CN101814628A - Hyperbranched polyester lithium ion battery gel electrolyte and preparation method thereof - Google Patents
Hyperbranched polyester lithium ion battery gel electrolyte and preparation method thereof Download PDFInfo
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- CN101814628A CN101814628A CN200910214062A CN200910214062A CN101814628A CN 101814628 A CN101814628 A CN 101814628A CN 200910214062 A CN200910214062 A CN 200910214062A CN 200910214062 A CN200910214062 A CN 200910214062A CN 101814628 A CN101814628 A CN 101814628A
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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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a hyperbranched polyester lithium ion battery gel electrolyte and a preparation method thereof. The gel electrolyte is formed by mixed liquor prepared from 5-30 percent by mass of hyperbranched photopolymer resin, 5-25 percent by mass of cross-linking agent, 1-10 percent by mass of initiator, 20-50 percent by mass of plasticizer, 20-50 percent by mass of lithium salt and the like by using a radiation crosslinking method or a heating crosslinking method and the like. In the invention, the hyperbranched structure of a hyperbranched polyester can effectively prevent chain segments from being crystallized, whereas the molecular conformation similar to a spheric shape can increase the free volume of the polyester; bigger space and fewer -COO- and ether bond structures among branch points of the hyperbranched polyester have very strong interreaction with oxygen in the carbonic ester plasticizer, and therefore, a large amount of liquid electrolyte can be contained, and the gel electrolyte has very high dissolving capacity on salts, which is beneficial to ionic migration and the increase of electrical conductivity so that a lithium ion battery prepared from the hyperbranched polyester lithium ion battery gel electrolyte has long service life, small internal resistance, better specific energy, simple preparation process and no pollution.
Description
Technical field
The invention relates to the gel electrolyte that lithium ion battery is used, particularly have hyperbranched polyester lithium ion battery gel electrolyte that the lithium ion battery of high ionic conductance, suitable mechanical strength, pliability, pore structure and chemistry and electrochemical stability uses and preparation method thereof.
Background technology
The technological core of polymer Li-ion battery is to adopt polymer substrate as electrode and electrolytical skeleton structure, and the liquid electrolyte molecule is fixed therein, thereby electrode and electrolyte inside have high ionic conductivity.The key technology of polymer Li-ion battery is the preparation polymer dielectric, requires polymer dielectric to have high ionic conductance, suitable mechanical strength, pliability and chemistry and electrochemical stability etc.
Polymer substrate is that the development of solid electrolyte is broadly divided into 3 stages: 1. pure solid polymer electrolyte; 2. gel polymer electrolyte; 3. plural gel polymer dielectric.Pure solid polymer electrolyte does not contain any organic liquid, is solid solvent with the polymer only, and conductivity at room temperature has only 10
-8The order of magnitude of S/cm, the application in lithium ion battery is restricted.Gel polymer electrolyte is that plasticizer and lithium salts are formed by polymer, micromolecule solvent, has gathered the pliability of solid and the characteristics that liquid easily spreads, and is widely used.Gel polymer electrolyte has overcome liquid electrolyte and has easily generated combustible material and leakage defect at electrode surface, makes the design of battery freer.The existence of micromolecule solvent, make gel polymer electrolyte have solvent migration, volatility is big, electrochemical stability and thermal stability are relatively poor, ionic conductivity is relatively low, mechanical strength is low, deficiencies such as electrolyte and electrode interface poor stability, thereby have the people to propose plural gel polymer dielectric and porous gel polymer dielectric.These two kinds of electrolyte are the modifications to gel polymer electrolyte, two kinds of method of modifying commonly used at present are the hole density that adds the electrochemistry inert filler and increase polymer dielectric film, to increase ionic conductivity, to improve mechanical strength, improve the stability of electrolyte and electrode interface.
In recent years, the researcher has prepared the gel polymer electrolyte of following several types by methods such as blend, crosslinked, copolymerization and inorganic filler blend.
1, polyethylene glycol oxide system
Polyoxyethylene olefinic ether compound, its conduction is mainly finished by the sub-chain motion of amorphous area, itself electrolytic salt is had solvation, can be applicable to the preparation of polymer dielectric, but room-temperature conductivity is low.In order to improve this shortcoming, people have attempted multiple improving one's methods, and mainly contain crosslinked, blend and copolymerization etc.Someone adds crosslinking agent in the polyethylene glycol oxide oligomer, utilize initiated polymerizations such as ultraviolet light, heat, light and electron beam irradiation, make its generation crosslinked, form a kind of network-like big molecule, reduced the solubility of linear polyethylene glycol oxide in organic plasticizer, and improved storage capacity electrolyte solution.From present research situation, the conductivity of polyoxyethylene thiazolinyl gel polymer electrolyte approaches liquid electrolyte, but mechanical strength has much room for improvement.
2, polymethacrylates system
Polymethyl methacrylate is as the basis material of gel polymer electrolyte, owing in its construction unit a carbonyl side group is arranged, with the oxygen in the carbonates plasticizer very strong interaction is arranged, therefore can contain a large amount of liquid electrolytes, and polymethacrylates series gel electrolyte has interface stability preferably to lithium electrode, and is low with the interface impedance of metal lithium electrode.But polymethyl methacrylate base gel polymer electrolyte mechanical strength is lower, structural stability is relatively poor, Li
+Transference number of ions is on the low side, and its cation transport number generally is no more than 0.5, is difficult to fully contact with electrode, has influenced its further application.
3, Kynoar system
Kynoar is a kind of crystalline polymer, and the C-F group on the macromolecular chain is that very strong electronics shrinks group, and the Kynoar base polymer electrolyte has higher anti-anodic oxidation ability.This polymer serondary lithium battery function admirable that gel-type Kynoar-hexafluoropropylene copolymer electrolyte is made can satisfy the needs of equipment such as the mobile phone that develops towards little, the in light weight portability direction of volume, portable type Communication Equipment, notebook computer.Compound by polymer and polymer, inorganic matter and organic plasticizer can be improved the room-temperature conductivity of polymer dielectric effectively, improves the state of interface of electrode/electrolyte, and can keep certain mechanical strength.And present topmost problem is to compare with liquid electrolyte, and this electrolyte conductivity at room temperature also is not very high, and the performance that discharges and recharges repeatedly also awaits improving.
4, polyacrylonitrile system
The polyacrylonitrile based gel electrolyte is to study gel-form solid polymer electrolyte comparatively widely.In the polyacrylonitrile strand because of the oxygen-free atom, and a little less than contained nitrogen-atoms and the lithium ion effect, and the dispersion that the lithium salts in the polyacrylonitrile system gel electrolyte, solvent all can reach molecular level forms homogeneous phase, thereby transport number is big than the polyethylene glycol oxide system, can reach 0.5.Because contain strong polar group-CN on the polyacrylonitrile chain, poor with the metal lithium electrode compatibility, gel electrolyte film and lithium electrode interface passivation phenomenon are serious.Simultaneously, the crystallinity of polyacrylonitrile is strong, and when temperature rose, electrolyte was separated out, from and become liquid electrolyte.Therefore, must carry out modification, the method for modification is generally copolymerization and crosslinked.
Summary of the invention
The objective of the invention is in order to remedy the deficiency that prior art exists, a kind of hyperbranched polyester lithium ion battery gel electrolyte and preparation method thereof is provided, and this gel electrolyte has high ionic conductance, suitable mechanical strength, pliability, pore structure and chemistry and electrochemical stability.
For achieving the above object, the technical scheme that the present invention takes is: this hyperbranched polyester lithium ion battery gel electrolyte: by mass percent 5%～30% hyperbranched photopolymer resin, the mixed liquor that 5%～25% crosslinking agent, 1%～10% initator, 20%～50% plasticizer, 20%～50% lithium salts etc. form forms by methods such as crosslinking with radiation or heat cross-linkings.
Described hyperbranched photopolymer resin is passed through A
2+ B
3Method is synthetic, its concrete synthetic method is as follows: with hydroxyl value is that 2 or 3 polyalcohol or polyethers and carboxyl number are that 3 or 2 polyacid or acid anhydrides are reactant, carboxyl or anhydride reaction by hydroxyl groups and polyacid, synthesis of super branched polyester, utilize the monomer that has epoxy radicals and double bond structure in the carboxyl of this polymer molecule periphery and the molecular structure as: the epoxy reaction synthetic molecules periphery in the glycidyl methacrylate contains the hyperbranched photopolymer of unsaturated group.
Described polyalcohol comprises ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene-glycol, various molecular weight polyethylene glycol, propylene glycol, DPG, tripropylene glycol, glycerol, trimethylolpropane.
Described polyacid comprises terephthalic acid (TPA), phthalic acid, succinic acid, adipic acid and the binary acid with following structure:
Or ternary acid with following structure:
Described acid anhydrides comprises succinic anhydride, maleic acid anhydride, phthalic anhydride, trimellitic anhydride and the acid anhydrides with following structure:
Described monomer with epoxy radicals and double bond structure is as glycidyl methacrylate, allyl glycidyl ether, and the compound with following structure:
Described hyperbranched photopolymer resin is a standard with the polystyrene, adopts gel osmoticing chromatogram analysis, and molecular weight is at 500～2000g/mol, and molecule chain end contains hydroxyl and following building stone:
Described crosslinking agent comprises acrylate, methacrylate, vinylacetate, vinyl ethers etc., allyl glycidyl ether, ethoxy ethoxy ethoxy acrylate, ethoxy ethoxy ethyl propylene acid esters, the ring trimethylolpropane dimethoxym ethane acrylate of simple function group; Also comprise difunctionality and trifunctional acrylate etc., as tripropylene glycol diacrylate, ethoxyquin 1,6-hexanediyl ester, third oxidation 1,6-hexanediyl ester, propylene glycol diacrylate, ethoxyquin propylene glycol diacrylate, Macrogol 200 diacrylate, PEG400 diacrylate, Macrogol 600 diacrylate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate etc.
Described initator comprises, as: benzoyl peroxide, cumyl peroxide, di-t-butyl peroxide, dilauroyl peroxide, peroxidized t-butyl perbenzoate, the peroxidating trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.
Described lithium salts comprises: lithium perchlorate LiClO
4, lithium bromide LiBr, lithium chloride L iCl, lithium iodide LiI, lithium rhodanate LiSCN, LiBF4 LiBF
4, LiFePO 4 LiFePO
4, hexafluoroarsenate lithium LiAsF
6Deng.
Described plasticizer comprises: gamma-butyrolacton, ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate, 1, and 2-propylene glycol carbonic ester, polyethylene glycol etc., or multiple above-mentioned plasticizer mixes the mixed liquor that obtains by a certain percentage.
A kind of preparation method of hyperbranched polyester lithium ion battery gel electrolyte: with the hyperbranched photopolymer resin of mass percent 5%～30%, 5%～25% crosslinking agent, 1%～10% initator, 20%～50% plasticizer, after mixing, 20%～50% lithium salts etc. is prepared into lithium ion battery cell, lithium ion battery cell with preparation in the baking oven slowly was warming up to 30～45 ℃ of polymerizations about 24 hours, be warming up to the interior polymerization of 60～80 ℃ of scopes again and carry out heat cross-linking about 24 hours, or under the normal temperature, at energy is the crosslinking electron beam irradiation of 0.15～0.35MeV, or under the normal temperature with
60Crosslinking with radiation is carried out in Co gamma-radiation source, and preparation forms the network polymers gel electrolyte.
Advantage of the present invention:
The present invention proposes to prepare lithium ion battery gel electrolyte with hyper-branched polyester, be because dissaving polymer has the molecular conformation of almost spherical, its free volume is relatively large, there is not crystalline polamer, simultaneously, between the side chain in bigger space and the hyper-branched polyester oxygen in a large amount of-COO-group and diether linkage structure and the carbonates plasticizer very strong interaction is arranged, therefore can contain a large amount of liquid electrolytes, and make hyper-branched polyester stronger solvability be arranged to salt, help the migration of ion and the raising of conductivity, thereby make lithium ion battery gel electrolyte have high ionic conductance, suitable mechanical strength, pliability, pore structure and chemistry and electrochemical stability.
Hyperbranched polyester lithium ion battery gel electrolyte of the present invention, can effectively prevent the crystallization of segment because of the highly branched structure of dissaving polymer, and the molecular conformation of almost spherical can increase the free volume of polymer, bigger space and the oxygen in more-COO-and diether linkage structure and the carbonates plasticizer have very strong interaction between the dissaving polymer branch point, therefore can contain a large amount of liquid electrolytes, and make it stronger solvability be arranged to salt, and help the migration of ion and the raising of conductivity, make the lithium ion battery for preparing by hyperbranched polyester lithium ion battery gel electrolyte have extended cycle life, internal resistance is little, and has a specific energy preferably, and preparation process is simple, and is pollution-free.
Description of drawings
Fig. 1 is the infrared spectrogram of GMA of the present invention, hyper-branched polyester resin and hyperbranched photopolymer;
Fig. 2 is hyper-branched polyester resin and the hyperbranched photopolymer thermal analysis curue that the present invention synthesizes.
Embodiment
Embodiment:
One, hyperbranched photopolymer resin is synthetic:
The mass percent of raw material and proportioning
1,2,4-trimellitic anhydride 40.0～70.0%
Ethylene glycol 10.0～40.0%
Glycidyl methacrylate 5.0～30.0%
MEHQ 1.0～5.0%
N, dinethylformamide 5.0～20.0%
Technology:
With 1; 2; 4-trimellitic anhydride, ethylene glycol, N; dinethylformamide adds in the four-hole bottle; water knockout drum is installed; under stirring and nitrogen protection, be warming up to and make the trimellitic anhydride dissolving about 110 ℃, be warming up to 170～180 ℃ of reactions 16 hours gradually; obtain hyper-branched polyester; synthetic polymer is cooled to below 70 ℃, adds glycidyl methacrylate and polymerization inhibitor MEHQ, under agitation; be warming up to 85～95 ℃ of reactions 2～3 hours; constant to acid number, be cooled to less than 50 ℃ of dischargings, obtain hyperbranched photopolymer.It is to precipitate in 1: 1 the methanol/water solution that synthetic polymer solution under agitation is added drop-wise to volume ratio, and isolated polymer is used acetone solution again.And the precipitation that uses the same method, separate, so purifying is 3 times, (pressure 0.08kPa, 30 ℃) dry hyperbranched photopolymer that obtained being used for lithium ion battery gel electrolyte in 24 hours in the decompression baking oven.
The infrared analysis of figure one shows 1730～1780cm
-1There is not C-O stretching vibration absworption peak in the acid anhydrides in the place, illustrates that trimellitic anhydride and ethylene glycol fully react; Hyper-branched polyester and hyperbranched photopolymer infrared spectrum analysis are compared, and hyperbranched photopolymer is at 1620cm
-1There is the stretching vibration absworption peak of C=C in the place, simultaneously at 3482cm
-1Place-OH stretching vibration absworption peak obviously strengthens than hyper-branched polyester, illustrates that glycidyl methacrylate has been introduced on the hyper-branched polyester molecular resin.Figure two hot analysis results show that in 160 ℃, synthetic hyperbranched photopolymer is stable, does not have weightlessness substantially; Slight weightlessness is arranged between 160～370 ℃, and temperature is seriously weightless during greater than 370 ℃; And hyper-branched polyester is stable in 160 ℃, does not have weightlessness substantially; Slight weightlessness is arranged between 160～350 ℃, serious weightless greater than 350 ℃, illustrate hyper-branched polyester and hyperbranched photopolymer at 300 ℃ with interior its better heat stability, its thermal stability does not have to change substantially after the peripheral introducing of the hyperbranched polymer molecule glycidyl methacrylate, and the hyperbranched photopolymer that obtains has stability preferably.
Two, the preparation of hyperbranched polyester lithium ion battery gel electrolyte:
The mass percent of raw material and proportioning
Hyperbranched photopolymer resin 5.0%～30.0%
Macrogol 600 diacrylate 5.0%～25.0%
Benzoyl peroxide 1.0%～10.0%
Gamma-butyrolacton+dimethyl carbonate 20.0%～50.0%
Lithium perchlorate 20.0%～50.0%
Preparation technology:
At N
2In the environment, behind hyperbranched photopolymer resin, Macrogol 600 diacrylate, benzoyl peroxide, gamma-butyrolacton+dimethyl carbonate and lithium perchlorate mixed dissolution, be prepared into lithium ion battery cell, lithium ion battery cell with preparation in the baking oven slowly was warming up to 30～45 ℃ of polymerizations about 24 hours, be warming up to the interior polymerization of 60～80 ℃ of scopes again and carry out heat cross-linking about 24 hours, obtain the lithium ion battery cell that forms by hyperbranched polyester lithium ion battery gel electrolyte.Also can be with electric core electron beam crosslinking, irradiation dose 5～20kGy.
Prepared its detailed performance characteristics of lithium ion battery of the hyperbranched polyester lithium ion battery gel electrolyte that is formed by embodiment is as follows:
1, cycle life:＞500 times;
2, internal resistance:＜50 milliohms
3, overcharge 1C * 12V; Do not fire not quick-fried
4, acupuncture: do not fire not quick-fried
5, heavy impact: do not fire not quick-fried
6, extruding: do not fire not quick-fried
7, high temperature, 85 ℃ * 4 hours: expanding, it was qualified to fill
8, thermal shock, 150 ℃ * 30min: do not fire not quick-fried
9, peeling force between barrier film and positive/negative plate: qualified
10, specific energy: 415Wh/L.
Claims (12)
1. hyperbranched polyester lithium ion battery gel electrolyte, it is characterized in that: the mixed liquor by mass percent 5%～30% hyperbranched photopolymer resin, 5%～25% crosslinking agent, 1%～10% initator, 20%～50% plasticizer, 20%～50% lithium salts etc. form forms by methods such as crosslinking with radiation or heat cross-linkings.
2. according to the described hyperbranched polyester lithium ion battery gel electrolyte of claim 1, it is characterized in that: described hyperbranched photopolymer resin is synthetic by the A2+B3 method, its concrete synthetic method is as follows: with hydroxyl value is that 2 or 3 polyalcohol or polyethers and carboxyl number are that 3 or 2 polyacid or acid anhydrides are reactant, carboxyl or anhydride reaction by hydroxyl groups and polyacid, synthesis of super branched polyester, utilize the monomer that has epoxy radicals and double bond structure in the carboxyl of this polymer molecule periphery and the molecular structure as: the epoxy reaction synthetic molecules periphery in the glycidyl methacrylate contains the hyperbranched photopolymer of unsaturated group.
3. according to the described hyperbranched polyester lithium ion battery gel electrolyte of claim 2, it is characterized in that: described polyalcohol comprises ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene-glycol, various molecular weight polyethylene glycol, propylene glycol, DPG, tripropylene glycol, glycerol, trimethylolpropane.
4. according to the described hyperbranched polyester lithium ion battery gel electrolyte of claim 2, it is characterized in that: described polyacid comprises terephthalic acid (TPA), phthalic acid, succinic acid, adipic acid and the binary acid with following structure:
Or ternary acid with following structure:
5. according to the described hyperbranched polyester lithium ion battery gel electrolyte of claim 2, it is characterized in that: described acid anhydrides comprises succinic anhydride, maleic acid anhydride, phthalic anhydride, trimellitic anhydride and the acid anhydrides with following structure:
Be chain or circulus
6. according to the described hyperbranched polyester lithium ion battery gel electrolyte of claim 2, it is characterized in that: described monomer with epoxy radicals and double bond structure is as methyl propenoic acid glycidyl, allyl glycidyl ether, and the compound with following structure:
7. according to claim 1 or 2 described hyperbranched polyester lithium ion battery gel electrolytes, it is characterized in that: described hyperbranched photopolymer resin, with the polystyrene is standard, adopt gel osmoticing chromatogram analysis, molecular weight is at 500～2000g/mol, and molecule chain end contains hydroxyl and following building stone:
A: have＞group of C=C＜structure
8. according to the described hyperbranched polyester lithium ion battery gel electrolyte of claim 1, it is characterized in that: described crosslinking agent, the acrylate that comprises simple function group, methacrylate, vinylacetate, vinyl ethers etc., allyl glycidyl ether, ethoxy ethoxy ethoxy acrylate, ethoxy ethoxy ethyl propylene acid esters, ring trimethylolpropane dimethoxym ethane acrylate; Also comprise difunctionality and trifunctional acrylate etc., as tripropylene glycol diacrylate, ethoxyquin 1,6-hexanediyl ester, third oxidation 1,6-hexanediyl ester, propylene glycol diacrylate, ethoxyquin propylene glycol diacrylate, Macrogol 200 diacrylate, PEG400 diacrylate, Macrogol 600 diacrylate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate etc.
9. according to the described hyperbranched polyester lithium ion battery gel electrolyte of claim 1, it is characterized in that: described initator comprises, as: benzoyl peroxide, cumyl peroxide, di-t-butyl peroxide, dilauroyl peroxide, peroxidized t-butyl perbenzoate, the peroxidating trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.
10. according to the described hyperbranched polyester lithium ion battery gel electrolyte of claim 1, it is characterized in that: described lithium salts comprises: lithium perchlorate LiClO
4, lithium bromide LiBr, lithium chloride LiCl, lithium iodide LiI, lithium rhodanate LiSCN, LiBF4 LiBF
4, LiFePO 4 LiFePO
4, hexafluoroarsenate lithium LiAsF
6Deng.
11. according to the described hyperbranched polyester lithium ion battery gel electrolyte of claim 1, it is characterized in that: described plasticizer comprises: gamma-butyrolacton, ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate, 1,2-propylene glycol carbonic ester, polyethylene glycol etc., or multiple above-mentioned plasticizer mixes the mixed liquor that obtains by a certain percentage.
12. the preparation method of a hyperbranched polyester lithium ion battery gel electrolyte: with the hyperbranched photopolymer resin of mass percent 5%～30%, 5%～25% crosslinking agent, 1%～10% initator, 20%～50% plasticizer, after mixing, 20%～50% lithium salts etc. is prepared into lithium ion battery cell, lithium ion battery cell with preparation in the baking oven slowly was warming up to 30～45 ℃ of polymerizations about 24 hours, be warming up to the interior polymerization of 60～80 ℃ of scopes again and carry out heat cross-linking about 24 hours, or under the normal temperature, energy be under the crosslinking electron beam irradiation of 0.15～0.35MeV or the normal temperature with
60Crosslinking with radiation is carried out in Co gamma-radiation source, and preparation forms the network polymers gel electrolyte.
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