CN110521049A - Semisolid electrolyte, electrode, electrode and secondary cell with semisolid electrolyte layer - Google Patents
Semisolid electrolyte, electrode, electrode and secondary cell with semisolid electrolyte layer Download PDFInfo
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- CN110521049A CN110521049A CN201880023968.2A CN201880023968A CN110521049A CN 110521049 A CN110521049 A CN 110521049A CN 201880023968 A CN201880023968 A CN 201880023968A CN 110521049 A CN110521049 A CN 110521049A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0045—Room temperature molten salts comprising at least one organic ion
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- H01M2300/0085—Immobilising or gelification of electrolyte
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Abstract
It is an object of the invention to improve the service life of secondary cell.A kind of semisolid electrolyte, it includes semisolid electrolyte and particle containing semisolid electrolyte solvent and cathode interface additive, the weight of cathode interface additive is 0.6%~11.7% relative to the weight ratio of the sum of the weight of semisolid electrolyte and the weight of applied cathode.It is preferred that the weight of applied cathode interface additive is 1.7 weight of weight %~5.8 % relative to the weight ratio of the sum of the weight of semisolid electrolyte and the weight of cathode.In the secondary cell containing semisolid electrolyte, the capacity maintenance rate of the secondary cell when capacity maintenance rate of the secondary cell preferably after regulation time circulation is greater than without cathode interface additive.
Description
Technical field
The present invention relates to semisolid electrolyte, electrode, electrodes and secondary cell with semisolid electrolyte layer.
Background technique
As existing nonaqueous electrolytic solution secondary battery, a kind of nonaqueous electrolytic solution charge storage element is disclosed in patent document 1,
Comprising: the anode for the positive active material for being inserted into and being detached from containing anion, containing cation be inserted into and be detached from
Negative electrode active material cathode and dissolving electrolyte salt in nonaqueous solvents and formed nonaqueous electrolytic solution, which is characterized in that
In above-mentioned nonaqueous solvents, the linear carbonate and 0.1~15.0 of 85.0~99.9 mass % is contained relative to nonaqueous solvents total amount
The cyclic carbonate of quality %, above-mentioned cyclic carbonate at least contain fluoric cyclic carbonate, the electricity in above-mentioned nonaqueous electrolytic solution
The concentration for solving matter salt is 2mol/L or more.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2016-058252 bulletin
Summary of the invention
Problems to be solved by the invention
, it is specified that amount of the fluoric cyclic carbonate relative to nonaqueous solvents weight in the method for patent document 1, so two
The service life of primary cell is difficult to improve.
It is an object of the invention to improve the service life of secondary cell.
A technical solution to solve project
Feature of the invention for solving the above subject is for example as described below.
A kind of semisolid electrolyte, it includes contain the semisolid of semisolid electrolyte solvent and cathode interface additive electricity
Liquid and particle are solved, the weight of cathode interface additive is relative to the weight of semisolid electrolyte and the weight of applied cathode
The sum of amount is 0.6%~11.7%.
This specification includes Japanese patent application No. 2017-117337 public affairs of the basis for priority as the application
Open content.
Invention effect
In accordance with the invention it is possible to improve the service life of secondary cell.Project, structure and effect other than the above will be by following
Embodiment explanation and definitely.
Detailed description of the invention
Fig. 1 is the outside drawing of secondary cell.
Fig. 2 is the sectional view of secondary cell.
Fig. 3 is the table for indicating the result of embodiment and comparative example.
Fig. 4 is the relational graph of deterioration factor Yu cathode interface additive weight ratio.
Fig. 5 is the relational graph of cathode interface additive weight ratio Yu initial discharge capacity.
Fig. 6 is the relational graph of initial discharge capacity Yu cathode bulk density.
Fig. 7 is the relational graph of cathode bulk density Yu cathode interface additive weight ratio.
Specific embodiment
Hereinafter, using attached drawing etc., embodiments of the present invention will be described.The following description indicates the contents of the present invention
Concrete example, the present invention do not illustrate to limit by these, the art technology in the range of technical idea of this disclosure
Personnel are able to carry out various changes and amendment.In addition, for illustrating in whole attached drawings of the invention, portion with the same function
Minute mark infuses the same symbol, omits its repeat description sometimes.
"~" recorded in this specification indicates meaning of the numerical value recorded including its front and back as lower limit value and upper limit value.
In the numberical range periodically recorded in the present specification, the upper limit or lower limit recorded in a numberical range can be replaced
It is changed to another upper limit or lower limit periodically recorded.The upper limit value or lower limit for the numberical range recorded in this specification
Value also could alternatively be value shown in embodiment.
In the present specification, it is illustrated by taking lithium ion secondary battery as an example as secondary cell.Lithium ion secondary battery
Be can be stored by occlusion/release of electrode of the lithium ion into nonaqueous electrolyte or using electric energy electrochemical appliance.
Alias is referred to as lithium ion battery, non-aqueous electrolyte secondary battery, nonaqueous electrolytic solution secondary battery, these batteries are all the present invention
Object.Technical idea of the invention is other than it can be applied to lithium ion secondary battery, additionally it is possible to be applied to sodium ion two
Primary cell, magnesium ion secondary cell, aluminium ion secondary cell etc..
Fig. 1 is the outside drawing of the secondary cell of an embodiment of the invention.Fig. 2 is an embodiment of the invention
Secondary cell sectional view.Fig. 1 and Fig. 2 is laminated secondary cell, secondary cell 1000 have anode 100, cathode 200,
Exterior body 500 and semisolid electrolyte layer 300.Exterior body 500 accommodates semisolid electrolyte layer 300, positive 100, cathode 200.
As the material of exterior body 500, there can be corrosion proof material for nonaqueous electrolyte selected from aluminium, stainless steel, nickel-plated steel etc..
The present invention can also be applied to winding-type secondary cell.
Lamination has the electrode body being made of anode 100, semisolid electrolyte layer 300, cathode 200 in secondary cell 1000
400.Sometimes anode 100 or cathode 200 are known as electrode or electrode for secondary battery.Sometimes by anode 100, cathode 200 or half
Solid electrolyte layer 300 is known as secondary cell sheet material.Sometimes by semisolid electrolyte layer 300 and anode 100 or cathode 200 1
The structure of body is known as having the electrode of semisolid electrolyte layer.Electrode with semisolid electrolyte layer, which has, contains semisolid
The semisolid electrolyte layer and electrode of electrolyte, electrode are preferably cathode.
Anode 100 has positive electrode collector 120 and positive electrode material mixture layer 110.It is formed with just on the two sides of positive electrode collector 120
Pole mixture layer 110.Cathode 200 has negative electrode collector 220 and anode mixture layer 210.It is formed on the two sides of negative electrode collector 220
There is anode mixture layer 210.Sometimes positive electrode material mixture layer 110 or anode mixture layer 210 are known as electrode composition layer, by positive electrode collector
120 or negative electrode collector 220 be known as electrode collector.
Positive electrode collector 120 has positive terminal portion 130.Negative electrode collector 220 has anode connector portion 230.Sometimes will
Positive terminal portion 130 or anode connector portion 230 are known as electrode contact portion.Electrode composition layer is not formed in electrode contact portion.But
In the range of will not cause adverse effect to the performance of secondary cell 1000, electrode composition can also be formed in electrode contact portion
Layer.Positive terminal portion 130 and anode connector portion 230 are to external prominent, multiple positive terminal portions 130 outstanding of exterior body 500
Each other, multiple anode connector portions 230 ultrasonic fusing each other such as by engaging, thus in secondary cell 1000
Interior formation is connected in parallel.The present invention can also apply to constitute in secondary cell 1000 be electrically connected in series it is ambipolar secondary
Battery.
Positive electrode material mixture layer 110 has positive active material, positive conductive agent and positive electrode binder.Anode mixture layer 210 has
There are negative electrode active material, cathode conductive agent and negative electrode binder.Semisolid electrolyte layer 300 has semisolid electrolyte adhesive
With semisolid electrolyte.Semisolid electrolyte contains particle and semisolid electrolyte.Sometimes positive active material or cathode is living
Property substance is known as electrode active material, and positive conductive agent or cathode conductive agent are known as electrodes conduct agent, by positive electrode binder or
Negative electrode binder is known as electrode adhesive.
Semisolid electrolyte can be filled into the pore of electrode composition layer.In this case, from the sky of package body 500
One side or liquid injection hole to secondary cell 1000 inject semisolid electrolyte, so that semisolid electrolyte is filled in electrode composition layer
In pore.In such a case it is not necessary to particle contained by semisolid electrolyte, electrode active material in electrode composition layer and
The particles such as electrodes conduct agent play the function of particle, these particles keep semisolid electrolyte.As in the thin of electrode composition layer
In hole fill semisolid electrolyte other methods, have preparation by semisolid electrolyte, electrode active material, electrodes conduct agent,
The slurry that electrode adhesive mixes, the method etc. slurry obtained being coated on together on electrode collector.
Forming semisolid electrolyte used in semisolid electrolyte layer 300 is by semisolid electrolyte and SiO2Equal particles
The material mixed, the semisolid electrolyte contain: dissolved with electrolytic salts such as lithium salts in ether solvent or ionic liquid
Semisolid electrolyte solvent, cathode interface additive and optional low viscosity organic solvent.Semisolid electrolyte layer 300 at
In addition to this medium transmitted between anode 100 and cathode 200 for lithium ion also functions to the effect of electronic body, prevents
The short circuit of anode 100 and cathode 200.
The diaphragms such as microporous membrane also can be used in semisolid electrolyte layer 300.As diaphragm, it is able to use polyethylene or poly-
The polyolefin such as propylene or glass fibre etc..In the case where diaphragm uses microporous membrane, pass through one side of the sky from exterior body 500
Or liquid injection hole injects semisolid electrolyte to secondary cell 1000, semisolid electrolyte is filled in semisolid electrolyte layer 300.
Only either one or two of anode 100, cathode 200 or semisolid electrolyte layer 300 it can contain half above admittedly
Body electrolyte.
< electrodes conduct agent >
Electrodes conduct agent can be improved the electric conductivity of electrode composition layer.As electrodes conduct agent, it is preferable to use Ketjen black, second
Acetylene black etc., but not limited to this.
< electrode adhesive >
Electrode adhesive bonds electrode active material and electrodes conduct agent in electrode etc..It, can as electrode adhesive
To enumerate SBR styrene butadiene rubbers, carboxymethyl cellulose, Kynoar (PVDF) and their mixture etc., but not
It is limited to this.
< positive active material >
The positive active material lithium ion disengaging during the charging process for showing high potential, is closed from cathode during discharge
The lithium ion insertion that the negative electrode active material of oxidant layer is detached from.Material as a positive electrode active material, preferably comprises transition metal
Lithium composite xoide can enumerate LiMO as concrete example2, Li surplus composition Li [LiM] O2、LiM2O4、LiMPO4、
LiMVOx、LiMBO3、Li2MSiO4(wherein, M=contains Co, Ni, Mn, Fe, Cr, Zn, Ta, Al, Mg, Cu, Cd, Mo, Nb, W, Ru
Deng at least one of more than).Also, a part of the oxygen in these materials could alternatively be the other elements such as fluorine.It can be with
It enumerates: sulphur, TiS2、MoS2、Mo6S8、TiSe2Equal chalcogen compounds or V2O5Equal vanadium system oxide, FeF3Equal halide are constituted
Fe (the MoO of polyanion4)3、Fe2(SO4)3、Li3Fe2(PO4)3Deng, quinone system organic crystal etc., but not limited to this.Also, chemistry
Lithium or anion amount in composition can deviate above-mentioned fixed than composition.
120 > of < positive electrode collector
As positive electrode collector 120,10~100 μm of thickness of aluminium foil can be used or 10~100 μm of thickness and there is hole
The aluminum perforated foil in the hole of 0.1~10mm of diameter, expansion of metal net, foam metal plate etc., material can also use in addition to aluminum
Stainless steel, titanium etc..There is no limit be able to use arbitrary positive electrode collector 120 for material, shape, manufacturing method etc..
< negative electrode active material >
Lithium ion is detached from negative electrode active material during discharge, during the charging process from positive electrode material mixture layer 110 just
The lithium ion insertion that pole active material is detached from.As the material for the negative electrode active material for showing low potential, such as it is able to use
Carbon materials (such as graphite, easy graphitized carbon material, amorphous carbon material, organic crystal, active carbon etc.), electroconductive polymer
Material (such as polyacene, polyparaphenylene, polyaniline, polyacetylene), lithium composite xoide (such as lithium titanate: Li4Ti5O12Or
Li2TiO4Deng), lithium metal, with the metal (such as containing more than at least one of aluminium, silicon, tin etc.) of lithium alloyage or they
Oxide, but not limited to this.
220 > of < negative electrode collector
As negative electrode collector 220,10~100 μm of thickness of copper foil, 10~100 μm of thickness and aperture 0.1 can be used
The copper perforated foil of~10mm, expansion of metal net, foam metal plate etc..Stainless steel, titanium, nickel can also be used in addition to copper
Deng.There is no limit be able to use arbitrary negative electrode collector 220 for material, shape, manufacturing method etc..
< electrode >
By using scraper method, infusion process, spray coating method etc. make electrode active material, electrodes conduct agent, electrode adhesive and
The electrode slurry that organic solvent is obtained by mixing is attached on electrode collector, and electrode composition layer is made.Later, make organic solvent
It is dry, electrode composition layer is press-formed using roll squeezer, thus makes electrode.It can be electrolysed containing semisolid in electrode slurry
Liquid or semisolid electrolyte.It can also be multiple in electrode collector superimposed layer by carrying out repeatedly from being applied to dry operation
Electrode composition layer.The thickness of preferred electrode mixture layer is more than the average grain diameter of electrode active material.In the thickness of electrode composition layer
Hour is spent, the electronic conductivity that may cause between adjacent electrode active material is deteriorated.
< particle >
As particle, from the viewpoint of electrochemical stability, preferred insulating properties particle, and insoluble in containing organic molten
The semisolid electrolyte of agent or ionic liquid.As particle, such as it is preferable to use silica (SiO2) particle, gama-alumina
(Al2O3) particle, ceria (CeO2) particle, zirconium dioxide (ZrO2) the oxide inorganics particle such as particle.As particle,
Solid electrolyte can be used.As solid electrolyte, such as oxide system solid electrolyte or sulfide-based solid can be enumerated
The particle of inorganic system's solid electrolyte such as body electrolyte.
It is considered that the maintenance dose of semisolid electrolyte is directly proportional to the specific surface area of particle, it is advantageous to the primary of particle
The average grain diameter of particle is 1nm~10 μm.When the average grain diameter of the primary particle of particle is big, there are particles suitably to keep
A possibility that formation of an adequate amount of semisolid electrolyte, semisolid electrolyte becomes difficult.In addition, the primary particle of particle
Average grain diameter hour, power increases, is easy aggregation, the formation of semisolid electrolyte change between particle between depositing surface between particles
Obtain a possibility that difficult.The average grain diameter of the primary particle of particle is more preferably 1nm~50nm, and further preferably 1nm~
10nm.The average grain diameter of the primary particle of particle is able to use the well known particle size distribution analyzer survey using laser scattering method
It is fixed.
< semisolid electrolyte >
Semisolid electrolyte contains semisolid electrolyte solvent, optional low viscosity organic solvent and cathode interface addition
Agent.Semisolid electrolyte solvent contains ionic liquid or shows the ether solvent and electrolytic salt with ionic liquid similarity
Mixture.In the case where semisolid electrolyte contains low viscosity organic solvent, it is solid that electrolytic salt can also be not included in half
In body electrolyte solvent, and it is included in low viscosity organic solvent.Furthermore it is also possible to be included in semisolid electrolyte solvent and
In low viscosity organic solvent both sides.Sometimes ionic liquid or ether solvent are known as main solvent.Ionic liquid be at normal temperature from
Solution is the compound of cation and anion, keeps the state of liquid.Ionic liquid is sometimes referred to as ionic liquid, low melting point
Fuse salt or room temperature fuse salt.Heat resistance about semisolid electrolyte solvent, out of stability and secondary cell in atmosphere
From the viewpoint of, the preferred solvent of low volatility, specifically vapour pressure when preferred room temperature is 150Pa solvent below.
In the case where containing semisolid electrolyte in electrode composition layer, semisolid electrolyte in electrode composition layer contains
Amount is preferably 20 volume of volume %~40 %.In the poor situation of semisolid electrolyte, there are inside electrode composition layer
Ion conduction pathway cannot be fully formed, multiplying power property reduce a possibility that.In addition, the content in semisolid electrolyte is more
In the case where, a possibility that leakage there are semisolid electrolyte from electrode composition layer.
Ionic liquid is made of cation and anion.As ionic liquid, imidazoles can be divided into according to cation type
Class, ammonium class, pyrrolidines, piperidines, pyridines, morpholine Lei, Phosphonium class, sulfonium class etc..Constitute imidazole-like ionic
The cationic alkyl miaow such as having 1- ethyl-3-methylimidazole (EMI) or 1- butyl -3- methylimidazole (BMI) of liquid
Azoles cation etc..The cation for constituting ammonium class ionic liquid for example has N, N- diethyl-N- methyl-N- (2- methoxy ethyl)
Ammonium (DEME) or four pentyl ammonium etc., in addition to this there are also N, N, the alkyl ammonium cations such as N- trimethyl-N- propyl ammonium.Constitute pyrroles
The cation of alkanes ionic liquid for example has N- Methyl-N-propyl pyrrolidines (Py13) or 1- butyl -1- crassitude
Equal alkyl pyrrolidines cation etc..The cation for constituting piperidines ionic liquid for example has N- Methyl-N-propyl piperidines
(PP13) or the Alkylpiperidines cation such as 1- butyl -1- methyl piperidine etc..Constitute pyridine ionic liquid sun from
Sub alkylpyridiniium cation such as having 1- butyl-pyridinium or 1- butyl -4- picoline etc..Constitute morpholine class from
Cationic alkyl morpholine such as having 4- ethyl -4- methyl morpholine of sub- liquid etc..Gou Cheng Phosphonium class ionic liquid sun from
Sub Wan Ji phosphonium cation such as having 4-butyl-phosphonium or tributyl Jia Ji Phosphonium etc..The cation for constituting sulfonium class ionic liquid for example has
Alkyl sulfonium cation such as trimethylsulfonium or tributyl sulfonium etc..As the anion pairs of with these cations, such as there are bis- (trifluoros
Methylsulfonyl) imines (TFSI), bis- (fluorine sulphonyl) imines (FSI), tetrafluoroborate (BF4), hexafluoro-phosphate radical (PF6), bis- (five fluorine
Second sulphonyl) imines (BETI), trifluoromethanesulfonic acid root (Triflate), acetate, dimethyl phosphate radical, cdicynanmide, trifluoro (trifluoro
Methyl) borate etc..These ionic liquids can be used alone or combine a variety of uses.
As the electrolytic salt being used together with ionic liquid, can be used being capable of evenly dispersed electrolyte in a solvent
Salt.It can be used by the salt constituted as cationic lithium and above-mentioned anion as lithium salts, such as bis- (fluorine sulphurs can be enumerated
Acyl) imine lithium (LiFSI), bis- (trifluoro methylsulfonyl) imine lithiums (LiTFSI), bis- (five fluorine second sulphonyl) imine lithiums (LiBETI), four
Lithium fluoroborate (LiBF4), lithium hexafluoro phosphate (LiPF6), trifluoromethanesulfonic acid lithium etc., but not limited to this.These electrolytic salts can be single
Solely use or combine a variety of use.
Ether solvent constitutes solvated ion liquid together with electrolytic salt.As ether solvent, it is able to use and shows
Similar to the well known glyme (R-O (CH of the property of ionic liquid2CH2O)n- R ' (R, R ' are saturated hydrocarbons, and n is integer)
Shown in symmetrical diol bisether general name)., it is preferable to use tetraethylene glycol dimethyl ether (tetrem two from the viewpoint of ionic conductance
Diethylene glycol dimethyl ether, G4), triglyme (triethylene glycol dimethyl ether, G3), five glymes (five ethylene glycol dimethyl ether, G5),
Hexaethylene glycol dimethyl ether (six glycol dimethyl ethers, G6).In addition, being able to use crown ether ((- CH as ether solvent2-CH2-O)n(n
For integer) shown in big cyclic ethers general name).Specifically, it is preferable that using 12-crown-4,15- crown- 5,18- crown- 6, dibenzo-
18- crown- 6 etc., but not limited to this.These ether solvents can be used alone or combine a variety of uses.Can be with electrolytic salt
On this point of forming coordination structure is, it is preferable to use tetraethylene glycol dimethyl ether, triglyme.
As the electrolytic salt being used together with ether solvent, the acid imides such as LiFSI, LiTFSI, LiBETI can be used
Lithium salts, but not limited to this.The mixture of ether solvent and electrolytic salt can be used alone or combine a variety of uses.
< low viscosity organic solvent >
Low viscosity organic solvent reduces the viscosity of semisolid electrolyte solvent, ionic conductivity improves.Because containing half
The internal resistance of the semisolid electrolyte of solid electrolyte solvent is big, so solid to improve half by addition low viscosity organic solvent
The ionic conductivity of body electrolyte solvent can reduce the internal resistance of semisolid electrolyte.But because semisolid electrolyte
Solvent is unstable in electrochemistry, so working relative to battery, decomposition reaction is promoted, existed with secondary cell 1000
The resistance that works repeatedly and lead to secondary cell 1000 increase or a possibility that capacity reduces.In turn, use graphite as
In the secondary cell 1000 of negative electrode active material, there are the cation insertion graphite of semisolid electrolyte solvent in charging reaction
Destroy a possibility that can not carrying out of working repeatedly of graphite-structure, secondary cell 1000.
Gluing when low viscosity organic solvent such as preferred viscosities are less than 25 DEG C of the mixture of ether solvent and electrolytic salt
Spend the solvent of 140Pas.As low viscosity organic solvent, can enumerate propene carbonate (PC), trimethyl phosphate (TMP),
Gamma-butyrolacton (GBL), ethylene carbonate (EC), triethyl phosphate (TEP), three (2,2,2- trifluoroethyl) phosphite esters
(TFP), dimethyl methyl phosphonate (DMMP) etc..These low viscosity organic solvents can be used alone or combine a variety of uses.It can
To dissolve above-mentioned electrolytic salt in low viscosity organic solvent.It is excellent from the viewpoint of the capacity maintenance rate of secondary cell 1000
Select EC as low viscosity organic solvent.
< semisolid electrolyte adhesive >
It is preferable to use fluorine resins for semisolid electrolyte adhesive.As fluorine resin, it is preferable to use Kynoar
(PVDF), the copolymer (P (VDF-HFP)) of Kynoar and hexafluoropropene, polytetrafluoroethylene (PTFE) (PTFE) etc..These semisolids
Electrolyte adhesive can be used alone or combine a variety of uses.By using PVDF, P (VDF-HFP), PTFE, semisolid electricity
The adaptation for solving matter layer 300 and electrode collector improves, so battery performance improves.
< semisolid electrolyte >
Semisolid electrolyte is constituted and semisolid electrolyte is held or kept using particle.As semisolid electrolyte
Production method, the methods of can be listed below: semisolid electrolyte is mixed with particle with specific volume ratio, addition is simultaneously
The organic solvents such as methanol are mixed, the slurry of semisolid electrolyte is prepared, later, spreads slurry in culture dish, make organic molten
Agent evaporation obtains the powder of semisolid electrolyte.In the case where semisolid electrolyte contains low viscosity organic solvent, consider
It is readily volatilized to low viscosity organic solvent, it is controlled such that the semisolid electrolysis in semisolid electrolyte containing final goal amount
Liquid.
300 > of < semisolid electrolyte layer
As the production method of semisolid electrolyte layer 300, have the powder of semisolid electrolyte using molding die etc.
Compression forming be partical method and semisolid electrolyte adhesive is added and mixed in the powder of semisolid electrolyte and
The method etc. that sheet is made.It, can by the way that the powder of semisolid electrolyte adhesive is added and mixed in semisolid electrolyte
Make the semisolid electrolyte layer 300 of the high sheet of flexibility.In addition, making half by adding and mixing in semisolid electrolyte
The solution of bonding agent obtained from solid electrolyte adhesive is dissolved in dispersion solvent, evaporates dispersion solvent, can make
Semisolid electrolyte layer 300.Semisolid electrolyte layer 300 can also be by adding above-mentioned and mixing in semisolid electrolyte
Conjunction has the coating of product obtained from the solution of bonding agent on the electrode and is dried and makes.
The content of semisolid electrolyte in semisolid electrolyte layer 300 is preferably 70 volume of volume %~90 %.Half is solid
In the case that the content of body electrolyte is small, a possibility that increase there are the interface resistance of electrode and semisolid electrolyte layer 300.Separately
Outside, in the case that the content of semisolid electrolyte is big, there are the possibility that semisolid electrolyte is leaked out from semisolid electrolyte layer 300
Property.
< cathode bulk density >
By the way that cathode bulk density (hereinafter also referred to as cathode density or density) is set to defined value, can be improved
The battery capacity of secondary cell 1000.Specifically, it is preferable that being set as (cathode bulk density (g/cm3))≤- 0.05042 (negative
Pole surfactant additives weight ratio (%))2+ 0.4317 (cathode interface additive weight ratio (%))+0.9032 is particularly preferably set
For (cathode bulk density (g/cm3))≤- 0.076 (cathode interface additive weight ratio (%))2+ 0.571 (cathode interface addition
Agent weight ratio (%))+0.6251.Here, above-mentioned cathode interface additive weight ratio refers to the weight phase of cathode interface additive
The weight ratio (similarly hereinafter) of the sum of the weight of weight and applied cathode for semisolid electrolyte.The survey of cathode bulk density
Amount method can be found out by measuring weight and the thickness of the anode mixture layer 210 being coated in collector foil.Specifically, logical
The weight for crossing the anode mixture layer 210 measured is found out divided by the thickness of anode mixture layer 210 and the product of area.
< cathode interface additive >
Cathode interface additive forms passivating film in negative terminal surface, inhibits the reduction decomposition of semisolid electrolyte.As
Cathode interface additive can enumerate vinylene carbonate (VC), dioxalic acid lithium borate (LiBOB), fluorinated ethylene carbonate
(FEC) and ethylene sulfite etc..These cathode interface additives can be used alone or combine a variety of uses.
Semisolid electrolyte of the invention includes containing semisolid electrolyte solvent, optional low viscosity organic solvent and to bear
The semisolid electrolyte and particle of pole surfactant additives, with the weight of cathode interface additive relative to semisolid electrolyte
Weight and applied cathode the sum of weight reach 0.6%~11.7% mode be applied to cathode.By providing cathode
Amount of the surfactant additives relative to the sum of the weight of semisolid electrolyte and the weight of cathode, semisolid electrolyte and contains graphite
Deng cathode 200 interface stability improve.Specifically, it is preferable that the weight of cathode interface additive is relative to semisolid electricity
The weight ratio (hereinafter referred to as cathode interface additive weight ratio) of weight and the sum of the weight of applied cathode for solving matter is
0.6%~11.7%, it is particularly preferably 1.7%~5.8%.In the case where cathode interface additive weight ratio is small, facilitate
The semisolid electrolyte of the steady operation of secondary cell 1000 and the interface of the cathode 200 containing graphite can not be formed, so depositing
The service life reduction of secondary cell 1000 a possibility that.In the case where cathode interface additive weight ratio is big, in anode 100
A possibility that decomposition reaction is caused on surface, reduces coulombic efficiency, and there are cell resistance raisings.Find out cathode interface additive phase
The value of the sum of weight for semisolid electrolyte used in cathode 200 and semisolid electrolyte layer 300, so can determine that
Cathode interface additive weight ratio.
Embodiment
Hereinafter, enumerating embodiment further illustrates the present invention, but the present invention is not limited to these embodiments.
1 > of < embodiment
The production > of < semisolid electrolyte
With 1: 1 molar ratio weighing tetraethylene glycol dimethyl ether (G4) and bis- (trifluoro methylsulfonyl) imine lithiums (LiTFSI), investment
In beaker, mixing is carried out until forming homogeneous solvent, makes glyme lithium complex.Claimed with 80: 20 volume ratio
The fumed silica nano particle of glyme lithium complex and partial size 7nm is measured, then will be organic molten as low viscosity
The propene carbonate (PC) of agent is put into together with stirrer as vinylene carbonate (VC), the methanol of cathode interface additive
In beaker, it is stirred using blender with 600rpm, obtains uniform mixture.The mixture is put into eggplant type flask,
Using evaporator, with 100mbar, 60 DEG C drying 3 hours.Powder is obtained powdered by the sieve of 100 μm of mesh after making drying
Semisolid electrolyte.
The production > of < anode 100
LiNi as a positive electrode active material is weighed with 84: 7: 9 weight ratio0.33Mn0.33Co0.33O2, as positive conductive
The acetylene black of agent, the Kynoar (PVDF) for being dissolved in N-Methyl pyrrolidone as positive electrode binder, are mixed, system
At anode sizing agent.It is coated on the stainless steel foil as positive electrode collector 120, it is 2 hours dry at 80 DEG C, remove N- methyl
Pyrrolidones obtains positive plate.Positive plate is punched with diameter 13mm and carries out uniaxial compacting, thus obtaining double-coated amount is
37.5g/cm2, density 2.5g/cm3Anode 100.
The production > of < cathode 200
As negative electrode active material, graphite is used.Cathode conductive agent and negative electrode binder and anode 100 are same.With 88: 2:
10 weight ratio weighs these raw materials, is mixed, and negative electrode slurry is made.It is coated on as negative electrode collector 220 not
It becomes rusty on steel foil, it is 2 hours dry at 80 DEG C, N-Methyl pyrrolidone is removed, negative electrode tab is obtained.By negative electrode tab with diameter 13mm punching
It cuts, then carries out uniaxial compacting, thus obtaining double-coated amount is 17mg/cm2, density 1.6g/cm3Cathode 200.Measurement institute
The weight of obtained cathode.
The production > of < semisolid electrolyte layer 300
Semisolid electrolyte is weighed respectively using 95: 5 weight ratio and as the polytetrafluoroethylene (PTFE) (PTFE) of adhesive, is put into
In mortar, uniformly mixed.The mixture is placed on hydraulic press across teflon plate, with 400kgf/cm2It carries out
Compacting.The roll squeezer that recycling gap is set as 500 is rolled, the semisolid electrolyte layer of the sheet of 200 μm of thickness of production
300.It is punched out with diameter 16mm, the production for lithium ion secondary battery below.Obtained semisolid electrolysis
The weight ratio of glyme lithium complex and PC in matter layer 300 is 55.5: 44.5.The weight of VC is relative to semisolid
The sum of weight and the weight of cathode 200 of electrolyte are 0.6% (cathode interface additive weight ratio).
The production > of < lithium ion secondary battery
Positive 100, cathode 200,300 lamination of semisolid electrolyte layer are enclosed in 2032 type button cells, be made lithium from
Sub- secondary cell.
2~9 > of < embodiment
In addition to the weight of VC is relative to (the cathode interface addition of the sum of the weight of semisolid electrolyte and the weight of cathode 200
Agent weight ratio) as shown in Figure 3 other than, operate similarly to Example 1.
10~11 > of < embodiment
In addition to using dioxalic acid lithium borate (LiBOB) as the weight of cathode interface additive and LiBOB relative to half
Other than the sum of the weight of solid electrolyte and the weight of cathode 200 (cathode interface additive weight ratio) are as shown in Figure 3, with implementation
Example 1 equally operates.
12~14 > of < embodiment
It is solid relative to half as the weight of cathode interface additive and FEC in addition to using fluorinated ethylene carbonate (FEC)
Other than the sum of the weight of body electrolyte and the weight of cathode 200 (cathode interface additive weight ratio) are as shown in Figure 3, with embodiment
1 same operation.
15 > of < embodiment
In addition to using ethylene carbonate (EC) as low viscosity organic solvent, using vinylene carbonate (VC) as cathode
The weight ratio of glyme lithium complex and EC in surfactant additives, semisolid electrolyte layer 300 as shown in Figure 3,
And the weight of VC is other than 1.7%, with embodiment 1 relative to the sum of the weight of semisolid electrolyte and the weight of cathode 200
Same operation.
16~33 > of < embodiment
In addition to the density of cathode 200, the weight of VC are relative to the sum of the weight of semisolid electrolyte and cathode 200 (cathode
Surfactant additives weight ratio) as shown in Figure 3 other than, operate similarly to Example 1.
1 > of < comparative example
Other than without using cathode interface additive, operate similarly to Example 1.
2~3 > of < comparative example
In addition to the weight of VC is relative to (the cathode interface addition of the sum of the weight of semisolid electrolyte and the weight of cathode 200
Agent weight ratio) as shown in Figure 3 other than, operate similarly to Example 1.
4~9 > of < comparative example
Other than without using cathode interface additive, equally operated with embodiment 16~21.
The measurement > of < discharge capacity
For the lithium ion secondary battery of embodiment and comparative example, measurement voltage range is set as 2.7V~4.2V, makes electricity
Discharge capacity (initial discharge of the pond with the constant current-constant voltage mode that charges, electric discharge constant current mode work, after measurement first cycle electric discharge
Capacity), 30 times circulation electric discharge after discharge capacities (30 cyclic discharge capacities).
< considers >
The measurement result of Fig. 3 expression embodiment and comparative example.By initial discharge capacity divided by 30 cyclic discharge capacity institutes
Obtained value (discharge capacity sustainment rate) is shown in Fig. 3.It is considered that battery capacity of the initial discharge capacity to secondary cell 1000
There is larger impact, discharge capacity sustainment rate has larger impact to the service life of secondary cell 1000.Therefore, commenting as battery capacity
Valence benchmark, with initial discharge capacity, in 105 (mAh/g), the above are conditions to be maintained as the evaluation criteria in service life with discharge capacity
The above are conditions 65% for rate.
Regardless of the composition of cathode interface additive, discharge capacity sustainment rate is all expected in any embodiment
Value.Especially in the case where cathode interface additive weight ratio is 1.7%~5.8%, 30 cyclic discharge capacities are more viscous than low
It is big to spend the identical but comparative example without cathode interface additive of solvent.
Regardless of cathode bulk density is added to cathode circle compared with the comparative example for being not added with cathode interface additive
The initial discharge capacity of the embodiment of face additive is all big.
The relational graph of Fig. 4 expression deterioration factor and cathode interface additive weight ratio.By discharge capacity sustainment rate relative to
1/2 power of cycle-index draws curve, by straight line approximation, finds out slope, is defined as deterioration factor.Deterioration factor is total
It is to take negative value, the smaller expression capacity maintenance rate of absolute value is higher.As shown in figure 4, relative to cathode interface additive weight ratio,
Deterioration factor is drawn, when being fitted the relationship of the two by least square method, there is (the cathode of (deterioration factor)=- 0.1375
Surfactant additives weight ratio)2The relationship of+2.0857 (cathode interface additive weight ratios) -7.5141.By the relationship it is found that bad
Change the absolute value of coefficient than comparative example 1 hour without cathode interface additive, cathode interface additive weight ratio is 15.2%
Below.In addition, expecting that the deterioration factor of the secondary cell 1000 without cathode interface additive is -7.5141, and 100 times are followed
Discharge capacity sustainment rate after ring is 24.9%.Deterioration factor become -5 (100 times circulation after discharge capacity sustainment rate be
50%) when, cathode interface additive weight ratio is 1.3%~13.9%, also, deterioration factor becomes -3 (after 100 circulations
Discharge capacity sustainment rate be 70%) when, cathode interface additive weight ratio be 2.6%~12.6%.
< cathode interface additive is VC >
In the secondary cell that main solvent is G4, low viscosity organic solvent PC, cathode interface additive are VC, cathode circle
The weight of face additive relative to the sum of the weight of semisolid electrolyte and the weight of cathode 200 weight ratio be 0.6%~
When 11.7% (Examples 1 to 9), exist with comparative example 1, cathode interface additive weight ratio without cathode interface additive
14.6% or more comparative example 2 is compared with 3, and 30 times cyclic discharge capacity is bigger.It is 0.6% in cathode interface additive weight ratio
When~5.8% (Examples 1 to 7), 30 cyclic discharge capacities are bigger than Comparative Examples 1 and 22 and 3.Also, in cathode interface additive
When weight ratio is 1.7%~5.8% (embodiment 3~7), at least in 30 work of battery repeatedly, discharge capacity is up to
130mAh/g or more.
It is considered that in the case where cathode interface additive weight ratio is small, the interface of semisolid electrolyte and cathode 200
Non- sufficient stabilization, the total insertion of glyme lithium complex and reduction decomposition partly carry out, initial discharge capacity
Become smaller.On the other hand, it is believed that in the case where cathode interface additive weight ratio is big, with cycle operation, VC is in anode
100 surface is slowly decomposed, and high resistance is induced, thus discharge capacity becomes smaller.
The embodiment 15 for being EC for low viscosity organic solvent, since cathode interface additive weight ratio is 1.7%, thus
Initial discharge capacity and 30 cyclic discharge capacities are big.
< cathode interface additive is LiBOB >
In the embodiment 10 and 11 that cathode interface additive is LiBOB, by the maximum of cathode interface additive weight ratio
Value is set as 1.7%.This is because there is imported LiBOB can not be complete in the mixed solvent in the case where weight ratio is bigger
A possibility that fully dissolved.By the way that cathode interface additive weight ratio is set as 0.6%~1.7%, initial discharge capacity and 30 times
Cyclic discharge capacity is bigger than the comparative example 1 without LiBOB.
< cathode interface additive is FEC >
The embodiment 12~14 that cathode interface additive is FEC is compared with the comparative example 1 without FEC, initial discharge capacity
Bigger, 30 times cyclic discharge capacity shows 100mAh/g or more.
When cathode interface additive weight ratio is 1.7%, 3.5% and 5.8%, discharge capacity sustainment rate difference is monotonously
It is reduced to 97%, 88% and 85%.It is considered that itself main reason is that, cathode interface additive weight ratio be 1.7% with
On compositing range in, there is the stabilized effect in interface portion ground of the cathode 200 and semisolid electrolyte that make graphitiferous, separately
On the one hand, it can be sent out on interface of the anode 100 with semisolid electrolyte than optimum weight ratio excess with battery repeated work
The decomposition reaction of raw FEC, thus induces high resistance.
< cathode interface additive weight ratio and cathode bulk density >
In the case where electrode coating amount is certain, battery capacity depends not only upon cathode interface additive weight ratio, also according to
Rely in cathode bulk density.This is because cathode 200 thickens, thus there are secondary electricity in the case where cathode bulk density is small
A possibility that resistance in pond increases.Also as the gap of electrode interior becomes smaller, first in the case where cathode large bulk density
In charging, cathode interface additive is not reached near electrode collector, so inducing the decomposition reaction of semisolid electrolyte, is existed
A possibility that resistance of secondary cell increases.
Fig. 5 expression makes the certain (1.12~1.77g/ of cathode bulk density in embodiment 16~33 and comparative example 4~9
cm3), relationship of the initial discharge capacity relative to cathode interface additive weight ratio.In this case, initial discharge capacity according to
Rely in cathode interface additive weight ratio, it can be with quadratic function approximation.On the other hand, the constant term of curve of approximation is dependent on negative
Pole bulk density.
Fig. 6 expression make in embodiment 16~33 and comparative example 4~9 cathode interface additive weight ratio it is certain (0~
5.8%), relationship of the initial discharge capacity relative to cathode bulk density.In this case, initial discharge capacity is relative to negative
Pole bulk density can be approximate with the straight line with negative slope.The size of straight slope depends on cathode interface weight of additive
Than.These Fig. 5 and Fig. 6's the result shows that cathode bulk density and cathode interface additive both sides are used as initial discharge capacity
Parameter works.
According to the curve of approximation and near linear obtained by Fig. 5 and Fig. 6, initial discharge capacity certain in order to obtain is found out
The relationship of cathode bulk density and cathode interface additive weight ratio, is shown in Fig. 7 required for Q.Such as regardless of cathode bulk density
What, by adding cathode interface additive, initial discharge capacity Q can increase.In addition, in (cathode bulk density (g/cm3))
≤ -0.05042 (cathode interface additive weight ratio (%))2+ 0.4317 (cathode interface additive weight ratio (%))+
In region shown in 0.9032, initial discharge capacity Q is in 120mAh/g or more.In addition, in (cathode bulk density (g/cm3))
≤ -0.076 (cathode interface additive weight ratio (%))2+ 0.571 (cathode interface additive weight ratio (%))+0.6251 institute
In the region shown, initial discharge capacity Q is in 130mAh/g or more.
Symbol description
100: anode；110: positive electrode material mixture layer；120: positive electrode collector；130: positive terminal portion；200: cathode；210: negative
Pole mixture layer；220: negative electrode collector；230: anode connector portion；300: semisolid electrolyte layer；400: electrode body；500: exterior
Body；1000: secondary cell.
Whole publications for quoting in this specification, patents and patent applications are introduced directly into this specification by quoting.
Claims (8)
1. a kind of semisolid electrolyte, it is characterised in that:
Comprising semisolid electrolyte and particle containing semisolid electrolyte solvent and cathode interface additive,
The weight of the cathode interface additive is relative to the weight of the semisolid electrolyte and the weight of applied cathode
The sum of weight ratio be 0.6%~11.7%.
2. semisolid electrolyte according to claim 1, it is characterised in that:
The weight of the cathode interface additive is relative to the weight of the semisolid electrolyte and the weight of applied cathode
The sum of weight ratio be 1.7%~5.8%.
3. semisolid electrolyte according to claim 1, it is characterised in that:
The cathode interface additive is vinylene carbonate (VC).
4. semisolid electrolyte according to claim 1, it is characterised in that:
The semisolid electrolyte also contains low viscosity organic solvent.
5. a kind of electrode, it is characterised in that:
With the semisolid electrolyte layer comprising semisolid electrolyte described in claim 1.
6. a kind of electrode with semisolid electrolyte layer, it is characterised in that:
With semisolid electrolyte layer and electrode comprising semisolid electrolyte described in claim 1.
7. the electrode according to claim 6 with semisolid electrolyte layer, it is characterised in that:
The electrode is cathode, and meets the following conditions:
(cathode bulk density (g/cm3))≤- 0.05042 (weight of the cathode interface additive is relative to the semisolid
The weight ratio (%) of the sum of the weight of electrolyte and the weight of cathode)2+ 0.4317 (the weight phase of the cathode interface additive
The weight ratio (%) of the sum of the weight of weight and cathode for the semisolid electrolyte)+0.9032.
8. a kind of secondary cell, it is characterised in that:
With the semisolid electrolyte layer comprising semisolid electrolyte described in claim 1,
It is described when the capacity maintenance rate of the secondary cell after regulation time circulation is greater than without the cathode interface additive
The capacity maintenance rate of secondary cell.
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| JP2017-117337 | 2017-06-15 | ||
| JP2017117337 | 2017-06-15 | ||
| PCT/JP2018/018977 WO2018230238A1 (en) | 2017-06-15 | 2018-05-16 | Semisolid electrolyte, electrode, electrode having semisolid electrolyte layer, and secondary battery |
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| CN114792793A (en) * | 2021-01-25 | 2022-07-26 | 中国科学院物理研究所 | Sodium ion battery additive and high-power sodium ion battery |
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Also Published As
| Publication number | Publication date |
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| KR20190119654A (en) | 2019-10-22 |
| JP6875522B2 (en) | 2021-05-26 |
| WO2018230238A1 (en) | 2018-12-20 |
| JPWO2018230238A1 (en) | 2020-01-09 |
| KR102272029B1 (en) | 2021-07-01 |
| CN110521049B (en) | 2022-03-15 |
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