CN1362711A - Polymer gel electrolyte, lithium cell adopting said electrolytre and method for producing said electrolyte - Google Patents
Polymer gel electrolyte, lithium cell adopting said electrolytre and method for producing said electrolyte Download PDFInfo
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- CN1362711A CN1362711A CN01138425A CN01138425A CN1362711A CN 1362711 A CN1362711 A CN 1362711A CN 01138425 A CN01138425 A CN 01138425A CN 01138425 A CN01138425 A CN 01138425A CN 1362711 A CN1362711 A CN 1362711A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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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- 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
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The lithium secondary battery comprises a cathode, an anode, and the separator, wherein the separator is a framework-structured insulating resin sheet containing the gel-type polymer electrolyte in the framework-structure. The gel-type polymer electrolyte is produced by polymerizing a precursor comprising a polymer having a repeating unit represented by the formula 1, a crosslinking agent represented by the formula 2, and an electrolyte solution comprising lithium salts and a non-aqueous solvent. In the formula, x is 0.1-0.6, y is 0.1-0.8, z is 0.1-0.8, R is C1-C6 alkyl, and n is 3-30.
Description
Technical field
The present invention relates to a kind of gel-form solid polymer electrolyte and adopt this electrolytical lithium battery, more specifically, the present invention relates in battery the gel-form solid polymer electrolyte that generates by polymerization, and the method for producing this gel-form solid polymer electrolyte, the invention still further relates to the isolator that contains this gel-form solid polymer electrolyte by use, improved the lithium battery of high speed charge/discharge characteristics, and the method for producing this lithium battery.
Background technology
Lithium storage battery adopts liquid electrolyte or solid electrolyte, particularly polymer dielectric.Because lithium storage battery adopted polymer dielectric, with regard to can not be owing to the leakage of electrolyte damage equipment, and electrolyte self makes the battery miniaturization as a kind of barrier film, and the high-energy-density battery is achieved.Owing to have these advantages, can will use the lithium storage battery of this polymer dielectric, for example as the power supply of portable electric appts and Computer Storage backup, this has caused that people pay close attention to greatly.
For example, described a kind of lithium storage battery that uses polymer dielectric as barrier film in United States Patent (USP) 5 952 126, the polymer substrate that polymer dielectric contains in this patent is made up of copolymer and a kind of electrolyte of N-N-isopropylacrylamide and polyethylene glycol dimethacrylate.Polymer substrate and electrolyte are made into film and insert between negative electrode and the anode.In addition, the composition that forms polymer substrate comprises polyethylene glycol and/or dimethylacrylate, and this composition can further add when making electrode.
Yet the making of above-mentioned lithium storage battery is quite difficult.And because the content of electrolyte is low, the ionic conductivity between the anodic-cathodic is degenerated, and has influenced the performance of battery conversely, for example because the low capacity of high speed charge/discharge characteristics.
Summary of the invention
First and second purposes of the present invention provide a kind of gel-form solid polymer electrolyte, this electrolyte has good mechanical strength, and the electrolyte that uses more amount improved the ionic conductivity between the electrode, and the present invention simultaneously also provides the method for making this gel-form solid polymer electrolyte.
Third and fourth purpose of the present invention provides a kind of lithium battery, by using this gel-form solid polymer electrolyte, makes this lithium battery have improved high speed charge/discharge characteristics, and the method for making this lithium battery also is provided.
In order to realize first purpose, comprise the crosslinking agent shown in the polymer shown in the formula 1, the formula 2 and the polymer electrolyte precursor of the electrolyte formed by lithium salts and non-aqueous organic solvent by polymerization, prepare gel-form solid polymer electrolyte:
[formula 1]
[formula 2]
Wherein, x is 0.1～0.6mol, and y is 0.1～0.8mol, and z is 0.1～0.8mol, and R is the alkyl that contains 1～6 carbon atom, and n is 3～30 integer, and R ' is hydrogen or CH
3
In order to realize second purpose, the method for making gel-form solid polymer electrolyte is provided, this method may further comprise the steps:
(a-1) prepare polymer electrolyte precursor by crosslinking agent shown in the polymer shown in hybrid 1, the formula 2 and the electrolyte formed by lithium salts and non-aqueous organic solvent:
[formula 1]
[formula 2]
Wherein, x is 0.1～0.6mol, and y is 0.1～0.8mol, and z is 0.1～0.8mol, and R is the alkyl that contains 1～6 carbon atom, and n is 3～30 integer, and R ' is hydrogen or CH
3With
(b-1) this polymer electrolyte precursor of polymerization.
In order to realize the 3rd purpose, a kind of lithium battery that has cathode and anode and inserted a barrier film between these the two poles of the earth is provided, its septation is a kind of cancellated insulating resin plate that comprises gel-form solid polymer electrolyte, and this polymer dielectric is to comprise the crosslinking agent shown in the polymer shown in the formula 1, the formula 2 and the polymer electrolyte precursor of the electrolyte be made up of lithium salts and non-aqueous organic solvent prepares by polymerization:
[formula 1]
[formula 2]
Wherein x is 0.1～0.6mol, and y is 0.1～0.8mol, and z is 0.1～0.8mol, and R is the alkyl that contains 1～6 carbon atom, and n is 3～30 integer, and R ' is hydrogen or CH
3
In order to realize the 4th target, a kind of lithium battery manufacture method is provided, may further comprise the steps: (a-2) have cancellated insulating resin plate and form electrode assembly by one of insertion between negative electrode and anode, this electrode assembly battery case (b-2) of packing into is injected the battery case that this electrode assembly is housed to the polymer electrolyte precursor of the electrolyte that comprises the crosslinking agent shown in the polymer shown in the formula 1, the formula 2 and be made up of lithium salts and non-aqueous organic solvent, polymer electrolyte precursor is immersed have cancellated insulating resin plate.
[formula 1]
[formula 2]
Wherein x is 0.1～0.6mol, and y is 0.1～0.8mol, and z is 0.1～0.8mol, and R is the alkyl that contains 1～6 carbon atom, and n is 3～30 integer, and R ' is hydrogen or CH
3And (c-2) product that obtains by (b-2) of polymerization and generate gel-form solid polymer electrolyte.
Polymer weight average molecular weight shown in the preferred formula 1 is 5 000～2 000 000, and based on 100 parts by weight polymer electrolyte precursors, its content is 2～10 weight portions.
The weight average molecular weight of the crosslinking agent shown in the formula 2 is preferred 258～500 000, and based on 100 parts by weight polymer electrolyte precursors, its content is preferably 0.01～50 weight portion.
Based on 100 parts by weight polymer electrolyte precursors, polymer electrolyte precursor can also contain the N as crosslinking agent, N-(1, the 4-phenylene) dimaleimide 0.01～50 weight portion.
In the present invention, non-aqueous organic solvent is at least a from propylene carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate and ethylene carbonate preferably, and lithium salts is selected from LiClO
4, LiBF
4, LiPF
6, LiCF
3SO
3, LiN (CF
3SO
2)
2At least a.
And based on 100 parts by weight polymer electrolyte precursors, the content of electrolyte is preferably 40～98 weight portions.
Preferably, insulating resin plate is used in combination by polyvinyl resin, acrylic resin or with it and forms, and its porosity is 40～80%, and thickness is 10～30 μ m.
When preparation polymer dielectric and lithium battery, polymerization temperature is preferably 60～100 ℃.
Description of drawings
With reference to accompanying drawing, by describing the preferred embodiments of the invention in detail, above-mentioned purpose of the present invention and advantage can be more obvious:
The standard charge characteristic of the lithium storage battery that the curve representation embodiments of the invention 1～4 among Fig. 1 are made.
Discharge-the rate capability of the lithium storage battery that the curve representation embodiments of the invention 1 among Fig. 2 are made.
Embodiment
Among the present invention, gel-form solid polymer electrolyte is used as barrier film, or uses the plate that has cancellated insulating resin plate and contain gel-form solid polymer electrolyte in matrix.Because polymer dielectric exists with gel form in the network structure of plate, so the leakage of electrolyte can not take place.And ion motion free love degree is bigger when using pure solid electrolyte, helps the ionic conductance between negative electrode and the anode.
Insulating resin plate is used as the carrier of polymer dielectric, and has kept the intensity of barrier film.The specific example of this insulating resin plate comprises polyvinyl resin, acrylic resin, or it is used in combination.Here, the thickness of insulating resin plate is preferably 10～30 μ m, and porosity is preferably 40～80%.If the thickness of insulating resin plate surpasses 30 μ m, battery performance may be degenerated.If minute short circuit may take place less than 10 μ m in the thickness of insulating resin plate.If porosity is greater than 80%, battery performance may be degenerated.If porosity is less than 40%, barrier film just is difficult to make, and that is undesirable.
The polymer dielectric that contains in the preparation insulating resin plate network structure, be to contain the polymer electrolytic precursor of the crosslinking agent shown in the polymer shown in the formula 1, the formula 2 and the polymer electrolyte precursor of forming by lithium salts and non-aqueous organic solvent by polymerization, or polymerization is added with N, N-(1, the 4-phenylene) dimaleimide obtains as the polymer electrolyte precursor of crosslinking agent.
[formula 1]
[formula 2]
Wherein x is 0.1～0.6mol, and y is 0.1～0.8mol, and z is 0.1～0.8mol, and R is the alkyl that contains 1～6 carbon atom, and n is 3～30 integer, and R ' is hydrogen or CH
3
The specific example of R comprises methyl, ethyl etc. shown in the formula 1.The specific example of crosslinking agent comprises polyethylene glycol dimethacrylate, polyethyleneglycol diacrylate etc. shown in the formula 2.
Preferred 60～100 ℃ of the polymerization temperature of polymer electrolyte precursor.If polymerization temperature is higher than 100 ℃, undesirable evaporation can take place in electrolyte.If polymerization temperature is lower than 60 ℃, the cross-linking reaction between the crosslinking agent shown in polymer shown in the formula 1 and the formula 2 can not take place.
According to the present invention, the method for preparing lithium battery with gel-form solid polymer electrolyte now is described in detail as follows.
At first, adopt the commonsense method of making lithium battery to prepare negative electrode and anode respectively.Here, lithium metal composite oxides or sulfide are as active material of cathode, and lithium metal, material with carbon element or graphite are as active material of positive electrode.
To have cancellated insulating resin plate and insert between resulting negative electrode and the anode and roll or pile up, just form an electrode assembly thus.
The electrode assembly that form put into battery case thereafter.Then polymer electrolyte precursor is injected the battery case that electrode assembly is housed, make polymer electrolyte precursor immerse insulating resin plate.Here, suit under reduced pressure, to carry out the injection of polymer electrolyte precursor.
Polymer electrolyte precursor is to make by crosslinking agent shown in the polymer shown in hybrid 1, the formula 2 and the electrolyte of being made up of lithium salts and organic solvent.In addition, in polymer electrolyte precursor, can add polymerization initiator and polymerization catalyst, be beneficial to the cross-linking reaction between the crosslinking agent shown in polymer shown in the formula 1 and the formula 2.
The specific example of polymerization initiator comprises azo dibutyronitrile (AIBN), and it is a kind of thermal polymerization, based on polymer shown in the formula 1 of 100 weight portions, preferably uses the polymerization initiator of 0.01～5 weight portion.The specific example of polymerization catalyst comprises benzoyl peroxide, based on the polymer shown in the 100 weight portion formulas 1, preferably uses the polymerization catalyst of 0.01～10 weight portion.
The weight average molecular weight of the polymer shown in the formula 1 is preferably 5 000～2 000 000, and based on the polymer electrolyte precursor of 100 weight portions, its content is preferably 2～10 weight portions.
The weight average molecular weight of the crosslinking agent shown in the formula 2 is preferably 258～500 000, and based on the polymer electrolyte precursor of 100 weight portions, its content is preferably 0.01～50 weight portion.
Viscosity that the weight average molecular weight of the crosslinking agent shown in polymer shown in the formula 1 and the formula 2 and content depend on polymer electrolyte precursor and the battery performance after the polymerization reaction.
Preferably, non-aqueous organic solvent is be selected from propylene carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate and ethylene carbonate at least a.As lithium salts, preferably use LiClO
4, LiBF
4, LiPF
6, LiCF
3SO
3, LiN (CF
3SO
2)
2In at least a.Based on the polymer electrolyte precursor of 100 weight portions, the electrolyte content of being made up of lithium salts and non-aqueous organic solvent is preferably 40～98 weight portions.If the content of electrolyte is greater than 98 weight portions, polymerization reaction can not take place; If the content of electrolyte is lower than 40 weight portions, the battery performance possible deviation, this is undesirable.
In order to increase the mechanical strength of the polymer dielectric that comprises plate, preferably further N, N-(1, the 4-phenylene) dimaleimide joins in the polymer electrolyte precursor as crosslinking agent, based on the polymer electrolyte precursor of 100 weight portions, its content is preferably 0.01～50 weight portion.
Based on the polymer electrolyte precursor of 100 weight portions, the electrolyte content of being made up of lithium salts and non-aqueous organic solvent is preferably 40～98 weight portions.
Next step, the heating battery shell is equipped with cancellated insulating resin plate in this battery case, wherein immerse polymer electrolyte precursor.Here, heating-up temperature changes slightly according to the type of the crosslinking agent shown in polymer shown in the formula 1 and the formula 2, and preferred temperature is 60～100 ℃.If heating-up temperature is higher than 100 ℃, electrolyte will evaporate; If heating-up temperature is lower than 60 ℃, polymerization reaction just can not take place, and this is undesirable.
After the heating, polymer in the polymer electrolyte precursor and crosslinking agent generation polymerization generate gel-form solid polymer electrolyte, have formed the polymer dielectric that comprises plate thus.
The type of lithium battery of the present invention is not particularly limited, and in the present invention, lithium primary cell and lithium storage battery all have embodiment.
Describe the present invention by the following examples now, but the present invention is not limited to this.
Embodiment 1
The LiCoO of 94 weight portions
2, the Super-P of 3 weight portions and 3 weight portions poly-inclined to one side vinylidene fluoride (PVDF) be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 80 weight portions, make the cathode active material slip.This cathode active material slip is applied on aluminium (Al) paper tinsel that 4.9cm is wide, 147 μ m are thick, dry then, suppress and be whittled into reservation shape, make negative electrode at this point.
89.8 the PVDF of the mezophase carbon fiber (MFC) (Petoca Ltd., Japan) of weight portion, the oxalic acid of 0.2 weight portion and 10 weight portions is dissolved in the N-N-methyl-2-2-pyrrolidone N-of 120 weight portions, makes the anode active material slip.This anode active material slip is applied on the Copper Foil that 5.1cm is wide, 178 μ m are thick, dry then, suppress and be whittled into reservation shape, make anode at this point.
Wide for 5.35cm, thick be that 18 μ m, porosity are that (AsahiChemical Industry Co. Ltd.) is inserted between negative electrode and the anode, and rolls the formation electrode assembly for 60% polyethylene barrier film.Electrode assembly is put into battery case, and decompression is injected the decompression battery case to 5.6 following gram polymer electrolyte precursor then.
Shown in the 3 gram formulas 1, weight average molecular weight is that (Daiso Co. Ltd.) joins 97 grams and contains 1.15M LiPF for 1 000 000 polymer
6, EC: DMC: the DEC weight ratio is to make polymer electrolyte precursor in 3: 3: 4 the electrolyte, and dissolving and adding 1 grammes per square metre average molecular weight is 330 polyethylene glycol dimethacrylate, mixes.Adding 0.5 restrains AIBN and mixes in mixture then.
After this, product is put into water bath with thermostatic control, keeps 2h under 70 ℃, and is heated and makes polymer electrolyte precursor carry out heat polymerization, obtains one 18 thick polymer dielectric that comprises plate and the lithium storage battery of μ m thus.
Embodiment 2
Adopt the mode identical to make lithium storage battery,, use 91 to restrain and contain 1.15M LiPF except during producing polymer electrolyte precursor with embodiment 1
6, EC: DMC: DEC weight ratio in mixture be 3: 3: 4 electrolyte (Ube Industries, Ltd.), and use 6 the gram polyethylene glycol dimethacrylates.
Adopt the mode identical to make lithium storage battery, restrain N, N-(1, the 4-phenylene) dimaleimide except also further in polymer electrolyte precursor, adding 0.1 with embodiment 1.
Embodiment 4
Adopt the mode identical to make lithium storage battery with embodiment 1, except wide for 5.35cm, thick be that 18 μ m, porosity are 60% polyethylene barrier film (Asahi Chemical IndustryCo., Ltd.) be inserted between negative electrode and the anode, and stacked formation electrode assembly.
Embodiment 5
Shown in the 3 gram formulas 1, weight average molecular weight is that (Daiso Co. Ltd.) joins 97 grams and contains 1.15M LiPF for 1 000 000 polymer
6, EC: DMC: the DEC weight ratio be 3: 3: 4 electrolyte (Ube Industries, Ltd.) in, dissolving and adding 1 grammes per square metre average molecular weight is 330 polyethylene glycol dimethacrylate, mixes.Adding 0.5 restrains AIBN and mixes in mixture then, makes polymer electrolyte precursor.Polymer electrolyte precursor is applied on the carrier thin film, and drying is heated to 70 ℃ then.Then, product is stripped down from carrier thin film, make gel-form solid polymer electrolyte thus.
Embodiment 6
Adopt the mode identical to make gel-form solid polymer electrolyte,, use 91 to restrain and contain 1.15M LiPF except when making polymer electrolyte precursor with embodiment 1
6, EC: DMC: DEC weight ratio in mixture be 3: 3: 4 electrolyte (Ube Industries, Ltd.) and 6 the gram polyethylene glycol dimethacrylates.
Embodiment 7
Adopt the mode identical to make gel-form solid polymer electrolyte, restrain N, N-(1, the 4-phenylene) dimaleimide except further in polymer electrolyte precursor, adding 0.1 with embodiment 1.
The ionic conductivity and the mechanical strength of the gel-form solid polymer electrolyte that evaluation embodiment 5～7 makes.
Evaluation test shows that the ionic conductivity of the gel-form solid polymer electrolyte that embodiment 5～7 makes is good, promptly is approximately 0.0001～0.001S/cm, and its mechanical strength is also good, this means to have good workability.
Fig. 1 shows is the standard charge characteristic of the lithium storage battery made of the embodiment of the invention 1～4, and Fig. 2 shows is the discharge-rate capability of the lithium storage battery made of the embodiment of the invention 1.Here, charge condition is as follows.At first, charge to 4.2V with constant flow method, and under the 4.2V constant voltage, keep 2.5h at 0.2C.Then, being discharged to 2.75V cuts off.And under the 4.2V constant voltage, keep 2.5h.Then, being discharged to 2.75V cuts off.
With reference to Fig. 1, can confirm that the standard charge characteristic of the lithium storage battery that embodiment 1～4 makes is good.With reference to Fig. 2, the lithium storage battery that embodiment 1 makes can be kept good discharge performance when moderate rate 1C, low rate 0.5C and two-forty 2C.
Lithium storage battery of the present invention has reduced between electrode and the electrolyte resistance at the interface, by will be by the crosslinking agent shown in polymer shown in the formula 1 and the formula 2, the gel-form solid polymer electrolyte that the generation crosslinked action is made in the network structure of the insulating resin plate that insulate is as barrier film, improve the ionic conductance between the electrode, and improved the high speed charge/discharge characteristics.
Claims (19)
1. gel-form solid polymer electrolyte, it contains the crosslinking agent shown in the polymer shown in the formula 1, the formula 2 by polymerization and the polymer electrolyte precursor of the electrolyte be made up of lithium salts and non-aqueous organic solvent prepares:
[formula 1]
[formula 2]
Wherein x is 0.1～0.6mol, and y is 0.1～0.8mol, and z is 0.1～0.8mol, and R is the alkyl that contains 1～6 carbon atom, and n is 3～30 integer, and R ' is hydrogen or CH
3
2. according to the gel-form solid polymer electrolyte of claim 1, the polymer weight average molecular weight shown in its Chinese style 1 is 5 000～2 000 000, and based on the polymer electrolyte precursor of 100 weight portions, its content is 2～10 weight portions.
3. according to the gel-form solid polymer electrolyte of claim 1, the weight average molecular weight of the crosslinking agent shown in its Chinese style 2 is 258～500 000, and based on the polymer electrolyte precursor of 100 weight portions, its content is 0.01～50 weight portion.
4. according to the gel-form solid polymer electrolyte of claim 1, wherein polymer electrolyte precursor also contains the N as crosslinking agent, N-(1, the 4-phenylene) dimaleimide, and based on the polymer electrolyte precursor of 100 weight portions, its content is 0.01～50 weight portion.
5. according to the gel-form solid polymer electrolyte of claim 1, wherein non-aqueous organic solvent is selected from least a of propylene carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate and ethylene carbonate, and lithium salts is selected from LiClO
4, LiBF
4, LiPF
6, LiCF
3SO
3, LiN (CF
3SO
2)
2In at least a.
6. according to the gel-form solid polymer electrolyte of claim 1, wherein the content of electrolyte based on the polymer electrolyte precursor of 100 weight portions, is 40～98 weight portions.
7. method for preparing gel-form solid polymer electrolyte may further comprise the steps:
(a-1) prepare polymer electrolyte precursor by crosslinking agent shown in the polymer shown in hybrid 1, the formula 2 and the electrolyte formed by lithium salts and non-aqueous organic solvent:
[formula 1]
[formula 2]
Wherein x is 0.1～0.6mol, and y is 0.1～0.8mol, and z is 0.1～0.8mol, and R is the alkyl that contains 1～6 carbon atom, and n is 3～30 integer, and R ' is hydrogen or CH
3With
(b-1) this polymer electrolyte precursor of polymerization.
8. according to the method for claim 7, wherein polymer electrolyte precursor also contains the N as crosslinking agent, N-(1, the 4-phenylene) dimaleimide, and based on the polymer electrolyte precursor of 100 weight portions, its content is 0.01～50 weight portion.
9. according to the method for claim 7, wherein polymeric reaction temperature is 60～100 ℃ in (b-1) step.
One kind have a negative electrode, an anode and be inserted in negative electrode and anode between the lithium battery of barrier film, its septation is the insulating resin plate that contains gel-form solid polymer electrolyte in a kind of network structure, and this polymer dielectric is to contain the crosslinking agent shown in the polymer shown in the formula 1, the formula 2 and the polymer electrolyte precursor preparation of the electrolyte be made up of lithium salts and non-aqueous organic solvent by polymerization:
[formula 1]
[formula 2]
Wherein x is 0.1～0.6mol, and y is 0.1～0.8mol, and z is 0.1～0.8mol, and R is the alkyl that contains 1～6 carbon atom, and n is 3～30 integer, and R ' is hydrogen or CH
3
11. according to the lithium battery of claim 10, the weight average molecular weight of polymer is 5 000～2 000 000 shown in its Chinese style 1, based on the polymer electrolyte precursor of 100 weight portions, its content is 2～10 weight portions.
12. according to the lithium battery of claim 10, the weight average molecular weight of the crosslinking agent shown in its Chinese style 2 is 258～500 000, based on the polymer electrolyte precursor of 100 weight portions, its content is 0.01～50 weight portion.
13. according to the lithium battery of claim 10, wherein polymer electrolyte precursor also contains the N as crosslinking agent, N-(1, the 4-phenylene) dimaleimide, and based on the polymer electrolyte precursor of 100 weight portions, its content is 0.01～50 weight portion.
14. according to the lithium battery of claim 10, wherein non-aqueous organic solvent is selected from least a in propylene carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate and ethylene, the alkene ester.Lithium salts LiClO
4, LiBF
4, LiPF
6, LiCF
3SO
3, LiN (CF
3SO
2)
2In at least a.
15. according to the lithium battery of claim 10, wherein the content of electrolyte based on the polymer electrolyte precursor of 100 weight portions, is 40～98 weight portions.
16. according to the lithium battery of claim 10, wherein insulating resin plate is by polyvinyl resin, acrylic resin, or it is used in combination makes, the porosity of this insulating resin plate is 40～80%, and thickness is 10～30 μ m.
17. a method of making lithium battery may further comprise the steps:
(a-2) between negative electrode and anode, insert one and have cancellated insulating resin plate, make electrode assembly, and it is put into battery case;
(b-2) polymer electrolyte precursor of the electrolyte that contains the crosslinking agent shown in the polymer shown in the formula 1, the formula 2 and be made up of lithium salts and non-aqueous organic solvent is injected the battery case that electrode assembly is housed, makes it to immerse and have cancellated insulating resin plate:
[formula 1]
[formula 2]
Wherein x is 0.1～0.6mol, and y is 0.1～0.8mol, and z is 0.1～0.8mol, and R is the alkyl that contains 1～6 carbon atom, and n is 3～30 integer, and R ' is hydrogen or CH
3And
(c-2) product that obtains from (b-2) step of polymerization forms gel-form solid polymer electrolyte.
18. according to the method for claim 17, wherein polymer electrolyte precursor also contains the N as crosslinking agent, N-(1, the 4-phenylene) dimaleimide, and based on the polymer electrolyte precursor of 100 weight portions, its content is 0.01～50 weight portion.
19. according to the method for claim 17, wherein the polymeric reaction temperature of (c-2) step is 60～100 ℃.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2001-0000669A KR100373731B1 (en) | 2001-01-05 | 2001-01-05 | Lithium secondary battery and preparing method thereof |
| KR669/01 | 2001-01-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1362711A true CN1362711A (en) | 2002-08-07 |
| CN1229816C CN1229816C (en) | 2005-11-30 |
Family
ID=19704315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011384255A Expired - Lifetime CN1229816C (en) | 2001-01-05 | 2001-11-09 | Polymer gel electrolyte, lithium cell adopting said electrolytre and method for producing said electrolyte |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4418138B2 (en) |
| KR (1) | KR100373731B1 (en) |
| CN (1) | CN1229816C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100370639C (en) * | 2002-12-02 | 2008-02-20 | 日东电工株式会社 | Porous membrane for crosslinking polymer support of battery separator and method for manufacturing battery employing the same |
| CN100466362C (en) * | 2003-09-09 | 2009-03-04 | 三洋电机株式会社 | Non-aqueous solvent secondary battery |
| US7799471B2 (en) | 2005-04-19 | 2010-09-21 | Lg Chem, Ltd. | Functional electrolyte additives and electrochemical device comprising the same |
| US7910249B2 (en) | 2005-07-01 | 2011-03-22 | Lg Chem, Ltd. | Additive for nonaqueous electrolyte and secondary battery using the same |
| CN109037771A (en) * | 2018-07-25 | 2018-12-18 | 江苏合志锂硫电池技术有限公司 | Polymer Li-ion battery and preparation method thereof |
| CN111164818A (en) * | 2017-12-01 | 2020-05-15 | 株式会社Lg化学 | Electrolyte composition for lithium secondary battery and lithium secondary battery comprising the same |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3932511B2 (en) * | 2003-04-09 | 2007-06-20 | ソニー株式会社 | battery |
| CN100561776C (en) * | 2005-04-19 | 2009-11-18 | 株式会社Lg化学 | By introducing the electrochemical appliance that crosslinkable polymer improves the electrode of fail safe and contains this electrode |
| US8057938B1 (en) | 2005-11-09 | 2011-11-15 | The United States Of America As Represented By The Secretary Of The Army | Structural fuel cells and components thereof |
| US7855017B1 (en) * | 2005-11-09 | 2010-12-21 | The United States Of America As Represented By The Secretary Of The Army | Structural batteries and components thereof |
| US8576542B2 (en) | 2005-11-09 | 2013-11-05 | The United States Of America As Represented By The Secretary Of The Army | Structural electrochemical capacitor |
| TWI422089B (en) * | 2006-12-29 | 2014-01-01 | Ind Tech Res Inst | Gel-type polymer electrolyte precursor and rechargeable cells employing the same |
| CN110556576B (en) * | 2019-08-15 | 2022-12-23 | 中山大学 | Semi-interpenetrating network double-salt solid electrolyte and preparation method thereof |
-
2001
- 2001-01-05 KR KR10-2001-0000669A patent/KR100373731B1/en active IP Right Grant
- 2001-11-09 CN CNB011384255A patent/CN1229816C/en not_active Expired - Lifetime
-
2002
- 2002-01-07 JP JP2002000876A patent/JP4418138B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100370639C (en) * | 2002-12-02 | 2008-02-20 | 日东电工株式会社 | Porous membrane for crosslinking polymer support of battery separator and method for manufacturing battery employing the same |
| US9533475B2 (en) | 2002-12-02 | 2017-01-03 | Nitto Denko Corporation | Crosslinking polymer-supported porous film for battery separator and method for producing battery using the same |
| CN100466362C (en) * | 2003-09-09 | 2009-03-04 | 三洋电机株式会社 | Non-aqueous solvent secondary battery |
| US7799471B2 (en) | 2005-04-19 | 2010-09-21 | Lg Chem, Ltd. | Functional electrolyte additives and electrochemical device comprising the same |
| US7910249B2 (en) | 2005-07-01 | 2011-03-22 | Lg Chem, Ltd. | Additive for nonaqueous electrolyte and secondary battery using the same |
| CN111164818A (en) * | 2017-12-01 | 2020-05-15 | 株式会社Lg化学 | Electrolyte composition for lithium secondary battery and lithium secondary battery comprising the same |
| CN111164818B (en) * | 2017-12-01 | 2023-04-14 | 株式会社Lg新能源 | Electrolyte composition for lithium secondary battery and lithium secondary battery comprising the same |
| US11658340B2 (en) | 2017-12-01 | 2023-05-23 | Lg Energy Solution, Ltd. | Electrolyte composition for lithium secondary battery and lithium secondary battery including the same |
| CN109037771A (en) * | 2018-07-25 | 2018-12-18 | 江苏合志锂硫电池技术有限公司 | Polymer Li-ion battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020057571A (en) | 2002-07-11 |
| CN1229816C (en) | 2005-11-30 |
| JP2002305031A (en) | 2002-10-18 |
| JP4418138B2 (en) | 2010-02-17 |
| KR100373731B1 (en) | 2003-02-25 |
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