CN103915651B - A kind of starch-based polymer electrolyte and preparation method thereof for lithium ion battery - Google Patents
A kind of starch-based polymer electrolyte and preparation method thereof for lithium ion battery Download PDFInfo
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention relates to a kind of lithium ion battery starch-based polymer electrolyte and preparation method thereof, specifically that porous-starch is first carried out to pre-gelatinization processing, then under the effect of coagulant and pore creating material, make the starch film of porous, this starch film not only has loose structure on film, and the starch granules inside of component film also exists loose structure; Can be grafted on the hole wall in two kinds of holes that porous-starch film has with the group of lithium ion complexing having again, finally immerse in the solution of lithium salts and carry out complex reaction, take out and make a kind of lithium battery starch-based polymer dielectric film through super-dry, this polymer dielectric not only has very high ionic conductivity and transportable lithium ion density, and mechanical property excellence, production cost is low, is easy to suitability for industrialized production, has its using value.
Description
Technical field
The present invention relates to a kind of lithium battery material field, be specifically related to the starch-based polymer electrolysis of a kind of lithium ion batteryMatter and preparation method thereof.
Background technology
Lithium ion battery is to have now one of secondary cell of development potentiality most, has that operating voltage is high, energy densityHigh, discharge and recharge the features such as the life-span is long, self discharge is little, volume is little, memory-less effect, environmental protection. Although lithium ion battery at presentBe widely used in multiple fields such as military and national defense, electric automobile, portable digital equipments, but simultaneously also to its performanceRequirement also more and more higher, especially need in the defect aspect security, specific energy, high temperature performance and cyclical stabilityImprove. Along with attention and the development of people to lithium ion battery, the selection of the negative material of lithium ion battery and preparationTechnique is comparative maturity, and also has many defects in selection and the preparation of positive electrode, electrolyte and diaphragm materialNeed to improve.
Polymer dielectric for lithium ion battery mainly will meet following requirement: first will have higher ion-conductanceConductance. For can reach that liquid electrolytic plastidome has 10-3A/cm2The level of discharge current density, polymer dielectricRoom-temperature conductivity must reach or approach 10-5The level of S/cm; It is less important has certain mechanical strength, and processability isThe most important factor that will consider when actual production, although there are a lot of electrolyte can make self-supporting film, and have fineChemical property, but their mechanical strength need improve, to adapt to traditional extensive coating process; Less important againThere is higher lithium ion transference number. High lithium ion transference number can reduce the concentration polarization in charge and discharge process, thereby makesLithium ion battery has higher energy density. The electrolyte that lithium ion battery uses is at present the non-water power containing lithium salts substantiallySeparate liquid, exist lithium ion conducting rate low, the defect of bad mechanical strength, and can not degrade, and starch is as there being most now prospectOne of bioabsorbable polymer material, there is active group many, can film forming, degradable, the plurality of advantages such as renewable, have performance andAdvantage in price is one of trend of Future Development.
China Patent Publication No. CN103441300A discloses the gel polymer electrolyte that contains natural macromolecular materialAnd preparation method thereof with application, in this invention, use the natural macromolecular materials such as starch as matrix material, then mix with lithium saltsMake gel polymer electrolyte Deng compound, it is good, compatible with electrode material that this kind of gel electrolyte not only has security performanceProperty is fine, cyclicity and the good feature of high rate performance, and good biocompatibility, degradable, eco-friendly feature, but byIn the method, only the bioabsorbable polymer materials such as starch have been carried out to simple modification, can with the group number of lithium ion complexingAmount is few, also not for lithium ion migration provides passage, thereby has that lithium ion transference number is low, ionic conductivity is low, mechanical strengthPoor defect.
China Patent Publication No. CN103155267A discloses a kind of starch base battery system. In this invention, use through placeThe starch of reason is as the electrolyte of battery system, and this cell discharge performance excellence is safe and reliable, environment-protecting asepsis, but due to this electricityThe starch electrolyte using in cell system has just carried out simple kneading crosslinking Treatment, therefore energy and lithium in this starch electrolyteThe group quantity of ion complexation is few, causes the defect that lithium ion transference number is low, also, not for lithium ion migration provides passage, causesIonic conductivity is also lower.
According to above-mentioned, also can be as the matrix material of polymer dielectric, at lithium battery through certain processing using starchIn energy storage, also can be utilized. Using at present starch to prepare polymer dielectric is all only starch have been done to simple modification placeReason, there is bad mechanical strength in the starch polymer electrolyte making, and lithium ion transference number is low, the defect that ionic conductivity is low.
Summary of the invention
The ionic conductivity existing for current starch polymer electrolyte is lower, and lithium ion transference number is low, mechanical strengthPoor defect has proposed a kind of lithium ion battery starch-based polymer electrolyte and preparation method thereof, for achieving the above object,Porous-starch is first carried out pre-gelatinization processing by the present invention, then under the effect of coagulant and pore creating material, makes the starch of porousFilm, this starch film not only has loose structure on film, and the starch granules inside of component film also exists loose structure; Again by toolHave and can be grafted on the hole wall in two kinds of holes that porous-starch film has with the group of lithium ion complexing, finally immerse the solution of lithium saltsIn carry out complex reaction, take out make a kind of lithium battery starch-based polymer dielectric film, this polymer electrolytic through super-dryMatter not only has very high ionic conductivity and transportable lithium ion density, and mechanical property excellence, and production cost is low.
A kind of lithium ion battery starch-based polymer electrolyte and preparation method thereof of the present invention, is characterized in that its each groupDivide and count by weight:
Porous-starch 65-80 part,
NaOH 2-4 part,
Coagulant 2-5 part,
Pore creating material 5-10 part,
Modifier 3-5 part,
Lithium salt solution 5-10 part,
Wherein said porous-starch is to refer to use the enzyme with raw amylase activity acting on lower than under gelatinization pointIn raw starch and the cellular wheaten starch of porous that forms, potato starch, cornstarch, tapioca, konjak starch oneKind or multiple, starch surface is covered with the aperture that diameter is 10nm-500nm, and by surface to center deeply, the volume in hole accounts for apertureThe 45%-55% of particle volume; Described coagulant is one or more of borate family, thiazoles, diphenylguanidine class; Described pore-creatingAgent is one or more in methyl alcohol, ethanol, propyl alcohol, ethylene glycol; Described modifier is with activity hydroxy, carboxyl and aminoLittle molecule straight chain polymer; Described lithium salt solution is that LiBF4 solution, two oxalic acid close lithium borate solution, trifluoromethylOne or more in Sulfonic Lithium solution, lithium hexafluoro phosphate solution, two (trimethyl fluoride sulfonyl) imine lithium solution.
Above-mentioned a kind of lithium ion battery is used in the electrolytical each component of starch-based polymer, wherein said modifier polymerizationDegree is 10-50.
Above-mentioned a kind of lithium ion battery is with in the electrolytical each component of starch-based polymer, and wherein said modifier is preferredOne or more in polyurethane, polycarboxylate, polyethers.
A kind of lithium ion battery of the present invention is as follows by the electrolytical concrete preparation process of starch-based polymer:
1) porous-starch of 65-80 weight portion is dissolved in reactor in the distilled water of 30-40 degree Celsius, forms moltenLiquid, is then warming up to 60-80 degree Celsius, adds the NaOH of 2-4 part to carry out pre-gelatinization processing, obtains porous-starch colloidal sol;
2) in the porous-starch colloidal sol obtaining in step 1), add the pore-creating of coagulant and the 5-10 weight portion of 2-5 weight portionAgent, is uniformly mixed fully reaction 30-60min and obtains casting solution, and vacuum defoamation is processed rear blade coating on glass plate, natural coagulation2-3h, film forming is placed on 1-2h in the baking oven that is heated to 50-80 degree Celsius, makes pore creating material volatilization, obtains porous-starch film;
3) by step 2) the porous-starch film that obtains immerses and is equipped with in the irradiation tube of 3-5 weight portion modifier, penetrate at irradiationCondition under carry out graft modification and process 20-40min, take out and obtain the porous-starch film of modification;
4) the porous-starch film of modification step 3) being obtained is immersed in the solution of lithium salts of 5-10 weight portion and carries out networkClose reaction 10-20min, take out and be placed in vacuum drying chamber, in vacuum or nitrogen atmosphere, be dried and obtain a kind of lithium-ion electricPond starch-based polymer electrolyte.
The electrolytical concrete preparation process 4 of starch-based polymer for above-mentioned a kind of lithium ion battery) described in irradiation tubeFor quartz glass tube.
The electrolytical concrete preparation process 4 of starch-based polymer for above-mentioned a kind of lithium ion battery) described in irradiation penetrateFor the one in ultraviolet irradiation, low temperature plasma irradiation or high-energy ray irradiation.
The porous-starch that the present invention uses has a microcellular structure in starch granules, for lithium ion in starch granulesMigration provides passage, has improved the migration rate of lithium ion; By pre-gelatinization processing, under the effect of coagulant and pore creating materialObtain a kind of starch film of porous, this porous-starch film not only has excellent mechanical performance, and porous in starch film knotStructure further provides passage for the migration of lithium ion in starch film, has improved lithium ion migration velocity; To there is in a large number again positionHinder little, can with lithium ion complexing be grafted to starch granules with activity hydroxy, carboxyl and amino little molecule straight chain polymerWith the surface of hole wall in starch film, thus increased can with the group quantity of lithium ion complexing, ensured this starch-based polymerVery high transportable lithium ion density in electrolyte, is conducive to the migration of lithium ion; Not only tool of this starch-based polymer electrolyteHave that high ionic conductivity very, mechanical property are good, nontoxic, the advantage of green environmental protection degradable, and preparation method is simple, is produced intoThis is low, is easy to suitability for industrialized production.
The outstanding feature of the present invention is:
1, the present invention use porous-starch in starch granules, there is microcellular structure, for lithium ion in starch granulesMigration passage is provided, improved the migration rate of lithium ion, lithium ion conducting rate is improved.
2, the present invention by have in a large number steric hindrance little, can with lithium ion complexing with activity hydroxy, carboxyl and amino littleMolecule straight chain polymer is grafted to starch film surface, increased can with the group quantity of lithium ion complexing, ensured this starch baseVery high lithium ion transference number in polymer dielectric.
3, the present invention is by pre-porous-starch gelatinization processing, the shallow lake of then making porous under the effect of coagulant and pore creating materialPowder film, the porous-starch film obtaining not only has excellent mechanical performance, and loose structure in starch film is also lithium ionMigration in starch film provides passage, has improved lithium ion migration velocity, also improves lithium ion conducting rate.
4, the present invention uses the matrix material of porous-starch as polymer dielectric, and having nontoxic, environmental protection can fallThe advantage of separating.
5, production process of the present invention is simple, and production cost is lower, easy to operate, is easy to suitability for industrialized production.
Starch-based polymer electrolyte and other polymer dielectric that the present invention is made are tested, and result is as follows:
| Material | Ionic conductivity (S/cm) | Lithium ion transference number (individual/cm) |
| Pure solid polymer electrolyte | 1×10-4-8×10-3 | 102 |
| Gel polymer electrolyte | 5×10-4-4×10-3 | 103 |
| Polymer dielectric of the present invention | 4×10-4-6×10-3 | 104 |
Brief description of the drawings
Fig. 1 is preparation technology's flow chart of the present invention.
Detailed description of the invention
Below by detailed description of the invention, the present invention is described in further detail, but this should be interpreted as to the present inventionScope only limit to following example. In the situation that not departing from said method thought of the present invention, according to ordinary skillVarious replacements or change that knowledge and customary means are made, all should be within the scope of the present invention.
Embodiment 1
1) corn porous starch of 65 weight portions is dissolved in reactor in the distilled water of 30 degrees Celsius, forms solution,Then be warming up to 80 degrees Celsius, add the NaOH of 2 parts to carry out pre-gelatinization processing, obtain porous-starch colloidal sol;
2) in the porous-starch colloidal sol obtaining in step 1), add the Boratex of 2 weight portions and the methyl alcohol of 5 parts by weight, fillThe reaction 30min that is uniformly mixed dividing obtains casting solution, and vacuum defoamation is processed rear blade coating on glass plate, natural coagulation 2h, film formingBe placed on 1h in the baking oven that is heated to 50 degrees Celsius, make pore creating material volatilization, obtain porous-starch film;
3) by step 2) the porous-starch film that obtains immerses and is equipped with in the irradiation tube of polyurethane-modified dose of 5 weight portions,Under the condition that ultraviolet irradiation is penetrated, carry out graft modification and process 40min, take out the porous-starch film that obtains modification;
4) the porous-starch film of modification step 3) being obtained is immersed in the LiBF4 solution of 5 weight portions and carries out networkClose reaction 20min, take out and be placed in vacuum drying chamber, be dried and obtain the starch base polymerization of a kind of lithium ion battery in a vacuumThing electrolyte.
Embodiment 2
1) the potato porous-starch of 80 weight portions is dissolved in reactor in the distilled water of 30 degrees Celsius, forms solution,Then be warming up to 75 degrees Celsius, add the NaOH of 4 parts to carry out pre-gelatinization processing, obtain porous-starch colloidal sol;
2) in the porous-starch colloidal sol obtaining in step 1), add the second of thiazoles coagulant and 10 weight portions of 5 weight portionsAlcohol, is uniformly mixed fully reaction 60min and obtains casting solution, and vacuum defoamation is processed rear blade coating on glass plate, natural coagulation 3h,Film forming is placed on 2h in the baking oven that is heated to 80 degrees Celsius, makes pore creating material volatilization, obtains porous-starch film;
3) by step 2) the porous-starch film that obtains immerses and is equipped with in the irradiation tube of polycarboxylate modifier of 3 weight portions,Under the condition of penetrating at low temperature plasma irradiation, carry out graft modification and process 20min, take out the porous-starch film that obtains modification;
4) two oxalic acid that the porous-starch film of modification step 3) being obtained is immersed in 10 weight portions close in lithium borate solutionCarry out complex reaction 20min, take out and be placed in vacuum drying chamber, in vacuum or nitrogen atmosphere, be dried and obtain a kind of lithium ionBattery starch-based polymer electrolyte.
Embodiment 3
1) the konjaku porous-starch of 70 weight portions is dissolved in reactor in the distilled water of 40 degrees Celsius, forms solution,Then be warming up to 70 degrees Celsius, add the NaOH of 3 parts to carry out pre-gelatinization processing, obtain porous-starch colloidal sol;
2) in the porous-starch colloidal sol obtaining in step 1), add diphenylguanidine class coagulant and 10 weight portions of 2-5 weight portionPropyl alcohol, be uniformly mixed fully reaction 40min obtain casting solution, vacuum defoamation process after blade coating on glass plate, naturally coagulateGu 3h, film forming is placed on 1h in the baking oven that is heated to 80 degrees Celsius, makes pore creating material volatilization, obtains porous-starch film;
3) by step 2) the porous-starch film that obtains immerses and is equipped with in the irradiation tube of polyether-modified dose of 4 weight portions, at heightUnder the condition that energy x ray irradiation x is penetrated, carry out graft modification and process 40min, take out the porous-starch film that obtains modification;
4) the porous-starch film of modification step 3) being obtained is immersed in the trifluoromethyl sulfonic acid lithium solution of 8 weight portionsRow complex reaction 10min, takes out and is placed in vacuum drying chamber, is dried and obtains a kind of lithium ion battery starch base in a vacuumPolymer dielectric.
Embodiment 4
1) the wheat porous-starch of 65 weight portions is dissolved in reactor in the distilled water of 40 degrees Celsius, forms solution,Then be warming up to 65 degrees Celsius, add the NaOH of 3 parts to carry out pre-gelatinization processing, obtain porous-starch colloidal sol;
2) in the porous-starch colloidal sol obtaining in step 1), add the coagulant agent of diphenylguanidine class and 5 weight of 2-5 weight portionThe ethylene glycol of part, is uniformly mixed fully reaction 60min and obtains casting solution, and vacuum defoamation is processed rear blade coating on glass plate, fromSo solidify 3h, film forming is placed on 2h in the baking oven that is heated to 80 degrees Celsius, makes pore creating material volatilization, obtains porous-starch film;
3) by step 2) the porous-starch film that obtains immerses and is equipped with in the irradiation tube of polyurethane-modified dose of 5 weight portions,Under the condition that ultraviolet irradiation is penetrated, carry out graft modification and process 30min, take out the porous-starch film that obtains modification;
4) the porous-starch film of modification step 3) being obtained is immersed in the lithium hexafluoro phosphate solution of 10 weight portions and carries outComplex reaction 15min, takes out and is placed in vacuum drying chamber, in nitrogen atmosphere, is dried and obtains a kind of lithium ion battery starchBase polymer electrolyte.
Claims (5)
1. a lithium ion battery starch-based polymer electrolyte, it is characterized in that being prepared by weight by following raw material andBecome:
Porous-starch 65-80 part,
NaOH 2-4 part,
Coagulant 2-5 part,
Pore creating material 5-10 part,
Modifier 3-5 part,
Lithium salt solution 5-10 part,
Wherein said porous-starch refers to the enzyme with raw amylase activity lower than acting on raw starch under gelatinization pointAnd form the cellular starch of porous, starch surface is covered with the aperture that diameter is 10nm-500nm, aperture by surface to centerDeeply, the volume in hole accounts for the 45%-55% of particle volume; Described coagulant be a kind of of borate family, thiazoles, diphenylguanidine class orMultiple; Described pore creating material is one or more in methyl alcohol, ethanol, propyl alcohol, ethylene glycol; Described modifier is with activityHydroxyl, carboxyl and amino straight chain polymer; Described lithium salt solution is that mass fraction is that the LiBF4 of 35%-50% is moltenLiquid, two oxalic acid close lithium borate solution, trifluoromethyl sulfonic acid lithium solution, lithium hexafluoro phosphate solution, two (trimethyl fluoride sulfonyl) iminesOne or more in lithium solution; Described lithium ion battery starch-based polymer electrolyte, prepare by the following method and obtain:
1) porous-starch of 65-80 weight portion is dissolved in reactor in the distilled water of 30-40 degree Celsius, forms solution, soAfter be warming up to 60-80 degree Celsius, add the NaOH of 2-4 part to carry out pre-gelatinization processing, obtain porous-starch colloidal sol;
2) in the porous-starch colloidal sol obtaining in step 1), add the coagulant of 2-5 weight portion and the pore creating material of 5-10 weight portion,Be uniformly mixed fully reaction 30-60min and obtain casting solution, vacuum defoamation is processed rear blade coating on glass plate, natural coagulation 2-3h, film forming is placed on 1-2h in the baking oven that is heated to 50-80 degree Celsius, makes pore creating material volatilization, obtains porous-starch film;
3) by step 2) the porous-starch film that obtains immerses and is equipped with in the irradiation tube of 3-5 weight portion modifier, the bar of penetrating at irradiationUnder part, carry out graft modification and process 20-40min, take out the porous-starch film that obtains modification;
4) the porous-starch film of modification step 3) being obtained is immersed in that in the solution of lithium salts of 5-10 weight portion, to carry out complexing anti-Answer 10-20min, take out and be placed in vacuum drying chamber, in vacuum or nitrogen atmosphere, be dried and obtain a kind of lithium ion battery useStarch-based polymer electrolyte.
2. a kind of lithium ion battery starch-based polymer electrolyte according to claim 1, described in it is characterized in thatPorous-starch is one or more in wheaten starch, potato starch, cornstarch, tapioca, konjak starch; Described changesProperty agent is that the degree of polymerization is the polymer of 10-50.
3. according to a kind of lithium ion battery starch-based polymer electrolyte claimed in claim 1, it is characterized in that described changingProperty agent is one or more in polyurethane, polycarboxylate, polyethers.
4. a kind of lithium ion battery starch-based polymer electrolyte according to claim 1, described in it is characterized in thatIrradiation tube is quartz glass tube.
5. a kind of lithium ion battery starch-based polymer electrolyte according to claim 1, described in it is characterized in thatIrradiation is penetrated as the one in ultraviolet irradiation, low temperature plasma irradiation or high-energy ray irradiation.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103441300A (en) * | 2013-08-23 | 2013-12-11 | 浙江地坤键新能源科技有限公司 | Gel polymer electrolyte containing natural high molecular material as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103441300A (en) * | 2013-08-23 | 2013-12-11 | 浙江地坤键新能源科技有限公司 | Gel polymer electrolyte containing natural high molecular material as well as preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 《Electrical analysis of amorphous corn starch-based polymer electrolyte membranes doped with LiI》;M F Shukur等;《PHYSICA SCRIPTA》;20130703;第1-9页 * |
| 《Ionic conductivity studies and dielectric studies of Poly(styrene sulphonic acid)/starch blend polymer electrolyte containing LiClO4》;Y. N. Sudhakar等;《J Appl Electrochem》;20121021;第21-29页 * |
| 《NMR study of starch based polymer gel electrolytes: Humidity effects》;R.I. Mattos等;《Electrochimica Acta》;20070602;第1461-1465页 * |
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