the collector 31 of cathode 3, thus do not make special restriction to it.Example
Collector 31 such as can be formed using the metal of copper, steel, titanium composition.Collector 31 can use above-mentioned metal or its alloy
Foil, reticulate body or metal otter board etc. can also be used.When collector 31 is the foil of above-mentioned metal or alloy, from order to improve
From the viewpoint of the energy density of battery, the thickness of collector 31 is preferred with thin.But if excessively thin, then it is difficult to at it
Reason, productivity reduce.Therefore the thickness is preferably 1~100 μm of range.
Covering for the mixture of overlay film, these metals that any one metal of tin, lead, aluminum and zinc is separately formed may be used
The overlay film of film or alloy comprising these metals is as overlay film 32.
Overlay film 32 can by plated film selected from least one of the group being made of tin, lead, aluminum and zinc metal, heat, splash
It penetrates the modes such as plated film, vapor deposition and is formed on collector 31.By coating method formed overlay film 32 when, can also use copper,
The metals such as nickel, silver are co-precipitated plated film.
Alternatively, it is also possible to by ultrasonic bonding or it is friction welded make in the group being made of tin, lead, aluminum and zinc it is a kind of
The foil of metal or its alloy is formed onto collector 31, to form overlay film 32.Moreover, overlay film 32 can also pass through following manner
It is formed：Metal powder, binder and carbon material etc. selected from least one of the group being made of tin, lead, aluminum and zinc metal are led
Electric auxiliary agent is distributed in solvent and forms slurry together, and the slurry is applied on collector 31, then implements drying to be formed
Overlay film 32.Above-mentioned metal powder can also be covered by plated films such as nickel, copper, silver, gold.
When overlay film 32 is tin overlay film, such as can be formed by electroless plating method.At this moment, under electroless plating method passes through
Mode is stated to implement：Collector 31 is impregnated in the acid such as nitric acid, hydrochloric acid, sulfuric acid or removes the dirt on surface by washing
It after object, oxidation film etc., is impregnated into plating bath, the liquid temperature that plating is bathed is made to be warming up to set point of temperature, wherein above-mentioned plating bath is logical
It crosses and the pink salts such as stannic chloride and sodium hypophosphite as reducing agent is dissolved into sulfuric acid etc. and are formed.Above-mentioned plating bath can also lead to
It crosses and the pink salts such as stannic chloride and sodium hypophosphite as reducing agent is dissolved into instead of shape in the aqueous slkalis such as the sodium hydroxide of sulfuric acid
At.
Tin overlay film 32 is for example with 10nm less than 50 μm of thickness.The thickness of tin overlay film 32 can pass through above-mentioned plating
The mild dip time of liquid of bath is applied to be managed.
The tin overlay film 32 formed by above-mentioned electroless plating method is the more of the stomata for having pore diameter range and being 0.01~300nm
The porosity of porous material, the porous material is 0.01~20% volume ratio range.
In addition, when overlay film 32 is aluminium overlay film, such as galvanoplastic or electroless plating method can be utilized to be formed.At this moment, it can incite somebody to action
Aluminium chloride etc. is dissolved into the organic solvents such as acetone, ionic liquid, and is used the liquid of formation as plating bath.
It should be noted that the lithium rechargeable battery 1 of present embodiment may not possess overlay film 32, collector 31
Body is exactly any one metal or to be made of the alloy comprising these metals in tin, lead, aluminum and zinc.
On the other hand, the positive-electrode mixture layer that anode 4 has collector 41 and is formed on a side surface of collector 41
42, positive-electrode mixture layer 42 is configured to opposite with electrolyte layer 6.In addition, being connected with positive wire 43 on collector 41.Anode is mixed
As long as closing nitride layer 42 to be formed on an at least side surface for collector 41, positive and negative the two of collector 41 can also be formed in
Face.
As long as the conductive material of the collector 41 of anode 4, does not make special restriction, can use for example
The collector being made of aluminium, copper, steel, titanium etc..Above-mentioned metal or the foil of its alloy may be used in collector 41, can also use net
Shape body or metal otter board etc..It is thick in order to improve the energy density of battery when collector 41 is the foil of above-mentioned metal or alloy
Degree is preferred with thin.But if excessively thin, then it is difficult to handle it, productivity reduces.Therefore preferably above-mentioned thickness is 5~50 μm
Range.
The positive-electrode mixture layer 42 of anode 4 can be formed by following manner：By positive active material and poly- inclined difluoro second
The binders such as alkene (PVDF) mix in right amount, are diluted with N-Methyl pyrrolidone, and the slurry thus made is utilized scraper for coating method
Etc. being coated on collector 41, which is formed by coating.42 preferred positive-active of positive-electrode mixture layer
Substance is higher relative to the containing ratio of total amount, for example, the containing ratio is preferably 85% or more mass percent.In addition, anode is mixed
Nitride layer 42 is closed except comprising the positive active material and the binder, can also include conductive auxiliary agent.
As the positive active material, LiMnO can be enumerated2、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 part in its transition metal replaced by other metals made of compound；LiNi1/3Co1/3Mn1/3O2Etc. specific
Transition metal be no more than the lithium transition-metal oxide of whole half；Make Li and chemistry in these lithium transition-metal oxides
Metering composition is 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 made of the substitutions such as Al, Fe, P, Ti, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La.Particularly,
Preferably LiαNiβCoγAlδO2(+δ=1 β+γ, β >=0.4, γ≤0.2) or LiαNiβCoγMnδO2(+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 two or more
Above compound used.
In addition, as above-mentioned positive active material, iron sulfide, ferrous disulfide, sulphur, polythiaether, Li can also be used3VO4
Deng.Furthermore it is also possible to use the free sills such as the nitroxyl compound for forming nitroxyl free radical part-structure.
As the electrolyte for including in electrolyte layer 6, can use using the phosphate that the following general formula (1) is stated as solvent
And electrolyte obtained from supporting salt is used as dissolved with lithium salts 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, 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 by LiPF5(CF3)、LiPF5(C2F5)、LiPF5
(C3F7)、LiPF4(CF3)2、LiPF4(CF3)(C2F5)、LiPF3(CF3)3Deng.In addition it is also possible to replace above-mentioned lithium salts with sodium salt,
Lithium salts and the sodium salt can also be used in combination.
In addition, as long as the pH of electrolyte is 4~10, then the addition that mass percent is 50% amount 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 by substance etc..
The concentration range of above-mentioned support salt in above-mentioned electrolyte is preferably 0.1~3mol/L, further preferred 0.6~
1.5mol/L。
In the lithium rechargeable battery 1 of present embodiment, above-mentioned electrolyte can be made to be infiltrated up to isolation film 5 and form electricity
Matter layer 6 is solved, can also be that its gel is made by heating after so that the electrolyte for being added to Gelling Materials is infiltrated up to isolation film 5
Change and forms electrolyte layer 6.As isolation film 5, the isolation film being made of synthetic resin such as polyethylene can be used for example.As
Above-mentioned Gelling Materials, such as polyvinylidene fluoride-hexafluoropropene (PVDF-HFP), (poly-) acrylonitrile, (poly-) can be included
The polymer such as acrylic acid, polymethyl methacrylate.It should be noted that can also using polymerization initiator come substitute heat into
The gelation of the above-mentioned Gelling Materials of row.
Then, examples and comparative examples of the present invention are shown.
Embodiment
(embodiment 1)
In the present embodiment, it regard the copper foil (50mm × 50mm) that thickness is 20 μm as collector 31 first, it is clear with sulfuric acid
Its surface is washed, a side surface of above-mentioned copper foil is covered with epoxy glue band, is impregnated in the electroless plating bath for being warming up to 50 DEG C.
The tin overlay film 32 that thickness is 1.1 μm is formed on not shielded surface.Tin overlay film 32 is that have pore diameter range be 0.1~300nm
Stomata porous material, the porosity of the porous material is 0.1%.Then, the collector of tin overlay film 32 will be formd
31 are cut into the size of 26mm × 44mm, to which cathode 3 be made.
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 and is used as
On the aluminium foil (50mm × 50mm) that the thickness of collector 41 is 15 μm, positive-electrode mixture layer 42 is formed.Then, anode will be formd
The collector 41 of mixture layer 42 is cut into the size of 25mm × 44mm, to which anode 4 be made.
Then, cathode 3 and anode 4 between be arranged as isolation film 5 thickness for 25 μm polyethylene separators (30mm ×
Electrolyte layer 6 is vacuum sealed to laminated cell unit obtained from 50mm) and infiltrating electrolyte in the polyethylene separators
(Laminate cell), is made lithium rechargeable battery 1.
Above-mentioned electrolyte uses a kind of following electrolyte：With mixed phosphate triethyl (TEP) be solvent, in the solvent with
The concentration of 1.0mol/L dissolves LiPF6.Here, with pH analyzers, (Horiba Ltd manufactures, name of product：
LAQUA the pH for) measuring the above-mentioned electrolyte at 25 DEG C, it is 9.1 to measure pH.
Then, it will be placed 1 week lithium rechargeable battery 1 obtained in the present embodiment at 25 DEG C.
Then, in the environment of 25 DEG C, with the charging current for charging of 0.1mA until upper boundary potential 4.05V, stops 10 minutes
Afterwards, it is discharged to 2.5V.
In the present embodiment in lithium rechargeable battery 1 obtained, tin overlay film 32 will not dissolve, and can be filled
Electric discharge.
(comparative example 1)
In this comparative example 1, by ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) with 30:
30:40 volume ratio is mixed to form mixed solvent, in addition to use the mixed solvent as the solvent of electrolyte other than, other with
Lithium rechargeable battery 1 is made in 1 exact same way of embodiment.Here, it measures at 25 DEG C in the same manner as example 1
Above-mentioned electrolyte pH, measure pH be 3.1.
Then, it will be placed 1 week lithium rechargeable battery 1 obtained in this comparative example at 25 DEG C.
Then, in the environment of 25 DEG C, with the charging current of 0.1mA to lithium ion secondary electricity obtained in this comparative example
Charging is implemented in pond 1, still, even if charging have passed through 20 hours, also fails to charge to upper boundary potential 4.05V.By in this ratio
It is decomposed compared with lithium rechargeable battery 1 obtained in example, confirms tin overlay film 32 and have occurred that dissolving.
(comparative example 2)
In this comparative example 2, by propylene carbonate (PC) and dimethyl carbonate (DMC) with 50:50 volume ratio mixes shape
At mixed solvent, in addition to use the mixed solvent as the solvent of electrolyte other than, other with 1 identical side of embodiment
Lithium rechargeable battery 1 is made in formula.Here, the pH for measuring the above-mentioned electrolyte at 25 DEG C in the same manner as example 1, is surveyed
It is 3.9 to obtain pH.
Then, it will be placed 1 week lithium rechargeable battery 1 obtained in this comparative example at 25 DEG C.
Then, in the environment of 25 DEG C, with the charging current of 0.1mA to lithium ion secondary electricity obtained in this comparative example
Charging is implemented in pond 1, still, even if charging have passed through 20 hours, also fails to charge to upper boundary potential 4.05V.By in this ratio
It is decomposed compared with lithium rechargeable battery 1 obtained in example, confirms tin overlay film 32 and have occurred that dissolving.
(comparative example 3)
In this comparative example 3, in addition to use propylene carbonate (PC) as the solvent of electrolyte other than, other with implementation
Lithium rechargeable battery 1 is made in 1 exact same way of example.Here, it measures in the same manner as example 1 upper at 25 DEG C
The pH for stating electrolyte, it is 3.2 to measure pH.
Then, it will be placed 1 week lithium rechargeable battery 1 obtained in this comparative example at 25 DEG C.
Then, in the environment of 25 DEG C, with the charging current of 0.1mA to lithium ion secondary electricity obtained in this comparative example
Charging is implemented in pond 1, still, even if charging have passed through 20 hours, also fails to charge to upper boundary potential 4.05V.By in this ratio
It is decomposed compared with lithium rechargeable battery 1 obtained in example, confirms tin overlay film 32 and have occurred that dissolving.
(embodiment 2)
In the present embodiment, thickness is punched into diameter 15mm sizes for 10 μm of tinfoil paper first and forms collector 31,
Collector 31 itself is as cathode 3.
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 on 15 μm of aluminium foil, to be formed that obtained slurry, which is coated on as the thickness of collector 41, using scraper for coating method
Positive-electrode mixture layer 42.Then, the collector 41 for foring positive-electrode mixture layer 42 is punched into the material of diameter 14mm sizes,
To which anode 4 be made.
Then, the polythene material that arranging thickness is 20 μm between cathode 3 and anode 4 is as isolation film (diameter
20mm), electrolyte layer 6 obtained from electrolyte is infiltrated in isolation film 5.And using the electrolyte layer 6 be made coin shape lithium from
Sub- secondary cell 1.During making above-mentioned electrolyte layer 6, following electrolyte are used：With 50:50 volume ratio mixes phosphorus
Triethylenetetraminehexaacetic acid ester (TEP) and dimethyl carbonate (DMC), are made mixed solvent, molten with the concentration of 1.0mol/L in the in the mixed solvent
Solve LiPF6.The pH for measuring above-mentioned electrolyte in the same manner as example 1, it is 4.1 to measure pH.
Then, lithium rechargeable battery 1 made from use in the present embodiment is small by 10 after the secondary cell is made
Shi Hou carries out repeated charge with 1C electric currents under the voltage of 2.5~3.8V ranges to lithium rechargeable battery 1.Electric discharge is held
To be turned to charge-discharge characteristic at this time shown in Figure 2 for the change for measuring relative to charge and discharge cycles number.
(embodiment 3)
In the present embodiment, by triethyl phosphate (TEP) and dimethyl carbonate (DMC) with 75:25 volume ratio mixes shape
At mixed solvent, in addition to use the mixed solvent as the solvent of electrolyte other than, other with 2 identical side of embodiment
Lithium rechargeable battery 1 is made in formula.The pH for measuring above-mentioned electrolyte in the same manner as example 1, it is 7.7 to measure pH.
Then, other than using lithium rechargeable battery 1 obtained in the present embodiment, other are with complete with embodiment 2
Exactly the same mode carries out repeated charge to lithium rechargeable battery 1.And by discharge capacity relative to charge and discharge cycles number
It is shown in Figure 2 to become the charge-discharge characteristic being turned at this time.
(embodiment 4)
In the present embodiment, following collectors 31 are made, in addition to using the collector 31 itself other than cathode 3, remaining
Coin shape lithium rechargeable battery 1 is made with 3 exact same way of embodiment.Wherein, above-mentioned collector 31 passes through following sides
Formula is made：The tin alloy foil that the thickness being made of tin alloy is 10 μm is punched into diameter 15mm sizes and forms the collector
31, the mass percent that above-mentioned tin alloy contains opposite total amount is 10% copper.This reality is measured in the same manner as example 1
The pH for applying the electrolyte used in the lithium rechargeable battery of example, it is 7.7 to measure pH.
Then, other than using lithium rechargeable battery 1 obtained in the present embodiment, other are with complete with embodiment 2
Exactly the same mode carries out repeated charge to lithium rechargeable battery 1.And by discharge capacity relative to charge and discharge cycles number
It is shown in Figure 2 to become the charge-discharge characteristic being turned at this time.
(comparative example 4)
In this comparative example, by triethyl phosphate (TEP) and dimethyl carbonate (DMC) with 40:60 volume ratio mixes shape
At mixed solvent, other than using solvent of the mixed solvent as above-mentioned electrolyte, other are with identical with embodiment 2
Mode coin shape lithium rechargeable battery 1 is made.The pH for measuring above-mentioned electrolyte in the same manner as example 1, measures
PH is 3.7.
Then, other than using lithium rechargeable battery 1 obtained in the present embodiment, other are with complete with embodiment 2
Exactly the same mode carries out repeated charge to lithium rechargeable battery 1.And by discharge capacity relative to charge and discharge cycles number
It is shown in Figure 2 to become the charge-discharge characteristic being turned at this time.
(embodiment 5)
In the present embodiment, thickness is punched into diameter 15mm sizes for 15 μm of aluminium foil and forms collector 31, will collected
Electric body 31 itself is as cathode 3.By triethyl phosphate (TEP) and fluoroethylene carbonate (FEC) with 75:25 volume ratio mixing
Formed mixed solvent, other than using solvent of the mixed solvent as above-mentioned electrolyte, other with 2 complete phase of embodiment
The lithium rechargeable battery 1 of coin shape is made in same mode.The pH of above-mentioned electrolyte is measured in the same manner as example 1,
It is 6.72 to measure pH.
Then, use lithium rechargeable battery 1 obtained through this embodiment, under the voltage of 2.5~4.15V ranges with
1C electric currents carry out repeated charge to lithium rechargeable battery 1.Change by discharge capacity relative to charge and discharge cycles number is turned to
Charge-discharge characteristic at this time is shown in Figure 3.
(embodiment 6)
In the present embodiment, following collectors 31 are made, in addition to using the collector 31 itself other than cathode 3, other
Coin shape lithium rechargeable battery 1 is made with 5 exact same way of embodiment.Wherein, above-mentioned collector 31 passes through following sides
Formula is made：The alloy foil that the thickness being made of aluminium alloy is 15 μm is punched into diameter 15mm sizes and forms the collector
31, the mass percent that above-mentioned aluminium alloy contains opposite total amount is 10% copper.This reality is measured in the same manner as example 1
The pH for applying the electrolyte used in the lithium rechargeable battery of example, it is 6.72 to measure pH.
Then, other than using lithium rechargeable battery 1 obtained in the present embodiment, other are with complete with embodiment 5
Exactly the same mode carries out repeated charge to lithium rechargeable battery 1.And by discharge capacity relative to charge and discharge cycles number
It is shown in Figure 3 to become the charge-discharge characteristic being turned at this time.
(embodiment 7)
In the present embodiment, following collectors 31 are made, in addition to using the collector 31 itself other than cathode 3, other
Coin shape lithium rechargeable battery 1 is made with 5 exact same way of embodiment.Wherein, above-mentioned collector 31 passes through following sides
Formula is made：The alloy foil that the thickness being made of aluminium alloy is 15 μm is punched into diameter 15mm sizes and forms the collector
31, the mass percent that above-mentioned aluminium alloy contains opposite total amount is 15% lithium (Li).Then, with side same as Example 1
Formula measures the pH of the electrolyte used in the lithium rechargeable battery 1 of the present embodiment, and it is 6.72 to measure pH.
Then, other than using lithium rechargeable battery 1 obtained in the present embodiment, other are with complete with embodiment 5
Exactly the same mode carries out repeated charge to lithium rechargeable battery 1.And by discharge capacity relative to charge and discharge cycles number
It is shown in Figure 3 to become the charge-discharge characteristic being turned at this time.
(embodiment 8)
In the present embodiment, following electrolyte are prepared：With 75:25 volume ratio mixed phosphate triethyl (TEP) and fluoro
Ethylene carbonate (FEC), is made mixed solvent, dissolves LiPF in the in the mixed solvent with the concentration of 1.2mol/L6It is formed afterwards
Solution is with polyvinylidene fluoride-hexafluoropropene (PVDF-HFP) as Gelling Materials with 90:After 10 mass ratio mixing, obtain
To above-mentioned electrolyte.
Then, other than using the electrolyte comprising above-mentioned Gelling Materials, other are with identical with embodiment 5
The lithium rechargeable battery 1 of coin shape is made in mode.The pH for measuring above-mentioned electrolyte in the same manner as example 1, measures
PH is 6.3.In the present embodiment, it is kept for 1 hour at a temperature of lithium rechargeable battery 1 being placed in 60 DEG C, makes above-mentioned electrolysis
Pension gelation and after forming electrolyte layer 6, returns to and is placed at room temperature for 10 hours.
Then, other than using lithium rechargeable battery 1 obtained in the present embodiment, other are with complete with embodiment 5
Exactly the same mode carries out repeated charge to lithium rechargeable battery 1.And by discharge capacity relative to charge and discharge cycles number
It is shown in Figure 3 to become the charge-discharge characteristic being turned at this time.
(comparative example 5)
In this comparative example, by ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate with 30:30:40 volume ratio is mixed
Conjunction forms mixed solvent, and other than using solvent of the mixed solvent as above-mentioned electrolyte, other are with complete with embodiment 5
Coin shape lithium rechargeable battery 1 is made in identical mode.The pH of above-mentioned electrolyte is measured in the same manner as example 1,
It is 3.1 to measure pH.
Then, other than using lithium rechargeable battery 1 obtained in this comparative example, other are with complete with embodiment 5
Exactly the same mode carries out repeated charge to lithium rechargeable battery 1.And by discharge capacity relative to charge and discharge cycles number
It is shown in Figure 3 to become the charge-discharge characteristic being turned at this time.
(embodiment 9)
In the present embodiment, first by aluminium powder (grain size 150nm), as the acetylene black of conductive auxiliary agent and as binder
Polyvinylidene fluoride (PVDF) with 80:10:It is distributed in n-methyl-2-pyrrolidone (NMP), makes after 10 mass ratio mixing
At slurry.At this moment, the mass ratio of conductive auxiliary agent/binder is 1.It is 10 that above-mentioned slurry, which is applied to as the thickness of collector 31,
μm copper foil on, formed overlay film 32.Then, the collector 31 for foring overlay film 32 is cut into diameter 15mm, cathode 3 is made.
Then, anode 4 is made in the same way as in example 2.
Then, with 75:25 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 1.0mol/L6, it is prepared into electrolyte.
Then, in addition to using manufactured cathode 3 and anode 4 in the present embodiment and preparing in the present embodiment above-mentioned
Other than electrolyte, other with 2 exact same way of embodiment to be made coin shape lithium rechargeable battery 1.With with embodiment 1
Identical mode measures the pH of above-mentioned electrolyte, and it is 6.72 to measure pH.
Then, use lithium rechargeable battery 1 obtained in the present embodiment, under the voltage of 2.5~4.0V ranges with
1C electric currents carry out repeated charge to lithium rechargeable battery 1.Change by discharge capacity relative to charge and discharge cycles number is turned to
Charge-discharge characteristic at this time is shown in Figure 4.
(embodiment 10)
In the present embodiment, first by aluminium powder (grain size 150nm), as the acetylene black of conductive auxiliary agent and as binder
Polyvinylidene fluoride (PVDF) with 85:5:10 mass ratio is mixed, other with 9 exact same way system of embodiment
At slurry.At this moment, the mass ratio of conductive auxiliary agent/binder is 0.5.Then, using above-mentioned slurry, so that containing in overlay film 32
The amount mode same as Example 9 of aluminium form overlay film 32.In addition to this, to be made with 9 exact same way of embodiment
Coin shape lithium rechargeable battery 1.Then, the lithium ion two for being used in the present embodiment is measured in the same manner as example 1
The pH of electrolyte in primary cell 1, it is 6.72 to measure pH.
Then, other than using lithium rechargeable battery 1 obtained in the present embodiment, other are with complete with embodiment 9
Exactly the same mode carries out repeated charge to lithium rechargeable battery 1.Change by discharge capacity relative to charge and discharge cycles number
The charge-discharge characteristic being turned at this time is shown in Figure 4.
(comparative example 6)
In this comparative example, by ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate with 30:30:40 volume ratio is mixed
Conjunction forms mixed solvent, and other than using solvent of the mixed solvent as above-mentioned electrolyte, other are with complete with embodiment 9
Lithium rechargeable battery 1 is made in identical mode.At this moment, the mass ratio of conductive auxiliary agent/binder is 1.With same as Example 1
Mode measure the pH of above-mentioned electrolyte, it is 3.1 to measure pH.
Then, other than using lithium rechargeable battery 1 obtained in this comparative example, other are with complete with embodiment 9
Exactly the same mode carries out repeated charge to lithium rechargeable battery 1.And by discharge capacity relative to charge and discharge cycles number
It is shown in Figure 4 to become the charge-discharge characteristic being turned at this time.
(embodiment 11)
In the present embodiment, thickness is punched into diameter 15mm sizes for 20 μm of aluminium foil first and forms collector 31,
And using collector 31 itself as cathode 3.Then, thickness is punched into diameter 16mm sizes for 50 μm lithium (Li) foil to be formed
Collector 41, and using collector 41 itself as to pole 4.Then, in addition to using above-mentioned cathode 3 and to pole 4 and with 75:25
Volume ratio mixed phosphate triethyl (TEP) and the mixed solvent that is formed afterwards of fluoroethylene carbonate (FEC) as above-mentioned electrolysis
Except the solvent of liquid, other are the lithium rechargeable battery 1 of coin shape to be made with 5 exact same way of embodiment.And with
1 identical mode of embodiment measures the pH of above-mentioned electrolyte, and it is 6.72 to measure pH.
Then, use lithium rechargeable battery 1 obtained through this embodiment, under the voltage of 0.1~2.5V ranges with
0.1C electric currents to 1 cycle charge-discharge of lithium rechargeable battery twice.The appearance of electric discharge and charging when then, by charge and discharge at this time
Amount is shown in Table 1.
(comparative example 7)
In this comparative example, by ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate with 30:30:40 volume ratio is mixed
Conjunction forms mixed solvent, and other than using solvent of the mixed solvent as above-mentioned electrolyte, other are with complete with embodiment 11
The lithium rechargeable battery 1 of coin shape is made in exactly the same mode.Above-mentioned electrolyte is measured in the same manner as example 1
PH, it is 3.1 to measure pH.
Then, other than using lithium rechargeable battery 1 obtained in this comparative example, other are with complete with embodiment 11
Exactly the same mode carries out cycle charge-discharge twice to lithium rechargeable battery 1.Electric discharge when then, by charge and discharge at this time and
The capacity of charging is shown in Table 1.
(table 1)
(embodiment 12)
In the present embodiment, in addition to use thickness be 20 μm of zinc foil as collector 31 other than, other with embodiment
The lithium rechargeable battery 1 of coin shape is made in 11 exact same ways.It measures in the same manner as example 1 and is used in this
The pH of electrolyte in the lithium rechargeable battery 1 of embodiment, it is 6.72 to measure pH.
Then, use lithium rechargeable battery 1 obtained in this comparative example, under the voltage of 0.1~2.5V ranges with
0.1C electric currents carry out charge and discharge to lithium rechargeable battery 1.Also, by efficiency for charge-discharge (charging capacity/put for the first time at this time
Capacitance) it is shown in Table 2.
(comparative example 8)
In this comparative example, by ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) with 30:
30:40 volume ratio is mixed to form mixed solvent, other than using solvent of the mixed solvent as above-mentioned electrolyte, other
The lithium rechargeable battery 1 of coin shape to be made with 12 exact same way of embodiment.It surveys in the same manner as example 1
The pH of fixed above-mentioned electrolyte, it is 3.1 to measure pH.
Then, other than using lithium rechargeable battery 1 obtained in this comparative example, other are with complete with embodiment 12
Exactly the same mode carries out charge and discharge to lithium rechargeable battery 1.Also, (charging is held by efficiency for charge-discharge for the first time at this time
Amount/discharge capacity) it is shown in table 2.
(table 2)
| Embodiment 12 | Comparative example 8 | |
| Coulombic efficiency (%) for the first time | 63 | 26 |
It will be apparent that according to the lithium rechargeable battery 1 of following embodiments 1, even if be in contact with electrolyte in cathode 3
Pass through 1 week under state, also can carry out charge and discharge in the case where tin overlay film 32 does not dissolve.Wherein, above-described embodiment 1
In lithium rechargeable battery 1, the tin overlay film 32 that cathode 3 has collector 31 and is formed on 31 surface of collector, electrolyte layer 6
The pH of the electrolyte contained is 9.1.
On the other hand, it is therefore evident that, according to the lithium rechargeable battery 1 of following comparative examples 1~3, in cathode 3 and electrolyte
Pass through 1 week in the state of being in contact, tin overlay film 32 is dissolved, and can not be charged.Wherein, in above-mentioned comparative example 1~3
Lithium rechargeable battery 1 in, cathode 3 has collector 31 and the tin overlay film 32 that is formed on 31 surface of collector, electrolyte
The pH for the electrolyte that layer 6 contains is less than 4 3.1~3.9 range.
In addition, it will be apparent that, being to be made of tinfoil paper and the pH of electrolyte that electrolyte layer 6 contains according to cathode 3 from Fig. 2
It is the lithium rechargeable battery 1 of the embodiment 2,3 of 4.1~7.7 ranges, even if can if being repeated after charge and discharge cycles
Enough inhibit the deterioration of capacity；And it is to be made of tin alloy foil and the pH of electrolyte that electrolyte layer 6 contains is 7.7 according to cathode 3
Embodiment 4 lithium rechargeable battery 1, have the effect of in terms of further suppressing capacity deterioration excellent.
On the other hand, it is therefore evident that, it is to be made of tinfoil paper and the pH of electrolyte that electrolyte layer 6 contains is according to cathode 3
The lithium rechargeable battery 1 of 3.7 comparative example 4 less than 4, when charge and discharge cycles are repeated, the deterioration of capacity is notable.
In addition, it will be apparent that, being made of aluminium foil or alloy foil according to cathode 3 from Fig. 3 and electrolyte layer 6 containing
The pH of electrolyte is the lithium rechargeable battery 1 of the embodiment 5~8 of 6.3~6.72 ranges, even if charge and discharge have been repeated
After cycle, it can also inhibit the deterioration of capacity.Further, it is the embodiment 7 being made of Li- alloy foils according to cathode 3
The lithium rechargeable battery 1 for the embodiment 8 that lithium rechargeable battery 1 or electrolyte comprising Gelling Materials are gelled,
Compared to the lithium rechargeable battery 1 of embodiment 5,6, capacity can be improved.
The lithium of the capacity and embodiment 5,6 of the lithium rechargeable battery 1 for the embodiment 7 that cathode 3 is made of Li- alloy foils
The reasons why ion secondary battery 1 is improved compared to acquisition is you can think of it because following reason：In addition to the lithium in aluminium alloy is by conduct
Except capacity takes out, the reaction of the less following formula of volume expansion (2) mainly has occurred, so that the burden that cathode 3 is born
It is mitigated.
2LiAl+Li→Li3Al2···(2)
In addition, the capacity of the lithium rechargeable battery 1 for the embodiment 8 that the electrolyte comprising Gelling Materials is gelled with
The lithium rechargeable battery 1 of embodiment 5,6 is compared to obtaining the reasons why improving you can think of it because following reason：With embodiment
5,6 lithium rechargeable battery 1 is compared to obtaining the reasons why improving you can think of it because following reason：Electrolysis through gelation
The barrier that liquid plays the role of the micronized of inhibitory activity substance, active material is spread to electrolyte.
On the other hand, it is therefore evident that, it is to be made of aluminium foil and the pH of electrolyte that electrolyte layer 6 contains is according to cathode 3
The lithium rechargeable battery 1 of 3.1 comparative example 5 less than 4, when charge and discharge cycles are repeated, the deterioration of capacity is notable.
In addition, it will be apparent that, according to the lithium rechargeable battery 1 of embodiment 9,10, being able to confirm that charge and discharge from Fig. 4
Work.Wherein, in embodiment 9,10, cathode 3 has the overlay film 32 being made of aluminium powder, conductive auxiliary agent and binder, electrolysis
The pH for the electrolyte that matter layer 6 contains is 6.72.Here, conductive auxiliary agent/binder (mass ratio) is that 1 embodiment 9 is helped with conduction
Agent/binder (mass ratio) is that 0.5 embodiment 10 is compared, and cycle capacity maintenance rate higher, therefore, the composition of embodiment 9 is more
For ideal.That is, conductive auxiliary agent/binder (mass ratio) is bigger than 0.5, then it is even more ideal.
On the other hand, it is therefore evident that, according to the lithium rechargeable battery 1 of comparative example 6, carrying out charge and discharge cycles the 3rd time
Later, it is virtually impossible to obtain charge/discharge capacity, the deterioration of capacity is notable.Wherein, in comparative example 6, cathode 3 has by aluminium powder
The overlay film 32 that end, conductive auxiliary agent and binder are constituted, the pH for the electrolyte that electrolyte layer 6 contains are less than the 3.1 of 4.Comparative example 6
Lithium rechargeable battery 1 carried out the reasons why obtaining capacity almost without method after the 3rd time in charge and discharge cycles and may be considered
Because of following reason：3.1 electrolyte that the aluminium powder contained in overlay film 32 is less than 4 by pH dissolves, and causes cathode 3 can not
Play the effect as cathode 3.
In addition, it will be apparent that, being to be made of lead foil and the pH of electrolyte that electrolyte layer 6 contains is according to cathode 3 from table 1
The lithium rechargeable battery 1 of 6.72 embodiment 11, after charge and discharge cycles proceed to the 2nd time, lead foil is also no to be dissolved,
Thus obtain capacity.
And on the other hand, it is therefore evident that, it is to be made of lead foil and the pH of electrolyte that electrolyte layer 6 contains according to cathode 3
It is less than the lithium rechargeable battery 1 of the comparative example 7 of the 3.1 of 4, when charge and discharge cycles proceed to the 2nd time, it is virtually impossible to obtain
Capacity.The reasons why lithium rechargeable battery 1 of comparative example 7 can not almost obtain capacity when proceeding to the 2nd charge and discharge cycles
You can think of it because following reason：3.1 electrolyte that the cathode 3 being made of lead foil is less than 4 by pH dissolves, and leads
It causes that the effect as electrode can not be played.
In addition, it will be apparent that, being to be made of zinc foil and the pH of electrolyte that electrolyte layer 6 contains according to cathode 3 from table 2
It is the lithium rechargeable battery 1 of 6.72 embodiment 12, the pH of the electrolyte contained with electrolyte layer 6 is less than the 3.1 of 4 ratio
Lithium rechargeable battery 1 compared with example 8 is compared, and coulombic efficiency (coulombic efficiency) for the first time is significantly improved.Than
Compared in the lithium rechargeable battery 1 of example 8 for the first time the relatively low reason of coulombic efficiency you can think of it because following reason：By zinc foil
3.1 electrolyte that the cathode 3 of composition is less than 4 by pH dissolves, so as to cause the effect that can not be played as electrode.
Claims (12)
1. a kind of lithium rechargeable battery has cathode, anode and the electrolyte layer between cathode and anode, the lithium
Ion secondary battery is characterized in that,
The cathode includes to be selected from least one of the group being made of tin, lead, aluminum and zinc metal,
The electrolyte layer includes electrolyte, which includes solvent and support salt and pH ranging from 4~10.
2. lithium rechargeable battery according to claim 1, which is characterized in that
The solvent includes phosphate.
3. lithium rechargeable battery according to claim 2, which is characterized in that
It is 3 alkyl below that the phosphate has carbon atom number on side chain.
4. lithium rechargeable battery according to claim 3, which is characterized in that
The phosphate is one in the group being made of trimethyl phosphate, triethyl phosphate, tricresyl phosphate (trifluoroethyl) ester
Kind compound.
5. lithium rechargeable battery according to claim 1, which is characterized in that
The cathode has the overlay film of collector and the metal being formed on the surface of the collector,
The overlay film selected from least one of the group being made of tin, lead, aluminum and zinc metal by constituting.
6. lithium rechargeable battery according to claim 5, which is characterized in that
The overlay film is that 10nm is constituted less than 50 μm of plated film by thickness range.
7. lithium rechargeable battery according to claim 1, which is characterized in that
The cathode selected from least one of the group being made of tin, lead, aluminum and zinc metal by constituting.
8. lithium rechargeable battery according to claim 1, which is characterized in that
The cathode is made of alloy, which includes selected from least one of the group being made of tin, lead, aluminum and zinc metal.
9. lithium rechargeable battery according to claim 8, which is characterized in that
Content selected from least one of the group being made of tin, lead, aluminum and zinc metal in the alloy is the alloy total quality
30% or more.
10. lithium rechargeable battery according to claim 1, which is characterized in that the electrolyte layer is by including the electricity
The isolation film for solving liquid is constituted.
11. lithium rechargeable battery according to claim 10, which is characterized in that
The electrolyte includes Gelling Materials and has been carried out gelation.
12. lithium rechargeable battery according to claim 11, which is characterized in that
The Gelling Materials are selected from by polyvinylidene fluoride-hexafluoropropene, (poly-) acrylonitrile, (poly-) acrylic acid and poly- methyl
A kind of compound in the group of methyl acrylate composition.
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| JP2017012578 | 2017-01-26 | ||
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| JP2017-236443 | 2017-12-08 | ||
| JP2017236443A JP2018120848A (en) | 2017-01-26 | 2017-12-08 | Lithium ion secondary battery |
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