CN104744722A - Porous self-crosslinking polymer film and preparation method, electrolyte prepared from the film and application of electrolyte in lithium ion battery - Google Patents
Porous self-crosslinking polymer film and preparation method, electrolyte prepared from the film and application of electrolyte in lithium ion battery Download PDFInfo
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Abstract
The invention discloses a porous self-crosslinking polymer film. The film is prepared by mixing pure acrylic emulsion and modified polyethylene glycol solution, crosslinking and pore forming, the hydroxyl groups at two ends of the polyethylene glycol are substituted by methoxy groups to obtain the modified polyethylene glycol; the pore forming aims at contacting the self-crosslinking type polymer film with polyethylene glycol good solvent; the porosity of the self-crosslinking type gel polymer film is 40-70%. The invention further discloses the preparation method of the film, and a lithium ion battery using the film as the electrolyte. The prepared self-crosslinking type gel polymer electrolyte film can be used as the electrolyte of the lithium ion battery, the resistance is low, the ionic conductivity is high, and the electrolyte is hard to polarize in high-magnification charging/discharging.
Description
Technical field
The present invention relates to a kind of porous self-cross linking type polymeric film, and the preparation method of this film, also relate to the ionogen obtained by this film, and the application of this ionogen in lithium ion battery, belong to technical field of lithium ion.
Background technology
The energy density of conventional lithium ion battery is low, electrolytic solution is easy to reveal, and therefore easily causes safety problem.The gel polymer electrolyte of rising in recent years, its lithium ion transmission speed is fast, and its matrix can adsorb a large amount of liquid electrolyte, not easily leak of liquid occur, and therefore alternative electrolyte is used in lithium ion battery gradually.
At present, the gel polymer electrolyte of lithium ion battery mainly contains polyvinylidene difluoride (PVDF) and Pian Fu Yi Xi – hexafluoropropylene copolymer, and its charge/discharge rates is fast, good mechanical property.But, the affinity of polyvinylidene difluoride (PVDF) and Pian Fu Yi Xi – hexafluoropropylene copolymer and electrolytic solution is poor, and the electrolytical ability of adsorptive liquid is weak, easily causes battery liquid to leak, and above-mentioned two gellike polyelectrolytes and interelectrode interface resistance are large, cannot stablize compatible with electrode.
In order to overcome the above-mentioned shortcoming of polyvinylidene difluoride (PVDF) and Pian Fu Yi Xi – hexafluoropropylene copolymer gel polymer electrolyte, have and adopt polymethylmethacrylate to carry out modification to above-mentioned two class materials.As Chinese patent literature CN101062987A discloses a kind of multi-hole type polymer electrolyte film, it contains polyvinylidene difluoride (PVDF), the acrylonitrile-methacylate poly glycol monomethyl ether ester copolymer of 3-15%, the 1M lithium hexafluoro phosphate carbonate electrolyte of 43-52% that mass percent is 33-54%.Preparation process is first synthesis of acrylonitrile-Methylacrylic acid polyethylene glycol single armor ether ester multipolymer, then itself and polyvinylidene blending are dissolved in N, N-dimethylacetamide solvent, obtains porous membrane by immersion precipitation, then it is obtained to adsorb lithium hexafluoro phosphate carbonate electrolyte.Gel polymer electrolyte ionic conductance in this technology is high, good mechanical property, receives the ability of electrolytic solution and polyvinylidene fluoride olefinic substance simple compared with the compatibility of electrode to have certain raising; But be matrix because this gel polymer electrolyte remains with polyvinylidene difluoride (PVDF), it receives electrolytic solution ability and still not high with the consistency of electrode, and the gel polymer electrolyte in above-mentioned technology in use for some time serious problem of phase separation can occur, the use properties of battery is caused to reduce.
Due to the above-mentioned gel polymer electrolyte that is matrix with polyvinylidene difluoride (PVDF) or Pian Fu Yi Xi – hexafluoropropylene copolymer all exist receive electrolytic solution ability low and with the shortcoming of electrode poor compatibility, thus have investigator to consider the electrolyte ingredient adopting brand-new substance system as lithium ion battery.Because polyacrylate(s) material has similar functional group to the conventional electrolytic solution of lithium ion battery, it receives the ability of electrolytic solution strong, and the functional group of polyacrylate(s) and electrode component affinity good, make that interface impedance between polyacrylate(s) and electrode is low, consistency good, thus make polyacrylate(s) gelatin polymer quite concerned as the research of lithium ion battery electrolyte.As Chinese patent literature CN1317512A discloses the preparation method of a kind of gel-state lithium ion polymer electrolyte and battery, with series of acrylate derivative for monomer, itself and linking agent form polyacrylic ester by thermochemical crosslinking method under thermal initiator causes, polyacrylic ester forms polyacrylic ester gel-like gel polymer electrolyte with electrolytic solution further, and the ionogen that can be used as lithium ion battery uses.
Polyacrylate(s) gelatin polymer successfully uses as lithium ion battery electrolyte by above-mentioned technology, overcome this area all the time with polyvinylidene difluoride (PVDF) or Pian Fu Yi Xi – hexafluoropropylene copolymer for gel polymer electrolyte matrix time, existing receive electrolytic solution ability low and with the shortcoming of electrode poor compatibility; But because the polyacrylic ester gel polymer electrolyte body impedance in above-mentioned technology is higher, ionic conductivity is low, cause the polarizing effect of battery in high power charging-discharging situation large, the use properties of battery is low.
For the body impedance how reducing polyacrylic ester gel polymer electrolyte, thus improving this technical problem of use properties of the lithium ion battery using polyacrylate(s) material as polymer electrolyte matrix, those skilled in the art can not find applicable solution always.
Summary of the invention
Technical problem to be solved by this invention is that the impedance of polyacrylic ester gel polymer electrolyte body is higher, cause the use properties of battery low, and those skilled in the art cannot find applicable method to go to reduce the impedance of polyacrylic ester gel polymer electrolyte always; And then the porous self-cross linking type gel polymer electrolyte obtained by high porosity porous self-cross linking type gelatin polymer film that a kind of impedance is low, ionic conductivity is high, high rate capability is good is proposed.
On this basis, the invention allows for the lithium ion battery using porous self-cross linking type gel polymer electrolyte.
For solving the problems of the technologies described above, the invention provides a kind of porous self-cross linking type gelatin polymer film,
Mixed by pure-acrylic emulsion and modified poly (ethylene glycol) solution, be cross-linked and carry out pore-creating and obtain;
The hydroxyl at polyoxyethylene glycol two ends is obtained described modified poly (ethylene glycol) by methoxy substitution.
Described pore-creating is contacted with polyoxyethylene glycol good solvent by the crosslinked self-cross linking type polymeric film obtained.
Described polyoxyethylene glycol good solvent is solvent in water, lithium-ion battery electrolytes or lithium-ion battery electrolytes.
Described electrolytic solution is by lithium salts and solvent composition, and the concentration of described lithium salts is 0.8 ~ 1.5mol/L.
The porosity of described porous self-cross linking type gelatin polymer film is 40-70%.
The second-order transition temperature of described pure-acrylic emulsion is-30-70 DEG C.
The second-order transition temperature of described pure-acrylic emulsion is-18-60 DEG C.
The weight-average molecular weight of described polyoxyethylene glycol is less than 100,000 g/mol.
The weight-average molecular weight of described polyoxyethylene glycol is 100-5 ten thousand g/mol.
The solid content of described pure-acrylic emulsion is 40-60wt%, and the solid content of described modified poly (ethylene glycol) solution is 5-80wt%, and the solid weight of described modified poly (ethylene glycol) solution is the 1-50wt% of described pure-acrylic emulsion solid weight.
The solid weight of described modified poly (ethylene glycol) solution is the 5-30wt% of described pure-acrylic emulsion solid weight.
Film thickness is 0.01-110 μm.
Use the porous self-cross linking type gel polymer electrolyte of described porous self-cross linking type gelatin polymer film, contact electrolytic solution by porous self-cross linking type gelatin polymer film and obtain.
The specific conductivity of described porous self-cross linking type gel polymer electrolyte is 7-8.5mS/cm.
The preparation method of described porous self-cross linking type gelatin polymer film, comprises the steps,
(1) be methoxyl group by the hydroxyl modification at polyoxyethylene glycol two ends, obtain modified poly (ethylene glycol) and wiring solution-forming;
(2) by modified poly (ethylene glycol) solution, pure-acrylic emulsion Homogeneous phase mixing, mixed solution is formed;
(3) described mixed solution is coated on electrode surface, forms uncrosslinked film;
(4) described uncrosslinked film is toasted at 20-50 DEG C, form self-cross linking type polymeric film;
(5) by after the vacuum-drying of described self-cross linking type polymeric film, be soaked under dry oxygen-free environment in polyoxyethylene glycol good solvent, take out.
Baking time in step (4) is 0.01-24h, and storing temperature is 30-50 DEG C.
Vacuum drying temperature is 30-50 DEG C, the time is 10-30h; Soak time is no less than 24h.
Described porous self-cross linking type method for preparing gel polymer electrolyte, is soaked in the porous self-cross linking type gelatin polymer film of drying in an inert atmosphere in electrolytic solution, takes out.
Use the lithium ion battery of described porous self-cross linking type gelatin polymer film, comprise,
Battery cell body and barrier film, described battery cell body interior separation is positive pole conversion zone and negative reaction region by described barrier film;
Positive pole, is arranged in described positive pole conversion zone;
Negative pole, is arranged in described negative reaction region;
Electrolytic solution, is filled in described positive pole conversion zone and negative reaction region;
Described porous self-cross linking type gelatin polymer film is arranged between described positive pole and negative pole, and contacts with described positive pole and negative pole;
Described positive pole, negative pole, barrier film and porous self-cross linking type gelatin polymer film immersion are in described electrolytic solution.
The pure-acrylic emulsion used in the present invention makes the emulsion of coating for being generally used in prior art, be that what to be formed by Polyacrylate monomer, linking agent, emulsifying agent and water mixing copolymerization take polyacrylic ester as the emulsion of main component, wherein Polyacrylate monomer is acrylate or derivatives thereof.
The present invention has following beneficial effect compared with prior art:
(1) porous self-cross linking type gelatin polymer film of the present invention, mixed by pure-acrylic emulsion and modified poly (ethylene glycol) dissolution homogeneity, crosslinked and contact with polyoxyethylene glycol good solvent soak after obtain porous self-cross linking type gelatin polymer film.Self-crosslinking reaction is participated in order to prevent polyoxyethylene glycol, first the hydroxyl modification at polyoxyethylene glycol two ends is become methoxyl group by the application, obtain modified poly (ethylene glycol), by by pure-acrylic emulsion, the mixed solution heat cross-linking of modified poly (ethylene glycol) solution, mixture is occurred crosslinked, form three-dimensional crosslinked network structure, modified poly (ethylene glycol) is blended in wherein, then polyoxyethylene glycol good solvent is adopted to dissolve modified poly (ethylene glycol), the position that modified poly (ethylene glycol) dissolves just can leave hole, thus form porous self-cross linking type gelatin polymer film, this vesicular structure makes the gel polymer electrolyte ionic conductivity adopting this film greatly improve, impedance reduces greatly, thus the high rate performance of institute's assembled battery is improved greatly, avoid polyacrylic ester gel polymer electrolyte body impedance in prior art higher, cause the use properties of battery low, and those skilled in the art cannot find applicable method to go to reduce the problem of polyacrylic ester impedance always.
(2) porous self-cross linking type gelatin polymer film of the present invention, the solid content of described pure-acrylic emulsion is 40-60wt%, the solid content of described modified poly (ethylene glycol) solution is 5-80wt%, and the solid weight of described modified poly (ethylene glycol) solution is the 1-50wt% of described pure-acrylic emulsion solid weight.The mixed solution that the pure-acrylic emulsion of above-mentioned solid content, ratio, polyglycol solution are formed is cross-linked the porous self-cross linking type gelatin polymer film of rear final formation, better with the affinity of electrolytic solution, electrode, further reduce the generation of battery leakage problem, reduce further the impedance between ionogen and interface.
(3) porous self-cross linking type gelatin polymer film of the present invention, thickness is 0.01-110 μm, its obtained porous self-cross linking type gel polymer electrolyte after electrolytic solution dipping can form the film of any thickness as required, applied widely, can be used for the lithium ion battery making existing any capacity.
(4) preparation method of porous self-cross linking type gelatin polymer film of the present invention, is methyl by the hydroxyl modification at polyoxyethylene glycol two ends, obtains modified poly (ethylene glycol) and wiring solution-forming; By modified poly (ethylene glycol) solution, pure-acrylic emulsion Homogeneous phase mixing, form mixed solution; Mixed solution is coated on electrode surface and forms uncrosslinked film, uncrosslinked film is toasted at 20-50 DEG C crosslinked, be soaked under ambiance air tight condition in polyoxyethylene glycol good solvent afterwards and namely make porous self-cross linking type gelatin polymer film.The method is simple, easy to operate, and energy consumption is very low, greatly reduces production cost, and the body impedance of the porous self-cross linking type gel polymer electrolyte is simultaneously low, specific conductivity is high.
(5) in the lithium ion battery of use porous self-cross linking type gel polymer electrolyte of the present invention, porous self-cross linking type gel polymer electrolyte can be arranged between a positive electrode and a negative electrode, and contact with positive pole and negative pole, on the arbitrary surface being preferably arranged on one or several parts in positive pole, negative pole and barrier film or on all surface.
Accompanying drawing explanation
In order to make content of the present invention more easily be understood, the present invention is further detailed content of the present invention with embodiment by reference to the accompanying drawings;
Fig. 1 is the stereoscan photograph of porous self-cross linking type gelatin polymer film described in the embodiment of the present invention 2;
Embodiment
Embodiment 1
(1) be methoxyl group by the polyoxyethylene glycol two ends hydroxyl modification of weight-average molecular weight 80,000 g/mol, obtain Varonic DM 55; Its method of modifying is as follows:
In the polyoxyethylene glycol of 0.001mol, first add the sodium Metal 99.5 of 0.002mol, reaction generates polyoxyethylene glycol sodium and releasing hydrogen gas, the polyoxyethylene glycol sodium of the 0.001mol obtained and the methyl-iodide of 0.002mol are carried out Williamson synthesis, obtains Varonic DM 55.
(2) the Varonic DM 55 dissolution homogeneity mixing of to be pure-acrylic emulsion A, 18g solid content of 40wt% by 100g solid content be 11wt%, forms mixed solution;
Described pure-acrylic emulsion A is mixed by the P1005 of P1040 and 50g of 50g, P1040 and P1005 is the pure-acrylic emulsion product that Shanghai Ai Gao Chemical Co., Ltd. sells, METTLER DSC823e through being furnished with cryogenic system (FT100) tests, the second-order transition temperature of P1040 and P1005 is respectively 54 DEG C and-12 DEG C, and the second-order transition temperature calculating pure-acrylic emulsion A is according to the following equation 17 DEG C.
Wherein, W
1for the massfraction of P1040 in pure-acrylic emulsion A, W
2for the massfraction of P1005 in pure-acrylic emulsion A, Tg
1for the second-order transition temperature (Kelvin temperature) of P1040, Tg
2for the second-order transition temperature (Kelvin temperature) of P1005, Tg is the second-order transition temperature (Kelvin temperature) of pure-acrylic emulsion A.
(3) described mixed solution is coated on lithium ion battery positive plate, negative plate and PTFE plate with the thickness of 100 μm forms uncrosslinked film;
(4) the uncrosslinked film comprising positive plate and negative plate is cut into the disk that diameter is 13mm, uncrosslinked film on PTFE plate is stripped down and is cut into the disk that diameter is 17mm, and be again put on PTFE plate, then the uncrosslinked film (cut out disk) on positive plate, negative plate and PTFE plate is toasted 24h at 20 DEG C, form self-cross linking type polymeric film;
(5) above-mentioned self-cross linking type polymeric film (film on PTFE plate need be taken off) is immersed in water after 24h, at 30 DEG C after dry 30h, obtains positive plate, negative plate and self-supporting porous self-cross linking type gelatin polymer film Ca1, Cb1 and Cc1 respectively;
(6) by described porous self-cross linking type gelatin polymer film at 1x10
-3pa, at 30 DEG C after vacuum-drying 30h, transfer to rapidly and be full of in the glove box of argon gas, and Cc1 is soaked in 24h in electrolytic solution, after the EC/EMC/DMC that described electrolytic solution liquid is 1:1:1 by volume ratio mixes, add the LiPF of 2.5wt%VC and 1mol/L
6composition, takes out and namely obtains porous self-cross linking type gel polymer electrolyte Mc1;
Use barrier film in battery cell body, keep apart the lithium sheet negative potential that the positive electrode that is covered with Ca1 and diameter are 16mm, add electrolytic solution and seal into 2016 type Li/LiCoO
2polymer Li-ion battery 1.
Embodiment 2
(1) be methoxyl group by the polyoxyethylene glycol two ends hydroxyl modification of weight-average molecular weight 50,000 g/mol, obtain Varonic DM 55, concrete grammar is shown in embodiment 1;
(2) by 100g solid content be 60wt% pure-acrylic emulsion B, 50g solid content 18wt% Varonic DM 55 dissolution homogeneity mixing, formed mixed solution;
Described pure-acrylic emulsion B is mixed by the P1005 of P1040 and 20g of 80g, and the second-order transition temperature of mixed pure-acrylic emulsion B is 38 DEG C, and product producer and temperature computation method are with embodiment 1.
(3) described mixed solution is coated on lithium ion battery positive plate, negative plate and PTFE plate with the thickness of 100 μm forms uncrosslinked film;
(4) the uncrosslinked film comprising positive plate and negative plate is cut into the disk that diameter is 13mm, uncrosslinked film on PTFE plate is stripped down and is cut into the disk that diameter is 17mm, and be again put on PTFE plate, then the uncrosslinked film (cut out disk) on positive plate, negative plate and PTFE plate is toasted 0.01h at 50 DEG C, form self-cross linking type polymeric film;
(5) above-mentioned self-cross linking type polymeric film (film on PTFE plate need be taken off) is soaked in 24h in DMC under ambiance air-proof condition, at 30 DEG C after vacuum-drying 30h, obtain positive plate, negative plate and self-supporting porous self-cross linking type gelatin polymer film Ca2, Cb2 and Cc2 respectively;
(6) by described porous self-cross linking type gelatin polymer film at 1x10
-3pa, at 30 DEG C after vacuum-drying 30h, transfer to rapidly and be full of in the glove box of argon gas, and Cc2 is soaked in 24h in electrolytic solution, after the EC/EMC/DMC that described electrolytic solution liquid is 1:1:1 by volume ratio mixes, add the LiPF of 2.5wt%VC and 1mol/L
6composition, take out and namely obtain porous self-cross linking type gel polymer electrolyte Mc2, Mc2 structure is shown in Fig. 1.
Use barrier film in battery cell body, keep apart the lithium sheet negative potential that the positive electrode that is covered with Ca2 and diameter are 16mm, add electrolytic solution and seal into 2016 type Li/LiCoO
2polymer Li-ion battery 2.
Embodiment 3
(1) be methoxyl group by the polyoxyethylene glycol two ends hydroxyl modification of weight-average molecular weight 100g/mol, obtain Varonic DM 55; Method of modifying detailed in Example 1.
(2) by 100g solid content be 50wt% pure-acrylic emulsion C, 22g solid content 69wt% Varonic DM 55 dissolution homogeneity mixing, formed mixed solution;
Described pure-acrylic emulsion C is P1040, and its second-order transition temperature is 54 DEG C, and product producer is with embodiment 1.
(3) described mixed solution is coated on lithium ion battery positive plate, negative plate and PTFE plate with the thickness of 100 μm forms uncrosslinked film;
(4) the uncrosslinked film comprising positive plate and negative plate is cut into the disk that diameter is 13mm, uncrosslinked film on PTFE plate is stripped down and is cut into the disk that diameter is 17mm, and be again put on PTFE plate, then the uncrosslinked film (cut out disk) on positive plate, negative plate and PTFE plate is toasted 10h at 30 DEG C, form self-cross linking type polymeric film;
(5) above-mentioned self-cross linking type polymeric film (film on PTFE plate need be taken off) is soaked in 36h in EMC under ambiance air-proof condition, at 30 DEG C after vacuum-drying 30h, obtain positive plate, negative plate and self-supporting porous self-cross linking type gelatin polymer film Ca3, Cb3 and Cc3 respectively;
(6) by described porous self-cross linking type gelatin polymer film at 1x10
-3pa, at 30 DEG C after vacuum-drying 30h, transfer to rapidly and be full of in the glove box of argon gas, and Cc3 is soaked in 24h in electrolytic solution, after the EC/EMC/DMC that described electrolytic solution liquid is 1:1:1 by volume ratio mixes, add the LiPF of 2.5wt%VC and 1mol/L
6composition, takes out and namely obtains porous self-cross linking type gel polymer electrolyte Mc3;
Use barrier film in battery cell body, keep apart the lithium sheet negative potential that the positive electrode that is covered with Ca3 and diameter are 16mm, add electrolytic solution and seal into 2016 type Li/LiCoO
2polymer Li-ion battery 3.
Embodiment 4
(1) be methoxyl group by the polyoxyethylene glycol two ends hydroxyl modification of weight-average molecular weight 4000g/mol, obtain Varonic DM 55; Its method detailed in Example 1.
(2) the Varonic DM 55 dissolution homogeneity mixing of to be pure-acrylic emulsion A, 4.7g solid content of 50wt% by 100g solid content be 53wt%, forms mixed solution;
Described pure-acrylic emulsion A is mixed by the P1005 of P1040 and 50g of 50g.The second-order transition temperature of mixed pure-acrylic emulsion A is 17 DEG C, and product producer and temperature computation method are with embodiment 1.
(3) described mixed solution is coated on lithium ion battery positive plate, negative plate and PTFE plate with the thickness of 100 μm forms uncrosslinked film;
(4) the uncrosslinked film comprising positive plate and negative plate is cut into the disk that diameter is 13mm, uncrosslinked film on PTFE plate is stripped down and is cut into the disk that diameter is 17mm, and be again put on PTFE plate, then the uncrosslinked film (cut out disk) on positive plate, negative plate and PTFE plate is toasted 0.05h at 50 DEG C, form self-cross linking type polymeric film;
(5) above-mentioned self-cross linking type polymeric film (film on PTFE plate need be taken off) is soaked in 24h in deionized water under ambiance air-proof condition, at 30 DEG C after vacuum-drying 30h, obtain positive plate, negative plate and self-supporting porous self-cross linking type gelatin polymer film Ca4, Cb4 and Cc4 respectively;
(6) by described porous self-cross linking type gelatin polymer film at 1x10
-3pa, at 30 DEG C after vacuum-drying 30h, transfer to rapidly and be full of in the glove box of argon gas, and Cc4 is soaked in 24h in electrolytic solution, after the EC/EMC/DMC that described electrolytic solution liquid is 1:1:1 by volume ratio mixes, add the LiPF of 2.5wt%VC and 1mol/L
6composition, takes out and namely obtains porous self-cross linking type gel polymer electrolyte Mc4;
Use barrier film in battery cell body, keep apart the lithium sheet negative potential that the positive electrode that is covered with Ca4 and diameter are 16mm, add electrolytic solution and seal into 2016 type Li/LiCoO
2polymer Li-ion battery 4.
Embodiment 5
(1) be methoxyl group by the polyoxyethylene glycol two ends hydroxyl modification of weight-average molecular weight 200g/mol, obtain Varonic DM 55; Its method is: the sodium Metal 99.5 first adding 1mol in the polyoxyethylene glycol of 0.5mol, and reaction generates polyoxyethylene glycol sodium and releasing hydrogen gas.By the methyl-iodide of the polyoxyethylene glycol sodium of 0.5mol that obtains and 1mol by Williamson synthesis method, obtain Varonic DM 55.
(2) the Varonic DM 55 dissolution homogeneity mixing of to be pure-acrylic emulsion B, 12.5g solid content of 50wt% by 100g solid content be 60wt%, forms mixed solution;
Described pure-acrylic emulsion B is mixed by the P1005 of P1040 and 20g of 80g, and the second-order transition temperature of mixed pure-acrylic emulsion B is 38 DEG C, and product producer and temperature computation method are with embodiment 1.
(3) described mixed solution is coated on lithium ion battery positive plate, negative plate and PTFE plate with the thickness of 100 μm forms uncrosslinked film;
(4) the uncrosslinked film comprising positive plate and negative plate is cut into the disk that diameter is 13mm, uncrosslinked film on PTFE plate is stripped down and is cut into the disk that diameter is 17mm, and be again put on PTFE plate, then the uncrosslinked film (cut out disk) on positive plate, negative plate and PTFE plate is toasted 8h at 40 DEG C, form self-cross linking type polymeric film;
(5) above-mentioned self-cross linking type polymeric film (film on PTFE plate need be taken off) is soaked in 24h in water under ambiance air-proof condition, at 30 DEG C after vacuum-drying 30h, obtain positive plate, negative plate and self-supporting porous self-cross linking type gelatin polymer film Ca5, Cb5 and Cc5 respectively;
(6) by described porous self-cross linking type gelatin polymer film at 1x10
-3pa, at 30 DEG C after vacuum-drying 30h, transfer to rapidly and be full of in the glove box of argon gas, and Cc5 is soaked in 24h in electrolytic solution, after the EC/EMC/DMC that described electrolytic solution liquid is 1:1:1 by volume ratio mixes, add the LiPF of 2.5wt%VC and 1mol/L
6composition, takes out and namely obtains porous self-cross linking type gel polymer electrolyte Mc5;
Use barrier film in battery cell body, keep apart the lithium sheet negative potential that the positive electrode that is covered with Ca5 and diameter are 16mm, add electrolytic solution and seal into 2016 type Li/LiCoO
2polymer Li-ion battery 5.
Embodiment 6
(1) be methoxyl group by the polyoxyethylene glycol two ends hydroxyl modification of weight-average molecular weight 3000g/mol, obtain Varonic DM 55; Its method is: the sodium Metal 99.5 first adding 1mol in the polyoxyethylene glycol of 0.5mol, and reaction generates polyoxyethylene glycol sodium and releasing hydrogen gas.By the halohydrocarbon methyl-iodide of the polyoxyethylene glycol sodium of 0.5mol that obtains and 1mol by Williamson synthesis method, obtain Varonic DM 55.
(2) the Varonic DM 55 aqueous solution Homogeneous phase mixing of to be pure-acrylic emulsion C, 35.7g solid content of 50wt% by 100g solid content be 42wt%, forms mixed solution;
Described pure-acrylic emulsion C is P1040, and its second-order transition temperature is 54 DEG C., product producer is with embodiment 1.
(3) described mixed solution is coated on lithium ion battery positive plate, negative plate and PTFE plate with the thickness of 100 μm forms uncrosslinked film;
(4) the uncrosslinked film comprising positive plate and negative plate is cut into the disk that diameter is 13mm, uncrosslinked film on PTFE plate is stripped down and is cut into the disk that diameter is 17mm, and be again put on PTFE plate, then the uncrosslinked film (cut out disk) on positive plate, negative plate and PTFE plate is toasted 10h at 50 DEG C, form self-cross linking type polymeric film;
(5) above-mentioned self-cross linking type polymeric film (film on PTFE plate need be taken off) to be immersed in water after 24h, at 30 DEG C after vacuum-drying 30h, obtain positive plate, negative plate and self-supporting porous self-cross linking type gelatin polymer film Ca6, Cb6 and Cc6 respectively;
(6) by described porous self-cross linking type gelatin polymer film at 1x10
-3pa, at 30 DEG C after vacuum-drying 30h, transfer to rapidly and be full of in the glove box of argon gas, and Cc6 is soaked in 24h in electrolytic solution, after the EC/EMC/DMC that described electrolytic solution liquid is 1:1:1 by volume ratio mixes, add the LiPF of 2.5wt%VC and 1mol/L
6composition, takes out and namely obtains porous self-cross linking type gel polymer electrolyte Mc6;
Use barrier film in battery cell body, keep apart the lithium sheet negative potential that the positive electrode that is covered with Ca6 and diameter are 16mm, add electrolytic solution and seal into 2016 type Li/LiCoO
2polymer Li-ion battery 6.
Comparative example 1
In the glove box being full of argon gas, be the LiPF of 1M according to the methyl methacrylate of 9wt%, the PDDA of 2.5wt%, the dibenzoyl peroxide of 0.5wt% and 88wt% concentration
6the ratio of electrolytic solution is mixed to form the mixed solution of transparence, good fluidity mutually, in glove box, adopt coating method to be coated in by mixed solution on positive electrode, negative potential and PTFE plate, at 85-90 DEG C, thermopolymerization is carried out after sealing in glove box, time is 15-20min, obtained load self-cross linking type polymer dielectric Aa1, Ab1 and Ac1 on positive plate, negative plate and PTFE plate respectively.And Aa1, Ab1 of including positive plate and negative plate are cut into the disk that diameter is 13mm, and the Ac1 stripped down from PTFE plate is cut into the disk of diameter 17mm, whole process is carried out all under an inert atmosphere.(this step adds electrolytic solution, so what obtain is gel polymer electrolyte)
Use barrier film to keep apart in battery cell body negative potential that the positive electrode (disk) that is covered with Aa1 and diameter are the lithium sheet of 16mm, adds electrolytic solution and seals into 2016 type Li/LiCoO
2polymer Li-ion battery P.
Comparative example 2
(1) be that the pure-acrylic emulsion C of 50wt% is coated on lithium ion battery positive plate, negative plate and aluminium foil with the thickness of 100 μm and forms uncrosslinked film by 100g solid content; Described pure-acrylic emulsion C is P1040, and its second-order transition temperature is 54 DEG C, and product producer is with embodiment 1.
(2) the uncrosslinked film comprising positive electrode and negative potential is cut into the disk of diameter 13mm, and comprises
The uncrosslinked film of aluminium foil is cut into the disk that diameter is 17mm, then film uncrosslinked on aluminium foil is stripped down, be placed on PTFE plate, the uncrosslinked film comprised on positive electrode, negative potential and PTFE plate (cut out disk) is toasted 10h at 50 DEG C, namely obtains load self-cross linking type polymeric film Aa2, Ab2 and Ac2 on positive plate, negative plate and PTFE plate respectively;
3) by all self-cross linking type polymeric films at 1x10
-3pa, at 40 DEG C after vacuum-drying 20h, transfer to rapidly and be full of in the glove box of argon gas, and Ac2 is taken off from PTFE plate be soaked in 24h in electrolytic solution, after the EC/EMC/DMC that described electrolytic solution liquid is 1:1:1 by volume ratio mixes, add the LiPF of 2.5wt%VC and 1mol/L
6composition, takes out and namely obtains self-cross linking type gel polymer electrolyte Bc2;
Use barrier film in battery cell body, keep apart the lithium sheet negative potential that the positive electrode that is covered with Aa2 and diameter are 16mm, add electrolytic solution and seal into 2016 type Li/LiCoO
2polymer Li-ion battery Q.
Positive electrode in above-described embodiment and comparative example coats in tinsel make for the positive electrode material of lithium ion battery and conductive agent, binding agent furnishing slurry.Positive electrode material used is except the cobalt-lithium oxide (LiCoO of above-mentioned use
2), also comprise the positive electrode material that other can be used for arbitrarily lithium ion battery outward, as nickel oxide lithium (LiNiO
2), manganese oxide lithium (LiMn
2o
4), LiFePO 4 (LiFePO
4) and ternary composite cathode material and transformed lines show etc. thereof.Negative potential in above-described embodiment and comparative example is lithium sheet, in addition above-mentioned negative potential is also by coating in tinsel make for the negative material of lithium ion battery and conductive agent, binding agent furnishing slurry, negative material used comprises the negative material that can be used for arbitrarily lithium ion battery, as graphite, soft carbon, hard carbon etc.Described tinsel comprises the tinsel that can play arbitrarily electric action, as Copper Foil, aluminium foil etc.
Barrier film in above-described embodiment and comparative example is the barrier film being applicable to arbitrarily lithium ion battery, as PP barrier film, PE barrier film and PE/PP/PE tri-layers of barrier film etc.
Described electrolytic solution can by lithium salts and solvent composition, and wherein the concentration of lithium salts is 0.8-1.5mol/L; Described lithium salts can select lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4) and LiBF4 (LiBF
4) etc.; Solvent can select one or more the mixing in NSC 11801 (EC), propylene carbonate (PC), methylcarbonate (DMC), Methyl ethyl carbonate (EMC) and diethyl carbonate (DEC), vinylene carbonate (VC).
In above-described embodiment, be covered with except the positive plate of self-cross linking type polymeric film, lithium sheet negative potential except using, also can use as follows: as separated negative plate and the lithium sheet of overlay film in the glove box being full of argon gas with the general barrier film of lithium ion battery, add electrolytic solution, seal into polymer Li-ion battery; In the glove box being full of argon gas, separate the negative plate of overlay film positive plate and overlay film with the general barrier film of lithium ion battery, add electrolytic solution and seal into polymer Li-ion battery.
In addition, the pure-acrylic emulsion in above-described embodiment and comparative example is except P1040 and P1005 two kinds, and any pure-acrylic emulsion of the prior art is all applicable to the present invention.
Method of modifying in above-described embodiment is not unique, and in prior art, any method that the hydroxyl at polyoxyethylene glycol two ends can be substituted by methoxyl group is all applicable to the present invention.
Test case
(1) porosity of Cc1-Cc7 and Ac2 is measured: radius r and the thickness d of measuring disc-shaped film, weigh up mass M
0after be soaked in 2h in propyl carbinol, then taking-up filter paper blots the liquid on film surface and the mass M weighed now, according to following formulae discovery porosity, the results are shown in Table 1;
(2) measure the pick up of Cc1-Cc7 and Ac2: put into the glove box being full of argon gas after being dried by disc-shaped film, be immersed in 24h in electrolytic solution after weighing up quality W, then taking-up filter paper blots the liquid on film surface and the quality W weighed now
i, calculate pick up according to the following equation, the results are shown in Table 1;
(3) specific conductivity of Mc1-Mc6, Ac1 and Bc2 is measured: be placed between two stainless steel (SS) electrodes by the disc-shaped film after absorbing enough electrolytic solution, after being sealed in 2016 type button cells (East China, Shenzhen Zheng Tai mechanical & electronic equipment corporation, Ltd), the CHI604b type electrochemical workstation of Shanghai occasion China is adopted to carry out ac impedance measurement, record the body impedance R of film, calculate the specific conductivity of film according to the following formula, the results are shown in Table 1:
σ=L/A·R
Wherein, L represents thickness, and A is the real contact area of stainless steel electrode and film;
Table 1
As shown in Table 1, the specific conductivity of the porosity of porous self-cross linking type gelatin polymer film prepared by the method for the invention, pick up and porous self-cross linking type gel polymer electrolyte far above comparative example, therefore its to the acceptance of electrolytic solution and ionic conductivity all higher than comparative example.Meanwhile, the body impedance of porous self-cross linking type gel polymer electrolyte of the present invention is lower than the self-cross linking type gel polymer electrolyte in comparative example.
(4) charge-discharge property of lithium ion battery 1-6, P and Q measures: adopt BK6016 type performance of lithium ion battery test cabinet (Guangzhou Lanqi Electronic Industrial Co., Ltd.) to test, with 0.075mA/cm
2electric current first by constant-current charging of battery to 4.2V, then constant voltage charge at 4.2v, cut-off current is 0.038mA/cm
2, record charging capacity, then with 0.075mA/cm
2by battery constant-current discharge to 3.0V, record loading capacity.According to specific storage=loading capacity/LiCoO
2electrode quality, first charge-discharge efficiency=loading capacity first/initial charge capacity × 100%, obtains specific storage and first charge-discharge efficiency, the results are shown in Table 2;
Table 2
| Lithium ion battery | Specific storage (mAh/g) | First charge-discharge efficiency (%) |
| 1 | 144 | 98.14 |
| 2 | 143 | 97.96 |
| 3 | 146 | 97.93 |
| 4 | 141 | 98.33 |
| 5 | 142 | 97.99 |
| 6 | 145 | 99.27 |
| P | 140 | 95.59 |
| Q | 144 | 96.17 |
As shown in Table 2, the charge-discharge property of porous self-cross linking type gel polymer electrolyte prepared of the method for the invention is higher than comparative example.
(5) multiplying power of lithium ion battery 1-6, P and Q is charged and multiplying power discharging property test, BK6016 type performance of lithium ion battery test cabinet (Guangzhou Lanqi Electronic Industrial Co., Ltd.) is adopted to carry out multiplying power charging and multiplying power discharging test to the lithium ion battery after completing first charge-discharge, with loading capacity first for battery rated capacity:
I. first by battery with 0.1C constant-current constant-voltage charging to 4.2V, after shelving 5min, battery 0.1C is discharged to 3.0V, shelve 5min, use 0.2C/0.5C/1C/3C constant current charge to 4.2V more respectively, then constant voltage charge at 4.2v, cut-off current is 0.02C, record charging capacity under each multiplying power, the results are shown in Table 3;
Ii. by battery with 0.1C constant current charge to 4.2V, then constant voltage charge at 4.2v, cut-off current is 0.02C, shelves 5min, is discharged to 3.0V respectively with 0.2C/0.5C/1C/3C, records each multiplying power discharge capacity, the results are shown in Table 4;
Table 3
Table 4
From table 3-4, lithium ion battery each multiplying power charging of porous self-cross linking type gel polymer electrolyte prepared by the method for the invention and each multiplying power discharging property comparatively comparative example have and improve largely, this is because the impedance of the porous self-cross linking type gel polymer electrolyte in the present invention reduces, specific conductivity is high, the polarization phenomena in charge and discharge process can be reduced, be conducive to the migration of lithium ion.
Although the present invention has carried out detailed elaboration by above-mentioned specific embodiment to it; but; those skilled in the art should be understood that and made on this basis not exceed any form of claims and the change of details, all belong to invention which is intended to be protected.
Claims (19)
1. a porous self-cross linking type gelatin polymer film,
Mixed by pure-acrylic emulsion and modified poly (ethylene glycol) solution, be cross-linked and carry out pore-creating and obtain;
The hydroxyl at polyoxyethylene glycol two ends is obtained described modified poly (ethylene glycol) by methoxy substitution.
2. porous self-cross linking type gelatin polymer film according to claim 1, is characterized in that, described pore-creating is contacted with polyoxyethylene glycol good solvent by the crosslinked self-cross linking type polymeric film obtained.
3. porous self-cross linking type gelatin polymer film according to claim 2, is characterized in that, described polyoxyethylene glycol good solvent is solvent in water, lithium-ion battery electrolytes or lithium-ion battery electrolytes.
4. porous self-cross linking type gelatin polymer film according to claim 3, is characterized in that, described electrolytic solution is by lithium salts and solvent composition, and the concentration of described lithium salts is 0.8 ~ 1.5mol/L.
5., according to the arbitrary described porous self-cross linking type gelatin polymer film of claim 1-4, it is characterized in that, the porosity of described porous self-cross linking type gelatin polymer film is 40-70%.
6., according to the arbitrary described porous self-cross linking type gelatin polymer film of claim 1-5, it is characterized in that, the second-order transition temperature of described pure-acrylic emulsion is-30-70 DEG C.
7. porous self-cross linking type gelatin polymer film according to claim 6, it is characterized in that, the second-order transition temperature of described pure-acrylic emulsion is-18-60 DEG C.
8., according to the arbitrary described porous self-cross linking type gelatin polymer film of claim 1-7, it is characterized in that, the weight-average molecular weight of described polyoxyethylene glycol is less than 100,000 g/mol.
9. porous self-cross linking type gelatin polymer film according to claim 8, is characterized in that, the weight-average molecular weight of described polyoxyethylene glycol is 100-5 ten thousand g/mol.
10. according to the arbitrary described porous self-cross linking type gelatin polymer film of claim 1-9, it is characterized in that, the solid content of described pure-acrylic emulsion is 40-60wt%, the solid content of described modified poly (ethylene glycol) solution is 5-80wt%, and the solid weight of described modified poly (ethylene glycol) solution is the 1-50wt% of described pure-acrylic emulsion solid weight.
11. porous self-cross linking type gelatin polymer films according to claim 10, it is characterized in that, the solid weight of described modified poly (ethylene glycol) solution is the 5-30wt% of described pure-acrylic emulsion solid weight.
12. according to the arbitrary described porous self-cross linking type gelatin polymer film of claim 1-11, and it is characterized in that, film thickness is 0.01-110 μm.
The porous self-cross linking type gel polymer electrolyte of the arbitrary described porous self-cross linking type gelatin polymer film of 13. use claim 1-12, is characterized in that, contacts electrolytic solution obtain by porous self-cross linking type gelatin polymer film.
14. porous self-cross linking type gel polymer electrolytes according to claim 13, is characterized in that, the specific conductivity of described porous self-cross linking type gel polymer electrolyte is 7-8.5mS/cm.
The preparation method of the arbitrary described porous self-cross linking type gelatin polymer film of 15. claim 1-12, comprises the steps,
(1) be methoxyl group by the hydroxyl modification at polyoxyethylene glycol two ends, obtain modified poly (ethylene glycol) and wiring solution-forming;
(2) by modified poly (ethylene glycol) solution, pure-acrylic emulsion Homogeneous phase mixing, mixed solution is formed;
(3) described mixed solution is coated on electrode surface, forms uncrosslinked film;
(4) described uncrosslinked film is toasted at 20-50 DEG C, form self-cross linking type polymeric film;
(5) by after the vacuum-drying of described self-cross linking type polymeric film, be soaked under dry oxygen-free environment in polyoxyethylene glycol good solvent, take out.
16. preparation methods according to claim 15, is characterized in that, the baking time in step (4) is 0.01-24h, and storing temperature is 30-50 DEG C.
17. preparation methods according to claim 15 or 16, it is characterized in that, vacuum drying temperature is 30-50 DEG C, the time is 10-30h; Soak time is no less than 24h.
Porous self-cross linking type method for preparing gel polymer electrolyte described in 18. claims 13 or 14, is soaked in the porous self-cross linking type gelatin polymer film of drying in an inert atmosphere in electrolytic solution, takes out.
The lithium ion battery of the arbitrary described porous self-cross linking type gelatin polymer film of 19. use claim 1-12, comprises,
Battery cell body and barrier film, described battery cell body interior separation is positive pole conversion zone and negative reaction region by described barrier film;
Positive pole, is arranged in described positive pole conversion zone;
Negative pole, is arranged in described negative reaction region;
Electrolytic solution, is filled in described positive pole conversion zone and negative reaction region;
Described porous self-cross linking type gelatin polymer film is arranged between described positive pole and negative pole, and contacts with described positive pole and negative pole;
Described positive pole, negative pole, barrier film and porous self-cross linking type gelatin polymer film immersion are in described electrolytic solution.
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