CN110537284A - Polymer electrolyte composition and polymer secondary battery - Google Patents
Polymer electrolyte composition and polymer secondary battery Download PDFInfo
- Publication number
- CN110537284A CN110537284A CN201780089823.8A CN201780089823A CN110537284A CN 110537284 A CN110537284 A CN 110537284A CN 201780089823 A CN201780089823 A CN 201780089823A CN 110537284 A CN110537284 A CN 110537284A
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- salt
- electrolyte composition
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Classifications
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- H—ELECTRICITY
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
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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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The present invention discloses a kind of polymer electrolyte composition, contains: the polymer with structural unit represented by the following general formula (1)；And the complex compound of (poly-) glycol dialkyl ether represented by least one of the group being made of lithium salts, sodium salt, magnesium salts and calcium salt salt and the following general formula (2).[in formula (1), X‑Indicate counter anion.]R1O‑(CH2CH2O)m‑R2(2) [in formula (2), R1And R2The alkyl of carbon atom number 1~4 is each independently represented, m indicates 1~6 integer.]
Description
Technical field
The present invention relates to polymer electrolyte composition and polymer secondary batteries.
Background technique
Lithium secondary battery is the energy device with high-energy density, the power supply as portable electronic device and electric vehicle
And it popularizes.For example, cylindric battery inside accommodates rolled electrode bodies in the lithium secondary battery of 18650 types.Winding electricity
Polar body is micro- porous diaphragm to be sandwiched between positive electrode and negative electrode, and they are constituted with circinate winding, in diaphragm
In containing being soaked with flammable electrolyte.For such lithium secondary battery, if when abnormal conditions the temperature of battery it is unexpected on
It rises, then there is electrolyte to gasify and internal pressure raising, a possibility that rupture.In addition, if the temperature of battery is flown up,
A possibility that on fire there are electrolyte.
Prevent lithium secondary battery kindling or situation on fire critically important in the design of lithium secondary battery.In lithium secondary battery
In, in order to further realize high-energy density and enlargement from now on, it is desirable that further raising safety.
As the basic solution for the safety for improving lithium secondary battery, the exploitation of all-solid-state battery, institute are being carried out
Stating all-solid-state battery is that electrolyte is substituted for polymer dielectric or inorganic solid electrolyte, makes all solid-states of constituent material
Battery.Especially polymer dielectric is being accumulated due to being able to easily form sheet material by coated polymeric solution
It is studied polar region.
The material being widely studied in polymer dielectric is polyethylene glycol oxide (PEO).PEO 60 DEG C of displays more than 1 ×
10-4The high ion conductivity of S/cm, in a part of vehicle-mounted real achievement for also having functionization on the way (for example, referring to patent text
Offer 1, non-patent literature 1).
In addition, also actively studying the nonaqueous solvents combined with polymer dielectric to improve ionic conductivity.Make
The organic solvents such as dialkyl carbonate are widely used (for example, referring to special from the viewpoint of ionic conductivity for nonaqueous solvents
Sharp document 2).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2006-294326 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2007-141467 bulletin
Non-patent literature
Non-patent literature 1:P.Hovington et.al., Nano Lett.2015,15,2671-2678
Summary of the invention
Subject to be solved by the invention
However, that records in patent document 1 has used the polymer dielectric of PEO since oxidation stability is low, in room temperature
The reasons such as ionic conductivity significant decrease in a low temperature of below, thus it is not yet practical extensively.
In addition, although recording in patent document 2 show that high ion passes with organic solvent combination polymer dielectric
Conductance, but safety is troubling.In addition, organic solvent, due to readily volatilized, when being formed as sheet, operation is tired
It is difficult, it is difficult to dry moisture removal is utilized necessary to carrying out for improving battery behavior.In addition, according to polymer dielectric and
The type of organic solvent worries that polymer dielectric is separated with organic solvent, the ionic conductivity of polymer dielectric piece sometimes
It is significantly reduced with mechanical strength.
The present invention is in view of the foregoing and the invention made, main purpose are to provide even if without using organic molten
Agent can also be produced on the polymer with the high sheet material of excellent ionic conductivity and self-supporting under room temperature (such as 25 DEG C)
Electrolyte composition.
The method used for solving the problem
First form of the invention is polymer electrolyte composition, is contained: having knot represented by the following general formula (1)
The polymer of structure unit；And selected from least one of the group being made of lithium salts, sodium salt, magnesium salts and calcium salt salt and the following general formula
(2) complex compound of (poly-) glycol dialkyl ether (Glyme) represented by.
[changing 1]
[in formula (1), X-Indicate counter anion.]
R1O-(CH2CH2O)m-R2 (2)
[in formula (2), R1And R2The alkyl of carbon atom number 1~4 is each independently represented, m indicates 1~6 integer.]
It should be noted that in the present specification, it sometimes will be in the group being made of lithium salts, sodium salt, magnesium salts and calcium salt
At least one salt and general formula (2) represented by (poly-) glycol dialkyl ether complex compound referred to as " (poly-) ethylene glycol dialkyl group
Ether complexes ".
The polymer electrolyte composition that first form according to the present invention is related to also can even if not using organic solvent
The sheet material that enough production have excellent ionic conductivity and self-supporting high at room temperature.(poly-) glycol dialkyl ether complex compound
Due to drying process (for example, 60 DEG C, be less than or equal to 1.0 × 104The decompression of Pa (being less than or equal to 0.1 atmospheric pressure)
Lower drying 10 hours or more) in it is substantially non-volatile, therefore polymer electrolyte composition can become the high material of thermal stability.
It is counted on the basis of total composition, the content of (poly-) glycol dialkyl ether complex compound can be 10~70 matter
Measure %.
The anion of salt can be for selected from by PF6 -、BF4 -、N(FSO2)2 -、N(CF3SO2)2 -、B(C2O4)2 -And ClO4 -Composition
At least one of group.Salt can be lithium salts.
M in formula (2) can be 3 or 4.(poly-) glycol dialkyl ether represented by general formula (2) can be triethylene glycol
Dimethyl ether or tetraethyleneglycol dimethyl ether.
Polymer electrolyte composition can be formed as sheet.It can be with using the sheet material that polymer electrolyte composition is formed
As the sheet material for being able to maintain its shape s without substrate etc..It should be noted that in the present specification, will be formed sometimes
It is known as " polymer dielectric piece " for the polymer electrolyte composition of sheet.
Second form of the invention is a kind of polymer secondary battery, has anode, cathode and electrolyte layer, the electricity
Solution matter layer is set between anode and cathode and includes above-mentioned polymer electrolyte composition.
Invention effect
According to the present invention, it is possible to provide it is a kind of can be made not using organic solvent at room temperature have it is excellent from
The polymer electrolyte composition of sub- conductivity and the high sheet material of self-supporting.In addition, according to the present invention, it is possible to provide used this
The polymer secondary battery of kind polymer electrolyte composition.
Detailed description of the invention
Fig. 1 is the perspective view for the polymer secondary battery for indicating that first embodiment is related to.
Fig. 2 is the exploded perspective view for indicating an embodiment of the electrode group in polymer secondary battery shown in FIG. 1.
Fig. 3 is the schematic section for indicating an embodiment of the electrode group in polymer secondary battery shown in FIG. 1.
In Fig. 4, it is (b) to indicate that (a), which is the schematic section for the polymer dielectric piece for indicating that an embodiment is related to,
The schematic section for the polymer dielectric piece that other embodiments are related to.
Fig. 5 is the signal of an embodiment of the electrode group for the polymer secondary battery for indicating that second embodiment is related to
Sectional view.
Specific embodiment
Hereinafter, suitably referring to attached drawing on one side, embodiments of the present invention will be described on one side.But the present invention is unlimited
In the following embodiments and the accompanying drawings.In the following embodiments, constituent element (also comprising step etc.) is in addition to the feelings especially expressed
It is all not required other than condition.The size of constituent element in each figure is conceptual, the opposite pass of the size between constituent element
System is not limited to situation shown in each figure.
It closes numerical value in this manual and its range is also the same, do not limit the present invention."~" table is used in this specification
The numberical range shown indicates the range comprising numerical value documented by "~" front and back respectively as minimum value and maximum value.In this explanation
In book in the interim numberical range recorded, upper limit or lower limit documented by a numberical range could alternatively be other ranks
The upper limit or lower limit for the numberical range that section property is recorded.In addition, in the numberical range recorded in the present specification, numerical value model
The upper limit or lower limit enclosed also could alternatively be value shown in embodiment.
In this specification, use following label as referred to as sometimes.
[EMI]+: 1- ethyl-3-methylimidazoleCation
[DEME]+: N, N- diethyl-N- methyl-N- (2- methoxy ethyl) ammonium cation
[Py12]+: N- ethyl-N-methyl pyrrolidinesCation
[Py13]+: N- Methyl-N-propyl pyrrolidinesCation
[PP13]+: N- Methyl-N-propyl piperidinesCation
[LiG4]+: tetraethyleneglycol dimethyl ether lithium cation
[FSI]-: bis- (fluoro sulphonyl) imines anion
[TFSI]-: bis- (trifluoro methylsulfonyl) imines anion
[f3C]-: three (fluoro sulphonyl) carbonium anions
[BOB]-: double ethanedioic acid borate anions
[P (DADMA)] [Cl]: diallyl dimethyl ammoniumchloride
[P (DADMA)] [TFSI]: poly- (diallyl dimethyl ammonium) bis- (trifluoro methylsulfonyl) imines
[first embodiment]
Fig. 1 is the perspective view for the polymer secondary battery for indicating that first embodiment is related to.As shown in Figure 1, polymer two
Primary cell 1 has by the pouch type battery exterior body 3 of anode, the electrode group 2 and accommodate electrod group 2 that cathode and electrolyte layer are constituted.
Positive pole current collections tab 4 and negative collector electrode ear 5 are respectively equipped on anode and cathode.Positive pole current collections tab 4 and negative collector electrode
Ear 5 is prominent from the interior of battery exterior body 3 respectively, enable anode and cathode respectively with polymer secondary battery 1
External electrical connections.
Battery exterior body 3 can for example be formed by laminated film.Laminated film for example can be to make polyethylene terephthalate
The resin films such as ester (PET) film, stacking made of the sealant layers such as the metal foils such as aluminium, copper, stainless steel and polypropylene stack gradually
Film.
Fig. 2 is the exploded perspective for indicating an embodiment of the electrode group 2 in polymer secondary battery 1 shown in FIG. 1
Figure.Fig. 3 is the schematic section for indicating an embodiment of the electrode group 2 in polymer secondary battery 1 shown in FIG. 1.Such as
Shown in Fig. 2 and Fig. 3, electrode group 2A of the present embodiment successively has anode 6, electrolyte layer 7 and cathode 8.Anode 6 has
Positive electrode collector 9 and the positive electrode material mixture layer 10 being set on positive electrode collector 9.Positive collector electrode is equipped on positive electrode collector 9
Ear 4.The anode mixture layer 12 that cathode 8 has negative electrode collector 11 and is set on negative electrode collector 11.In negative electrode collector 11
It is equipped with negative collector electrode ear 5.
Positive electrode collector 9 can be formed by aluminium, stainless steel, titanium etc..Specifically, positive electrode collector 9 can be with hole
The aluminum perforated foil in the hole of 0.1~10mm of diameter, expanded metal mesh, foamable metal sheet etc..Than that described above, as long as making in battery
The variations such as dissolution, oxidation will not occur in, so that it may positive electrode collector 9 be formed by arbitrary material, in addition, its shape, system
Making method etc., also there is no limit.
The thickness of positive electrode collector 9 can be greater than or equal to 1 μm, be greater than or equal to 5 μm or more than or equal to 10 μm.Just
The thickness of electrode current collector 9 can be less than or equal to 100 μm, be less than or equal to 50 μm or less than or equal to 20 μm.
In one embodiment, positive electrode material mixture layer 10 contains positive active material, conductive agent and adhesive.
Positive active material can be LiCoO2、Li0.3MnO2、Li4Mn5O12、V2O5、LiMn2O4、LiNiO2、LiFePO4、
LiCo1/3Ni1/3Mn1/3O2、Li1.2(Fe0.5Mn0.5)0.8O2、Li1.2(Fe0.4Mn0.4Ti0.2)0.8O2、Li1+x(Ni0.5Mn0.5)1-xO2
(wherein, x=0~1.),LiNi0.5Mn1.5O4、Li2MnO3、Li0.76Mn0.51Ti0.49O2、LiNi0.8Co0.15Al0.05O2、Fe2O3、
LiCoPO4、LiMnPO4、Li2MPO4F (M=Fe, Mn), LiMn0.875Fe0.125PO4、Li2FeSiO4、Li2-xMSi1-xPxO4(M=
Fe, Mn) (wherein, x=0~1.),LiMBO3(M=Fe, Mn), FeF3、Li3FeF6、Li2TiF6、Li2FeS2、TiS2、MoS2、
FeS etc..
Positive active material can be the primary particle without granulation, be also possible to the offspring after being granulated.
The particle size adjustment of positive active material is the thickness less than or equal to positive electrode material mixture layer 10.In positive active material
In the presence of the partial size with the thickness more than or equal to positive electrode material mixture layer 10 coarse grain in the case where, pass through sieve classification, air-flow point
Grade etc. removes coarse grain in advance, selects the positive active material of the partial size with the thickness less than or equal to positive electrode material mixture layer 10.
From the deterioration for the fillibility for inhibiting the positive active material occurred with partial size reduction and the guarantor of raising electrolyte
From the viewpoint of holding ability, the average grain diameter of positive active material is preferably greater than or equal to 1 μm, more preferably equal to or greater than 3 μm,
Further preferably greater than or it is equal to 5 μm, additionally, it is preferred that it is less than or equal to 30 μm, it is more preferably less than or equal to 25 μm, further excellent
Choosing is less than or equal to 20 μm.The average grain diameter of positive active material refers to the ratio of the volume relative to positive active material entirety
Partial size (D when (volume fraction) is 50%50).Average grain diameter (the D of positive active material50) obtain as follows: use laser light scattering
Type particle size determination device (for example, Microtrac) makes positive active material suspend in water and obtains by laser scattering method
The suspension arrived.
It is counted on the basis of the total amount of positive active material, conductive agent and adhesive, the content of positive active material can be big
In or equal to 80 mass %, it is greater than or equal to 85 mass % or is greater than or equal to 90 mass %.With positive active material, conduction
It is counted on the basis of the total amount of agent and adhesive, the content of positive active material can for example be less than or equal to 99 mass %.
Conductive agent can be carbon black, graphite, carbon fiber, carbon nanotube, acetylene black etc..
It is counted on the basis of the total amount of positive active material, conductive agent and adhesive, the content of conductive agent can be greater than or wait
In 1 mass %, it is greater than or equal to 3 mass % or is greater than or equal to 5 mass %.From the volume increase for inhibiting anode 6 and with it
Polymer secondary battery 1 energy density reduce from the viewpoint of, with the total amount of positive active material, conductive agent and adhesive
On the basis of count, the content of conductive agent is preferably lower than or equal to 15 mass %, more preferably less than or equal to 12 mass %, further it is excellent
Choosing is less than or equal to 9 mass %.
Adhesive is as long as on the surface of anode 6, there is no limit without decompose as long as, for example, polymer.Adhesive can be poly-
Vinylidene, polyacrylonitrile, SBR styrene butadiene rubbers, carboxy-methyl cellulose, fluorubber, ethylene-propylene rubber, poly- third
The resins such as olefin(e) acid, polyimides, polyamide；With these resins as the copolymer of main framing resin (for example, polyvinylidene fluoride
Alkene-hexafluoropropylene copolymer etc.) etc..
It is counted on the basis of the total amount of positive active material, conductive agent and adhesive, the content of adhesive can be greater than or wait
In 1 mass %, it is greater than or equal to 3 mass % or is greater than or equal to 5 mass %.With positive active material, conductive agent and adhesive
Total amount on the basis of count, the content of adhesive can be less than or equal to 15 mass %, less than or equal to 12 mass % or be less than or
Equal to 9 mass %.
Positive electrode material mixture layer 10 also can according to need further containing fuse salts such as soft sticky crystal, ionic liquid etc..With
It is counted on the basis of anode mixture stratum total, the content of fuse salt can be 0.01~20 mass %.
From the viewpoint of further increasing conductivity, positive electrode material mixture layer 10 with a thickness of be greater than or equal to positive electrode active material
The thickness of the average grain diameter of matter, preferably greater than or equal to 10 μm, more preferably equal to or greater than 20 μm, further preferably greater than or are waited
In 30 μm.The thickness of positive electrode material mixture layer 10 is preferably lower than or equal to 100 μm, more preferably less than or equal to 80 μm, further preferably
Less than or equal to 60 μm.By being set as the thickness of positive electrode material mixture layer to be less than or equal to 100 μm, it is able to suppress because of positive electrode material mixture layer
Charge and discharge caused by the deviation of the charge level of positive active material of 10 surface nearby and near the surface of positive electrode collector 9
Electric is uneven.
From making, conductive agent and positive active material are closely sealed each other, reduce the viewpoint of electronic impedance of positive electrode material mixture layer 10 is examined
Consider, the mixture density of positive electrode material mixture layer 10 is preferably greater than or equal to 1g/cm3。
Negative electrode collector 11 can be formed by copper, stainless steel, titanium, nickel etc..Specifically, negative electrode collector 11 can be to roll
Copper foil (such as the copper perforated foil in the hole with 0.1~10mm of aperture) processed, expanded metal mesh, foamable metal sheet etc..Cathode collection
Electric body 11 can also be formed by any materials than that described above, in addition, also there is no limit for its shape, manufacturing method etc..
The thickness of negative electrode collector 11 can be greater than or equal to 1 μm, be greater than or equal to 5 μm or more than or equal to 10 μm.It is negative
The thickness of electrode current collector 11 can be less than or equal to 100 μm, be less than or equal to 50 μm or less than or equal to 20 μm.
In one embodiment, anode mixture layer 12 contains negative electrode active material and adhesive.
Negative electrode active material the negative electrode active material as the common energy device field such as secondary cell can be used and
The substance used.As negative electrode active material, such as lithium metal, lithium alloy, metallic compound, carbon material, metal network can be enumerated
Close object, organic high molecular compound etc..They can be used alone, and also can be used together two or more.In these substances, cathode
Active material is preferably carbon material.As carbon material, such as the stones such as natural graphite (flaky graphite etc.), electrographite can be enumerated
Ink；The carbon blacks such as acetylene black, Ketjen black, channel black, furnace black, lampblack, thermal crack black；Amorphous carbon, carbon fiber etc..
From obtain inhibit with partial size reduce and occur irreversible capacity increase while improve electrolyte
Holding capacity, from the viewpoint of balanced cathode 8, the average grain diameter (D of negative electrode active material50) it is preferably greater than or equal to 1 μ
M, more preferably equal to or greater than 3 μm further preferably greater than or are equal to 5 μm, additionally, it is preferred that being less than or equal to 20 μm, more preferably
Less than or equal to 18 μm, it is further preferably no larger than or equal to 16 μm.Average grain diameter (the D of negative electrode active material50) by with anode
Average grain diameter (the D of active material50) similarly method measurement.
The content of negative electrode active material can be same as the content of positive active material in above-mentioned positive electrode material mixture layer 10.
Adhesive and its content can in above-mentioned positive electrode material mixture layer 10 adhesive and its content it is same.
From the viewpoint of the resistance for further decreasing cathode 8, anode mixture layer 12 can also further contain conductive agent.
Conductive agent and its content can in above-mentioned positive electrode material mixture layer 10 conductive agent and its content it is same.
Anode mixture layer 12 can also be as needed further containing fuse salts such as soft sticky crystal, ionic liquid etc..It is molten
Melting salt may be exemplified fuse salt same as aftermentioned fuse salt.It is counted on the basis of cathode agent stratum total, the content of fuse salt
It can be 0.01~20 mass %.
From the viewpoint of further increasing conductivity, the thickness of anode mixture layer 12 is greater than or equal to negative electrode active material
Average grain diameter, preferably greater than or equal to 10 μm, more preferably equal to or greater than 15 μm, further preferably greater than or be equal to 20 μm.
The thickness of anode mixture layer 12 is preferably lower than or equal to 50 μm, more preferably less than or equal to 45 μm, is further preferably no larger than or waits
In 40 μm.By being set as the thickness of anode mixture layer 12 to be less than or equal to 50 μm, it is able to suppress the table because of anode mixture layer 12
Charge and discharge caused by the deviation of the charge level of positive active material of the face nearby and near the surface of negative electrode collector 11
Unevenly.
From making, conductive agent and negative electrode active material are closely sealed each other, reduce the viewpoint of electronic impedance of anode mixture layer 12 is examined
Consider, the mixture density of anode mixture layer 12 is preferably greater than or equal to 1g/cm3。
Electrolyte layer 7 can be formed by polymer electrolyte composition.Polymer electrolyte composition contains with specific
The polymer of structural unit and specific complex compound i.e. (poly-) glycol dialkyl ether complex compound.
[polymer]
Polymer electrolyte composition contains the polymer with structural unit represented by the following general formula (1).
[changing 2]
In general formula (1), X-Indicate counter anion.Here, as X-, such as BF can be enumerated4 -(tetrafluoroborate yin from
Son), PF6 -(hexafluoro-phosphate radical anion), N (FSO2)2 -(bis- (fluoro sulphonyl) imines anion, [FSI]-)、N(CF3SO2)2 -
(bis- (trifluoro methylsulfonyl) imines anion, [TFSI]-)、C(SO2F)3 -(three (fluoro sulphonyl) carbonium anions, [f3C]-)、B
(C2O4)2 -(double ethanedioic acid borate anions, [BOB]-)、BF3(CF3)-、BF3(C2F5)-、BF3(C3F7)-、BF3(C4F9)-、C
(SO2CF3)3 -、CF3SO2O-、CF3COO-、RCOO-(R is alkyl, phenyl or the naphthalene of carbon atom number 1~4.) etc..In them, X-
It is preferably selected from by BF4 -、PF6 -、[FSI]-、[TFSI]-[f3C]-At least one of group of composition, more preferably [TFSI]-
Or [FSI]-。
Viscosity average molecular weigh Mv (the gmol of polymer with structural unit represented by general formula (1)-1) do not limit especially
System, preferably greater than or equal to 1.0 × 105, more preferably equal to or greater than 3.0 × 105.In addition, the viscosity average molecular weigh of polymer is preferred
Less than or equal to 5.0 × 106, more preferably 1.0 × 106.If viscosity average molecular weigh is greater than or equal to 1.0 × 105, then exist poly-
The more excellent tendency of the self-supporting of polymer electrolyte piece.In addition, if viscosity average molecular weigh is less than or equal to 5.0 × 106, then
The tendency further increased in the presence of the treatability that coating is formed.
In this specification, " viscosity average molecular weigh " can be evaluated by the viscosimetry as common measuring method,
Such as it can be calculated by the Limiting Viscosity [η] measured based on JIS K 7367-3:1999.
From the viewpoint of ionic conductivity, the polymer with structural unit represented by general formula (1) preferably only by
Polymer, the i.e. homopolymer that structural unit represented by general formula (1) is constituted.
Polymer with structural unit represented by general formula (1) can be polymer represented by the following general formula (1a).
[changing 3]
In general formula (1a), n is 300~4000, Y-Indicate counter anion.Y-It can be used and in X-What place illustrated contends with
The same counter anion of anion.
N is greater than or equal to 300, preferably greater than or equal to 400, more preferably equal to or greater than 500.In addition, being less than or equal to
4000, preferably lower than or equal to 3500, more preferably less than or equal to 3000.In addition, n be 300~4000, preferably 400~
3500, more preferably 500~3000.If n is greater than or equal to 300, there are the self-supportings of polymer dielectric piece more
Excellent tendency.If n is less than or equal to 4000, there are what the ionic conductivity of polymer dielectric piece further increased to incline
To.
The manufacturing method of polymer with structural unit represented by general formula (1) is not particularly limited, such as can make
With the manufacturing method recorded in Journal of Power Sources 2009,188,558-563.
Polymer (X with structural unit represented by general formula (1)-=[TFSI]-) it can for example pass through manufacture below
Method obtains.
Firstly, diallyl dimethyl ammoniumchloride ([P (DADMA)] [Cl]) is dissolved in deionized water, stirred
Mixing makees [P (DADMA)] [Cl] aqueous solution.[P (DADMA)] [Cl] for example can directly use commercially available product.Then, in addition by Li
[TFSI] is dissolved in deionized water, and production includes the aqueous solution of Li [TFSI].
Then, molar ratio (mole/[P of Li [TFSI] according to Li [TFSI] relative to [P (DADMA)] [Cl]
(DADMA)] mole of [Cl]) two kinds of aqueous solutions are mixed and stirred for 2~8 hours as 1.2~2.0 mode, make solid
It is precipitated, obtained solid is recovered by filtration.Solid is cleaned using deionized water, be dried in vacuo within 12~48 hours, so as to
Access the polymer ([P (DADMA)] [TFSI]) with structural unit represented by general formula (1).
The content of polymer with structural unit represented by general formula (1) is not particularly limited, and is with total composition
Benchmark meter, preferably greater than or equal to 10 mass %, more preferably equal to or greater than 20 mass %, further preferably greater than or equal to 30
Quality %.In addition, being counted on the basis of total composition, the content of polymer is preferably lower than or equal to 80 mass %, more preferably small
In or equal to 70 mass %, 60 mass % are further preferably no larger than or are equal to.If the content of polymer is greater than or equal to 10 matter
% is measured, then there is the tendency that the intensity of polymer dielectric piece further increases.In addition, by the way that the content of polymer is set as small
In or be equal to 80 mass %, and increase the amount of other compositions ((poly-) glycol dialkyl ether complex compound etc.), can further mention
The ionic conductivity of high polymer electrolyte sheet.
[(poly-) glycol dialkyl ether complex compound]
Polymer electrolyte composition contains selected from least one of the group being made of lithium salts, sodium salt, magnesium salts and calcium salt
The complex compound ((poly-) glycol dialkyl ether complex compound) of (poly-) glycol dialkyl ether represented by salt and general formula (2).
(poly-) glycol dialkyl ether complex compound is liquid preferably under room temperature (for example, 25 DEG C).(poly-) ethylene glycol dioxane
For base ether complexes compared with (poly-) glycol dialkyl ether of not formed complex compound, oxidative resistance is excellent.In addition, (poly-) ethylene glycol
Dialkyl ether complex compound has anti-flammability, difficult volatile property, can have wide potential window.
The anion of salt can be halide ion (I-、Cl-、Br-Deng), SCN-、BF4 -、BF3(CF3)-、BF3(C2F5)-、BF3
(C3F7)-、BF3(C4F9)-、PF6 -、ClO4 -、SbF6 -、[FSI]-、[TFSI]-、N(C2F5SO2)2 -、BPh4 -、B(C2H4O2)2 -、
[f3C]-、C(CF3SO2)3 -、CF3COO-、CF3SO2O-、C6F5SO2O-、[BOB]-、RCOO-(R be carbon atom number 1~4 alkyl,
Phenyl or naphthyl.) etc..In them, the anion of electrolytic salt is preferably selected from by PF6 -、BF4 -、[FSI]-、[TFSI]-、
[BOB]-And ClO4 -At least one of group of composition, more preferably [TFSI]-Or [FSI]-。
Lithium salts as salt can be LiPF6、LiBF4、Li[FSI]、Li[TFSI]、Li[f3C]、Li[BOB]、LiClO4、
LiBF3(CF3)、LiBF3(C2F5)、LiBF3(C3F7)、LiBF3(C4F9)、LiC(SO2CF3)3、LiCF3SO2O、LiCF3COO、
(R is alkyl, phenyl or the naphthalene of carbon atom number 1~4 to LiRCOO.) etc..They can be used alone, and also can be used together two kinds
More than.
Sodium salt as salt can be NaPF6、NaBF4、Na[FSI]、Na[TFSI]、Na[f3C]、Na[BOB]、NaClO4、
NaBF3(CF3)、NaBF3(C2F5)、NaBF3(C3F7)、NaBF3(C4F9)、NaC(SO2CF3)3、NaCF3SO2O、NaCF3COO、
(R is alkyl, phenyl or the naphthalene of carbon atom number 1~4 to NaRCOO.) etc..They can be used alone, and also can be used together two kinds
More than.
It can be Mg (PF as the magnesium salts of salt6)2、Mg(BF4)2、Mg[FSI]2、Mg[TFSI]2、Mg[f3C]2、Mg
[BOB]2、Mg(ClO4)2、Mg[BF3(CF3)3]2、Mg[BF3(C2F5)]2、Mg[BF3(C3F7)]2、Mg[BF3(C4F9)]2、Mg[C
(SO2CF3)3]2、Mg(CF3SO2O)2、Mg(CF3COO)2、Mg(RCOO)2(R is alkyl, phenyl or the naphthalene of carbon atom number 1~4
Base.) etc..They can be used alone, and also can be used together two or more.
It can be Ca (PF as the calcium salt of salt6)2、Ca(BF4)2、Ca[FSI]2、Ca[TFSI]2、Ca[f3C]2、Ca
[BOB]2、Ca(ClO4)2、Ca[BF3(CF3)3]2、Ca[BF3(C2F5)]2、Ca[BF3(C3F7)]2、Ca[BF3(C4F9)]2、Ca[C
(SO2CF3)3]2、Ca(CF3SO2O)2、Ca(CF3COO)2、Ca(RCOO)2(R is alkyl, phenyl or the naphthalene of carbon atom number 1~4
Base.) etc..They can be used alone, and also can be used together two or more.
In them, from the viewpoint of ionic conductivity, salt is preferably lithium salts, more preferably selected from by LiPF6、LiBF4、
Li [FSI], Li [TFSI], Li [f3C], Li [BOB] and LiClO4At least one of group of composition, further preferably Li
[TFSI] or Li [FSI].
(poly-) glycol dialkyl ether is compound represented by the following general formula (2).
R1O-(CH2CH2O)m-R2 (2)
In formula (2), R1And R2The alkyl of carbon atom number 1~4 is each independently represented, m indicates 1~6 integer.
As R1And R2Alkyl, such as can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary fourth
Base etc..In them, alkyl is preferably methyl or ethyl.
M in formula (2) is 1~6, preferably 3 or 4, preferably 4.If being in (poly-) ethylene glycol of such range using m
Then there is the tendency for being easy that (poly-) glycol dialkyl ether complex compound is formed with salt in dialkyl ether.
(poly-) glycol dialkyl ether can be glycol dimethyl ether (referred to as " Monoglyme " or " G1 ".), diethylene glycol
Dimethyl ether (referred to as " Diglyme " or " G2 ".), triethylene glycol dimethyl ether (referred to as " Triglyme " or " G3 ".), tetraethylene glycol two
Methyl ether (referred to as " Tetraglyme " or " G4 ".), five ethylene glycol dimethyl ether (referred to as " Pentaglyme " or " G5 ".), six second two
Diethylene glycol dimethyl ether (referred to as " Hexaglyme " or " G6 ".) etc..In them, (poly-) glycol dialkyl ether is preferably triethylene glycol two
Methyl ether or tetraethyleneglycol dimethyl ether, more preferably tetraethyleneglycol dimethyl ether.
(poly-) glycol dialkyl ether complex compound is preferably the complex compound of lithium salts and tetraethyleneglycol dimethyl ether.Specifically,
The complex compound [LiG4] [TFSI], Li [TFSI] and tetraethyleneglycol dimethyl ether of Li [TFSI] and tetraethyleneglycol dimethyl ether can be enumerated
Complex compound [LiG4] [FSI] etc..
(poly-) glycol dialkyl ether complex compound for example can be by by above-mentioned salt and above-mentioned (poly-) ethylene glycol dioxane
Base ether mixes to obtain.
Mixing molar ratio ((poly-) ethylene glycol two of the molal quantity of (poly-) glycol dialkyl ether relative to the molal quantity of salt
Molal quantity/salt molal quantity of alkyl ether) it is preferably 0.5~2.0, more preferably 0.7~1.4, further preferably 0.9~
1.0.If mixing molar ratio is greater than or equal to 0.5, the viscosity that there is (poly-) glycol dialkyl ether complex compound becomes suitable
When the tendency of range.If mixing molar ratio is less than or equal to 2.0, there are (poly-) ethylene glycol dioxanes of not formed complex compound
The tendency that the ratio of base ether becomes smaller.
The manufacturing method of (poly-) glycol dialkyl ether complex compound is not particularly limited.The complexing of (poly-) glycol dialkyl ether
Object for example can by be less than or equal to (poly-) glycol dialkyl ether boiling point at a temperature of make salt and (poly-) ethylene glycol two
Alkyl ether mixes to obtain.Mixed time, temperature can be suitably set.
The content of (poly-) glycol dialkyl ether complex compound is not particularly limited, it is calculated as 10 on the basis of total composition~
70 mass %.It is counted on the basis of total composition, the content of (poly-) glycol dialkyl ether complex compound is preferably greater than or equal to 20
Quality %, more preferably equal to or greater than 30 mass %.In addition, being counted on the basis of total composition, (poly-) glycol dialkyl ether
The content of complex compound is preferably lower than or equal to 65 mass %, more preferably less than or equal to 55 mass %.(if poly-) ethylene glycol two
The content of alkyl ether complexes is greater than or equal to 10 mass %, then the ionic conductivity that there is polymer dielectric piece further mentions
High tendency.If the content of (poly-) glycol dialkyl ether complex compound is less than or equal to 70 mass %, there are electrostrictive polymers
Solve the more excellent tendency of the self-supporting of matter piece.
Polymer electrolyte composition, which can also further contain, does not form complex compound with (poly-) glycol dialkyl ether
Selected from least one of the group being made of lithium salts, sodium salt, magnesium salts and calcium salt.These salt can work as electrolytic salt.
These salt can be used with it is above-mentioned illustrated by the same salt of salt.
Not forming the salt of complex compound with (poly-) glycol dialkyl ether can be lithium salts.Lithium salts is preferably selected from by LiPF6、
LiBF4, Li [FSI], Li [TFSI], Li [f3C], Li [BOB] and LiClO4At least one of group of composition, more preferably Li
[TFSI] or Li [FSI].
The content for the salt for not forming complex compound with (poly-) glycol dialkyl ether is not particularly limited, and is with total composition
Benchmark meter is preferably greater than or equal to 3 mass %, more preferably equal to or greater than 5 mass %, further preferably greater than or equal to 7 matter
Measure %.It is counted on the basis of total composition, the content of salt is preferably lower than or equal to 30 mass %, more preferably less than or equal to 25 matter
% is measured, 20 mass % are further preferably no larger than or are equal to.If the content of salt is greater than or equal to 3 mass %, there are ion biographies
The tendency that conductance further increases.If the content of salt is less than or equal to 30 mass %, there are the soft of polymer dielectric piece
The soft tendency further increased.
Polymer electrolyte composition can also be further containing not and selected from being made of lithium salts, sodium salt, magnesium salts and calcium salt
At least one of group form (poly-) glycol dialkyl ether represented by the general formula (2) of complex compound.It is with total composition
Benchmark meter, the content that (poly-) glycol dialkyl ether of complex compound is not formed with salt can be less than or equal to 10 mass %, be less than
Or it is equal to 5 mass % or is less than or equal to 1 mass %.
[other compositions]
Polymer electrolyte composition also can according to need the grain further containing oxides such as silica, aluminium oxide
Son or fiber, Li7La3Zr2O12(LLZ) the adding with lithium salts dissociation capability such as inorganic solid electrolytes, borate, Aluminate such as
Add agent etc..They can be used alone or combine two or more use.In polymer electrolyte composition further
It in the case where containing these ingredients, is counted on the basis of total composition, the content of these ingredients can be 0.01~20 mass %.
Polymer electrolyte composition can be formed as sheet.
The thickness of polymer dielectric piece can be adjusted to desired thickness according to the composition of battery.Polymer dielectric
The thickness of piece is preferably greater than or equal to 1 μm, more preferably equal to or greater than 3 μm, further preferably greater than or equal to 5 μm.In addition, poly-
The thickness of polymer electrolyte piece is preferably lower than or equal to 200 μm, more preferably less than or equal to 100 μm, be further preferably no larger than or
Equal to 70 μm.If thickness is greater than or equal to 1 μm, there is the tendency of mutual short circuit between capable of more inhibiting electrode.If
Thickness is less than or equal to 200 μm, then in the presence of the tendency that can further increase energy density.
Then, the manufacturing method of above-mentioned polymer secondary battery 1 is illustrated.Polymer of the present embodiment
The manufacturing method of secondary cell 1 has: first step, forms positive electrode material mixture layer 10 on positive electrode collector 9 and obtains anode 6；
The second step forms anode mixture layer 12 on negative electrode collector 11 and obtains cathode 8；And the third step, in anode 6 and bear
Electrolyte layer 7 is set between pole 8.
In first step, anode 6 such as can obtain as follows: anode mixture will be used for using kneading machine, dispersion machine
The material of layer is scattered in decentralized medium, will by scraper method, infusion process, gunite etc. after obtaining the anode mixture of pulp-like
The anode mixture is coated on positive electrode collector 9, then decentralized medium is made to volatilize.It, can also basis after so that decentralized medium is volatilized
Need to be set using the compression forming process of roll squeezer.Positive electrode material mixture layer 10 can also be by carrying out repeatedly from above-mentioned anode mixture
The volatilization for being applied to decentralized medium until process, be formed as the positive electrode material mixture layer of multilayered structure.
The decentralized medium used in first step can be water, 1-Methyl-2-Pyrrolidone (hereinafter referred to as NMP.)
Deng.
In the second step, the method that anode mixture layer 12 is formed on negative electrode collector 11 can be and above-mentioned first
The same method of process.
In the third step, in one embodiment, electrolyte layer 7 on substrate for example by making comprising above-mentioned poly-
The polymer dielectric piece of polymer electrolyte composition is formed.Fig. 4 (a) is the electrostrictive polymer for indicating an embodiment and being related to
Solve the schematic section of matter piece.As shown in Fig. 4 (a), polymer dielectric piece 13A has substrate 14 and is set on substrate 14
Electrolyte layer 7.
Polymer dielectric piece 13A for example makes as follows: the polymer electrolyte composition by that will be used for electrolyte layer 7
It is scattered in decentralized medium and after obtaining slurry, is coated on substrate 14, then decentralized medium is made to volatilize.It will be used to be electrolysed
The decentralized medium of the polymer electrolyte composition dispersion of matter layer 7, such as can be acetone, methyl ethyl ketone, gamma-butyrolacton
Deng.
As long as substrate 14 have be resistant to when volatilize decentralized medium heat heat resistance, not with polymer dielectric group
Close object reaction and will not be swollen because of polymer electrolyte composition just there is no limit, for example, metal foil, be made of resin
Film etc..Specifically, substrate 14 can be the metal foils such as aluminium foil, copper foil, nickel foil；By polyethylene terephthalate, poly- four
The film etc. that the resins such as vinyl fluoride, polyimides, polyether sulfone, polyether-ketone (general engineering plastics) are constituted.
In the case where using the film being made of resin as substrate 14, from the decentralized medium for electrolyte layer 7
From the viewpoint of adaptability, the heat resisting temperature of substrate 14 is preferably greater than or equal to 50 DEG C, more preferably equal to or greater than 100 DEG C, into
One step is preferably greater than or equal to 150 DEG C, in addition, can for example be less than or equal to 400 DEG C.If using having above-mentioned heat resisting temperature
Substrate, then can compatibly use decentralized medium as described above.It should be noted that using the film being made of resin
When, the heat resisting temperature of substrate 14 indicates the fusing point or decomposition temperature of resin.
The thickness of substrate 14 is preferably as thin as possible in the case where maintaining the intensity for the drawing force for being resistant to apparatus for coating.
From while reducing the whole volume of polymer dielectric piece 13 when polymer electrolyte composition is coated on substrate 14
From the viewpoint of ensuring intensity, the thickness of substrate 14 is preferably greater than or equal to 5 μm, more preferably equal to or greater than 10 μm, further
Preferably greater than or equal to 25 μm, additionally, it is preferred that it is less than or equal to 100 μm, it is more preferably less than or equal to 50 μm, further preferably small
In or equal to 40 μm.
Polymer dielectric piece can also be continuously manufactured by while wound into rolls.In this case, due to electricity
It solves the surface of matter layer 7 and the rear-face contact of substrate 14 and is pasted onto a part of electrolyte layer 7 on substrate 14, electrolyte layer 7
It is damaged sometimes.This situation in order to prevent, as other embodiments, polymer dielectric piece can also be in electrolyte layer 7
With 14 opposite side of substrate be arranged protected material.Fig. 4 (b) is to indicate showing for polymer dielectric piece that other embodiments are related to
Meaning sectional view.As shown in Fig. 4 (b), polymer dielectric piece 13B further has electrolyte layer 7 with 14 opposite side of substrate
Standby protected material 15.
As long as protected material 15 can be easily peeled off from electrolyte layer 7, preferably polyethylene, polypropylene, polytetrafluoroethyl-ne
The nonpolar resin film such as alkene.If electrolyte layer 7 is not pasted each other with protected material 15, energy using nonpolar resin film
Enough it is easily peeled off protected material 15.
From reduce polymer dielectric piece 13B entirety volume while ensure intensity from the viewpoint of, protected material 15
Thickness be preferably greater than or equal to 5 μm, more preferably 10 μm, additionally, it is preferred that be less than or equal to 100 μm, more preferably less than or wait
In 50 μm, it is further preferably no larger than or equal to 30 μm.
From inhibit low temperature environment under deterioration and inhibit hot environment under softening from the viewpoint of, protected material 15 it is resistance to
Preferably greater than or equal to -30 DEG C of hot temperature, more preferably equal to or greater than 0 DEG C, additionally, it is preferred that being less than or equal to 100 DEG C, more preferably
Less than or equal to 50 DEG C.In the case where protected material 15 are arranged, since the volatilization process of above-mentioned decentralized medium is not required,
Therefore it does not need to improve heat resisting temperature.
It is arranged between anode 6 and cathode 8 in the method for electrolyte layer 7 using polymer dielectric piece 13A, such as from poly-
Anode 6, electrolyte layer 7 and cathode 8 are laminated by lamination, it is secondary to obtain polymer by polymer electrolyte piece 13A peeling base 14
Battery 1.At this moment, the side of 10 side of positive electrode material mixture layer of anode 6 and 12 side of anode mixture layer of cathode 8 is located at according to electrolyte layer 7
Formula stacking, i.e., according to configuring in order positive electrode collector 9, positive electrode material mixture layer 10, electrolyte layer 7, anode mixture layer 12 and cathode collection
The mode of electric body 11 is laminated.
In the third step, in other embodiments, electrolyte layer 7 is formed in the anode conjunction of anode 6 by being coated with
At least either side in 10 side of oxidant layer and 12 side of anode mixture layer of cathode 8 is preferably formed in the anode of anode 6 by being coated with
10 side of mixture layer and this two sides of 12 side of anode mixture layer of cathode 8.In this case, for example, making be equipped with electrolyte layer 7 just
Pole 6 and cathode 8 equipped with electrolyte layer 7 in such a way that electrolyte layer 7 is in contact with each other for example by being laminated, can
Obtain polymer secondary battery 1.
The method for forming electrolyte layer 7 by being coated in positive electrode material mixture layer 10 is, for example, following method, it may be assumed that is used in
The polymer electrolyte composition of electrolyte layer 7 is scattered in decentralized medium, after obtaining slurry, using applicator by electrostrictive polymer
Solution matter composition is coated in positive electrode material mixture layer 10.It is used in the dispersion of the polymer electrolyte composition dispersion of electrolyte layer 7
Medium can be for example acetone, methyl ethyl ketone, gamma-butyrolacton etc..
Formed on anode mixture layer 12 by being coated with electrolyte layer 7 method can for in positive electrode material mixture layer 10
The same method of method of electrolyte layer 7 is formed by being coated with.
[second embodiment]
Then, the polymer secondary battery that second embodiment is related to is illustrated.Fig. 5 is to indicate second embodiment
The schematic section of one embodiment of the electrode group in polymer secondary battery being related to.As shown in figure 5, the second embodiment party
It is bipolar that the difference of the polymer secondary battery of the polymer secondary battery and first embodiment of formula is that electrode group 2B has
Electrode 16.That is, electrode group 2B successively has positive 6, first electrolyte layer 7, bipolar electrode 16, the second electrolyte layer 7 and cathode
8。
Bipolar electrode 16 has the surface of bipolar electrode collector 17,8 side of cathode for being set to bipolar electrode collector 17
Positive electrode material mixture layer 10 and be set to bipolar electrode collector 17 6 side of anode surface anode mixture layer 12.
Bipolar electrode collector 17 can be formed by aluminium, stainless steel, titanium etc..Specifically, bipolar electrode collector 17 can
Think the aluminum perforated foil in the hole with 0.1~10mm of aperture, expanded metal mesh, foamable metal sheet etc..Than that described above, as long as
The variations such as dissolution, oxidation do not occur in the use of battery, so that it may bipolar electrode collector 17 be formed by arbitrary material, separately
Outside, also there is no limit for shape, manufacturing method etc..
The thickness of bipolar electrode collector 17 can be greater than or equal to 10 μm, more than or equal to 15 μm or be greater than or equal to
20μm.The thickness of bipolar electrode collector 17 can be less than or equal to 100 μm, is less than or equal to 80 μm or be less than or equal to 60 μ
m。
Then, the manufacturing method for the secondary cell being related to second embodiment is illustrated.It is of the present embodiment
The manufacturing method of secondary cell has following process: first step, forms positive electrode material mixture layer 10 on positive electrode collector 9 and obtains
Anode 6；The second step forms anode mixture layer 12 on negative electrode collector 11 and obtains cathode 8；The third step, in bipolar electric
One face of electrode current collector 17 forms positive electrode material mixture layer 10, forms anode mixture layer 12 in another face and obtains bipolar electrode
16；And the fourth step, electrolyte layer is set between anode 6 and bipolar electrode 16 and between cathode 8 and bipolar electrode 16
7。
First step and the second step can for in first embodiment first step and the same side of the second step
Method.
In the third step, bipolar electrode collector 17 a face formed positive electrode material mixture layer 10 method can for
The same method of first step in first embodiment.Anode mixture layer is formed in another face of bipolar electrode collector 17
12 method can be method same as the second step in first embodiment.
In the fourth step, as the method that electrolyte layer 7 is arranged between anode 6 and bipolar electrode 16, in a reality
It applies in mode, electrolyte layer 7 on substrate for example by manufacturing the polymer dielectric piece comprising polymer electrolyte composition
To be formed.The manufacturing method of polymer dielectric piece can be and polymer dielectric piece 13A, 13B of first embodiment
The same method of manufacturing method.
In the fourth step, between cathode 8 and bipolar electrode 16 be arranged electrolyte layer 7 method can for it is above-mentioned
The same method of method of electrolyte layer 7 is set between anode 6 and bipolar electrode 16.
Electrolysis is formed by being coated in the positive electrode material mixture layer 10 of anode 6 and on the anode mixture layer 12 of bipolar electrode 16
The method of matter layer 7 can be to be related to an embodiment of the third step in first embodiment in positive electrode material mixture layer 10
On form the method for electrolyte layer 7 by being coated with and form the side of electrolyte layer 7 by being coated on anode mixture layer 12
The same method of method.
As the method that electrolyte layer 7 is arranged between anode 6 and bipolar electrode 16 in the fourth step, in other implementations
In mode, electrolyte layer 7 is formed in the anode mixture layer of positive electrode material mixture layer 10 side and bipolar electrode 16 of anode 6 by being coated with
At least either side in 12 sides is preferably formed in 10 side of positive electrode material mixture layer of anode 6 and bearing for bipolar electrode 16 by being coated with
This two sides of 12 side of pole mixture layer.In this case, for example, the anode 6 of electrolyte layer 7 will be equipped with and equipped with electrolyte layer 7
Bipolar electrode 16 is in such a way that electrolyte layer 7 is in contact with each other by being laminated.
Embodiment
Hereinafter, further specifically describing the present invention by embodiment, but the present invention is not limited to these Examples.
[synthesis of polymer]
By by the counter anion Cl of diallyl dimethyl ammoniumchloride-It is changed to [TFSI]-To synthesize with general formula
(1) polymer of the structural unit represented by.
Firstly, 100 mass parts [P (DADMA)] [Cl] aqueous solution (20 mass % aqueous solutions, Aldrich system) is used
The dilution of 500 mass parts distilled water, makes diluted polymer aqueous solution.Then, by 43 mass parts Li [TFSI] (bank field chemistry strain formula
Commercial firm's corporation) it is dissolved in 100 mass parts water, make Li [TFSI] aqueous solution.By being added dropwise to diluted polymer water
It in solution, and stirs 2 hours, obtains white precipitate.Precipitate is separated by filtering, the distilled water with 400 mass parts is clear
After washing, it is filtered again.Cleaning and filtering repeat 5 times.Then, moisture is evaporated by 105 DEG C of vacuum drying, obtained
To [P (DADMA)] [TFSI].The viscosity average molecular weigh of [P (DADMA)] [TFSI] is 2.11 × 106g·mol-1。
About viscosity average molecular weigh Mv, uses polymethyl methacrylate (PMMA) as standard substance, use black formula viscosity
After viscosity [η] of the meter measurement polymer at 25 DEG C, based on [η]=KMv, (here, K indicates flare factor, which depends on temperature
Degree, polymer and solvent property.) calculate.
(embodiment 1)
[modulation of polymer dielectric piece]
As shown in table 1, relative to the obtained polymer of 8 mass parts, 10 mass parts is added and are used as (poly-) ethylene glycol dioxane
[LiG4] [TFSI] (content of (poly-) glycol dialkyl ether complex compound in composition: 50 mass %) of base ether complexes, 2
Mass parts are as the Li [TFSI] for the salt for not forming complex compound with (poly-) glycol dialkyl ether and 16 mass parts as dispersion
The acetone of medium is simultaneously stirred, and modulates slurry.It should be noted that [LiG4] [TFSI] is using in advance by tetraethylene glycol diformazan
What ether (Sigma-Aldrich corporation) and Li [TFSI] (bank field chemistry strain formula meeting corporation) were mixed to get with molar ratio 1:1
Composition.Using scraper method, 100 μm slurry is coated on aluminium foil with gap, it is 2 hours dry at 40 DEG C, so that acetone is volatilized.
Then, at 60 DEG C, less than or equal to 1.0 × 104It is 10 hours dry under the decompression of Pa (being less than or equal to 0.1 atmospheric pressure), it obtains
To 28 μm of thickness of polymer dielectric piece.
[measurement of quality residual rate]
Being dried under reduced pressure for 60 DEG C of measurement (is being less than or equal to 1.0 × 104Pa (being less than or equal to 0.1 atmospheric pressure) subtracts
Dry 10 hours of pressure) before and after polymer dielectric piece mass change, calculate the quality residual rate of polymer dielectric piece.
Quality residual rate is calculated based on following formula.It shows the result in table 2.
Quality residual rate [quality %]=[quality [g] of the polymer electrolyte composition after dry/(poly- before dry
(dispersion is situated between volatile ingredient contained in polymer electrolyte composition before the quality [g]-of polymer electrolyte composition is dry
Matter) quality [g])] × 100
Since the volatile ingredients such as acetone, water are possible to remain in polymer in polymer electrolyte composition before it is dried
In, therefore in said determination, it is remained in the polymer with being subtracted from the quality of the polymer electrolyte composition before drying
The obtained value of the quality of the volatile ingredients such as acetone, water is used as benchmark meter, finds out quality residual rate.About above-mentioned " before dry
The quality of volatile ingredient contained in polymer electrolyte composition (decentralized medium) ", in addition to not using (poly-) ethylene glycol
60 DEG C of the polymer electrolyte composition progress made and operating similarly to Example 1 other than dialkyl ether complex compound subtracts
It press dry dry, is found out by the mass change before and after it.
[evaluation of self-supporting sheet material formative]
The polymer dielectric piece being formed on aluminium foil obtained in embodiment 1 is removed from aluminium foil, verifies polymer
The self-supporting of electrolyte sheet.About evaluation, the polymer dielectric piece on the aluminium foil for being formed in 20cm square is used.It will
Be greater than 10cm square size polymer-stripping electrolyte sheet the case where be evaluated as A, will be with 5cm square~10cm square
Size polymer-stripping electrolyte sheet the case where be evaluated as B, will be less than 5cm square size polymer-stripping be electrolysed
The case where matter piece, is evaluated as C.It shows the result in table 2.
[measurement of ionic conductivity]
With aluminium foil sandwich embodiment 1 obtained in polymer dielectric piece, be punched intoMake ionic conductivity
Measurement sample.By sample configuration in the enclosed cell unit (HS Cell, precious Izumi Ltd.'s system) of bipolar system, use
AC impedance measuring device (1260 types, Solartron corporation) is measured.In thermostat between -5 DEG C~70 DEG C with
15 DEG C of intervals are adjusted, and measure AC impedance in the range of 10mV, 1Hz~2MHz.By the real axis with nyquist plot
Intersection point calculate resistance value, ionic conductivity is calculated by resistance value.The result of ionic conductivity at 25 DEG C is shown in table 2
In.It should be noted that it is the reality in the glove box of argon atmosphere that sample, which is configured in the operation in enclosed cell unit,
It applies.
[production of battery]
By 90 mass parts LiFePO4(conductive agent, trade name: HS-100 is put down for (positive active material), 5 mass parts acetylene blacks
Equal partial size 48nm (manufacture original directory value), Deuki Kagaku Kogyo Co., Ltd), (bonding of 100 mass parts Kynoar solutions
Agent, trade name: KUREHA KF Polymer#7305, solid component 5 mass %, Co., Ltd. KUREHA) and 28 mass parts
N-methyl-2-pyrrolidone (NMP) mixing, modulation anode mixture paste.The anode mixture muddle is distributed in positive electrode collector (thickness
20 μm of aluminium foil) on two sides, rolled after dry at 120 DEG C, form 91 μm of single side thickness, one side coating amount 50g/m2、
Mixture density 1.8g/cm3Positive electrode active material layer, production anode.In order to make the button-type battery of test, anode prepares
It is punched intoAnode.
As cathode, lithium foil is punched by preparationCathode.According to anode, polymer dielectric piece, lithium foil
Sequence stack, and configure in the button cell container of CR2032 type.At this moment, lithium foil works as negative electrode active material,
The stainless steel of button cell container works as negative electrode collector.It is by the washer across insulating properties that battery case top is tight
Gu and it is closed, to obtain lighium polymer secondary battery.
[evaluation of battery performance]
Using the lighium polymer secondary battery made by the above method, the evaluation of battery performance is carried out.Use charge and discharge
Device (System Co., Ltd., Japan, trade name: TOSCAT-3200) implements charge and discharge electrometric determination at 25 DEG C with 0.05C, right
In the discharge capacity that the 3rd recycles, design capacity ratio is calculated based on following formula.It shows the result in table 2.It should be noted that C
Refer to " current value [A]/design theory capacity [Ah] ", 1C represent in 1 hour by battery it is fully charged or completely discharge institute
The current value needed.
Design capacity ratio [%]=(discharge capacity [mAh]/battery design capacity [mAh]) × 100
(embodiment 2)
In addition to the content of (poly-) glycol dialkyl ether complex compound is changed to 4.3 mass parts (compositions from 10 mass parts
In (poly-) glycol dialkyl ether complex compound content: 30 mass %) other than, operate similarly with example 1 and make poly-
Polymer electrolyte piece, is evaluated similarly to Example 1.It shows the result in table 2.
(embodiment 3)
In addition to the content of (poly-) glycol dialkyl ether complex compound is changed to 1.1 mass parts (compositions from 10 mass parts
In (poly-) glycol dialkyl ether complex compound content: 10 mass %) other than, operate similarly with example 1 and make poly-
Polymer electrolyte piece, is evaluated similarly to Example 1.It shows the result in table 2.
(comparative example 1)
In addition to being changed to from [LiG4] [TFSI] as (poly-) glycol dialkyl ether complex compound as organic solvent
Other than dimethyl carbonate (DMC), operate similarly with example 1 and make polymer dielectric piece, similarly to Example 1 into
Row evaluation.It shows the result in table 2.
[table 1]
[table 2]
Contain polymer and (poly-) glycol dialkyl ether complex compound with structural unit represented by general formula (1)
The polymer electrolyte composition of the Examples 1 to 3 of [LiG4] [TFSI] passes at room temperature with excellent macroion
Conductance, even if being also able to maintain its shape with sheet material itself without substrate etc..In addition distinguish, the electrostrictive polymer of Examples 1 to 3
Even if solve matter composition 60 DEG C, be less than or equal to 1.0 × 104Drying under the decompression of Pa (being less than or equal to 0.1 atmospheric pressure)
10 hours, quality was not also reduced substantially, was the high material of thermal stability.In contrast, the poly- of the comparative example 1 of DMC has been used
If polymer electrolyte composition 60 DEG C, be less than or equal to 1.0 × 104The decompression of Pa (being less than or equal to 0.1 atmospheric pressure)
Lower drying 10 hours, then most DMC volatilization, ionic conductivity are greatly lowered.It is confirmed by these results: of the invention
Polymer electrolyte composition can make high with excellent high ion conductivity and self-supporting at room temperature
Sheet material.
Industrial availability
According to the present invention, it is possible to provide even if a kind of do not use organic solvent, can also make at room temperature with excellent
Ionic conductivity and the high sheet material of the self-supporting for being also able to maintain its shape with sheet material itself in the case wheres no substrate etc.
Polymer electrolyte composition.In addition, according to the present invention, it is possible to provide used the polymerization of this polymer electrolyte composition
Object secondary cell.
Symbol description
1: polymer secondary battery, 2,2A, 2B: electrode group, 3: battery exterior body, 4: positive pole current collections tab, 5: cathode collection
Electrode ear, 6: anode, 7: electrolyte layer, 8: cathode, 9: positive electrode collector, 10: positive electrode material mixture layer, 11: negative electrode collector, 12:
Anode mixture layer, 13A, 13B: polymer dielectric piece, 14: substrate, 15: protected material, 16: bipolar electrode, 17: bipolar electrode collection
Electric body.
Claims (7)
1. a kind of polymer electrolyte composition, contains: the polymer with structural unit represented by the following general formula (1)；
And (poly-) represented by least one of the group being made of lithium salts, sodium salt, magnesium salts and calcium salt salt and the following general formula (2)
The complex compound of glycol dialkyl ether,
[changing 1]
In formula (1), X-Indicate counter anion,
R1O-(CH2CH2O)m-R2 (2)
In formula (2), R1And R2The alkyl of carbon atom number 1~4 is each independently represented, m indicates 1~6 integer.
2. polymer electrolyte composition according to claim 1, the content of the complex compound is using total composition as base
Standard is calculated as 10~70 mass %.
3. polymer electrolyte composition according to claim 1 or 2, the anion of the salt is selected from by PF6 -、BF4 -、
N(FSO2)2 -、N(CF3SO2)2 -、B(C2O4)2 -And ClO4 -At least one of group of composition.
4. polymer electrolyte composition described in any one of claim 1 to 3, the salt is lithium salts.
5. polymer electrolyte composition according to any one of claims 1 to 4, the m in the formula (2) is 3 or 4.
6. polymer electrolyte composition according to any one of claims 1 to 5, is formed as sheet.
7. a kind of polymer secondary battery has anode, cathode and electrolyte layer,
The electrolyte layer is set between the anode and the cathode, and includes according to any one of claims 1 to 6
Polymer electrolyte composition.
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| JPWO2018193631A1 (en) | 2020-02-27 |
| CN110537284B (en) | 2023-07-21 |
| WO2018193631A1 (en) | 2018-10-25 |
| JP6881570B2 (en) | 2021-06-02 |
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