CN102709597B - Composite all solid-state polymer electrolyte lithium ion battery and preparation method of composite all solid-state polymer electrolyte lithium ion battery - Google Patents
Composite all solid-state polymer electrolyte lithium ion battery and preparation method of composite all solid-state polymer electrolyte lithium ion battery Download PDFInfo
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Abstract
The invention discloses a composite all solid-state polymer electrolyte lithium ion battery and a preparation method of the composite all solid-state polymer electrolyte lithium ion battery, and belongs to the all solid-state polymer electrolyte preparation technology and the lithium ion battery field. The composite all solid-state polymer electrolyte lithium ion battery disclosed by the invention comprises a battery case and an electrode core, wherein the electrode core is accommodated in the battery case in a sealed way and comprises a positive electrode, a negative electrode and composite all solid-state polymer electrolytes positioned between the positive electrode and the negative electrode, and the composite all solid-state polymer electrolytes comprise dimethyl siloxane-ethylene oxide copolymers, lithium salts and nanometer inorganic fillers. Compared with the existing composite all solid-state polymer electrolytes, the composite all solid-state polymer electrolytes adopted by the invention have the advantages that base materials are the dimethyl siloxane-ethylene oxide copolymers, the regularity of the polymer chain segment is reduced, and the crystallization degree of the polymers at the surface is reduced, so higher ionic conductivity is realized at normal temperature.
Description
Technical field
The present invention relates to a kind of lithium ion battery and preparation method thereof, particularly relate to a kind of compound all-solid polymer electrolyte lithium ion battery and preparation method thereof, belong to full solid state polymer electrolyte technology of preparing and field of lithium ion battery.
Background technology
Compared with other chemical power source, lithium rechargeable battery has the performance of many excellences, as high in energy density, have extended cycle life, open circuit voltage is high, memory-less effect, safety non-pollution etc., through the develop rapidly of recent two decades, be applied in the field of portable devices such as mobile phone, notebook computer, digital camera widely.In recent years, along with the further raising of lithium ion battery energy density, its application is just progressively extended to the high-tech sectors such as Aero-Space, satellite, guided missile electric automobile, and therefore, the fail safe of battery is most important.
The internal structure of commercial lithium ion battery generally includes at present: the amberplex composition of positive pole and negative pole and the liquid electrolyte containing lithium salts and isolation both positive and negative polarity.As everyone knows, the existence of a large amount of organic liquid electrolyte, not only increases the risk of battery leakage, and will speed up the speed of battery thermal runaway under abuse conditions, and then causes battery catches fire or blast, there is serious potential safety hazard.
All solid state electrolyte is adopted to be the important method improving battery security as the electrolyte of lithium ion battery, at present, all solid state electrolyte mainly comprises two large classes: one is inorganic solid electrolyte, as inorganic solid electrolyte, LiX, Li of LISICON, NASICON structure
3n and derivative etc. thereof, but this electrolytelike ionic conductivity generally 3 ~ 5 orders of magnitude lower than organic liquid electrolytes ionic conductivity at normal temperatures, mean that battery can not high rate charge-discharge, therefore limits its application in lithium battery greatly; Two is organic solid electrolyte baseds, as polyethers system (PEO), such electrolyte can form stable complex compound with lithium salts, be easy to the conduction realizing ion, due to polymeric material itself, there is higher plasticity in addition and be easy to the advantages such as film forming, the lithium ion battery of various shape can be applied to, but the full solid state polymer electrolyte formed due to PEO and lithium salts has higher crystalline phase when room temperature, the electrolyte formed also can only at high temperature could use, and therefore its practical application is restricted.The method being commonly used to reduce PEO degree of crystallinity adds organic liquid plasticizer, although liquid plasticizer add the ionic conductivity that improve full solid state polymer electrolyte, but simultaneously also destroy electrolytical mechanical performance and increase the activity of itself and lithium titanate cathode material, reduce life-span (H.J.Walls, J.Zhou, the J.A.Yerian of battery, et al.J.Power Sources, 2000,89, (2): 156-162).
In recent years, in order to improve mechanical property and the ionic conductivity of full solid state polymer electrolyte, in full solid state polymer electrolyte, add inorganic material particle, if Chinese patent CN03136183.8 is by inorganic oxide (montmorillonite, SiO
2or ZnO) join (PEO) in polyethylene glycol oxide solid electrolyte, prepare conductivity and be about 3 × 10
-4under S/cm(60 DEG C of condition) full solid state polymer electrolyte; The mesopore molecular sieve of modification is joined (PEO) in polyethylene glycol oxide solid electrolyte by Chinese patent CN200610036632.9, has prepared conductivity and has been about 1 × 10
-4under S/cm(60 DEG C of condition) full solid state polymer electrolyte.
But all solid state electrolyte of above-mentioned prior art and preparation method thereof exists following defect: first, polyethylene glycol oxide solid electrolyte at room temperature has higher degree of crystallinity, and therefore under electrolyte room temperature, ionic conductivity is lower; Secondly, in order to improve the problem that ionic conductivity is low and mechanical property is bad, need to add a large amount of inorganic nano-fillers, as everyone knows, the dispersion of nano particle difficulty is easily reunited, and not only affects electrolytical consistency but also is unfavorable for large-scale production; Finally, also there is the defect that thermal stability is bad and electrochemical stability is low in all solid state electrolyte of this system.
Summary of the invention
The object of the invention is to solve the defects such as all solid state electrolyte ionic conductivity is low, mechanical property is bad in prior art, a kind of compound all-solid polymer electrolyte lithium ion battery is provided, makes compound all solid state polyeletrolyte lithium ion battery ionic conductivity high, good mechanical property, Heat stability is good and electrochemical stability at normal temperatures.
Another one object of the present invention is to provide a kind of preparation method of above-mentioned compound all-solid polymer electrolyte lithium ion battery, and the above-mentioned compound all-solid polymer electrolyte lithium ion battery prepared is had, and consistency is high, good stability and production efficiency is high.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of compound all-solid polymer electrolyte lithium ion battery, comprise battery case and pole piece, described pole piece sealing is contained in battery case, described pole piece comprises positive pole, negative pole and the compound all-solid polymer electrolyte between positive pole and negative pole, it is characterized in that: described compound all-solid polymer electrolyte comprises dimethyl siloxane-ethylene oxide copolymer P (DMS-CO-EO), lithium salts and nanometer inorganic filler.
Dimethyl siloxane in dimethyl siloxane of the present invention-ethylene oxide copolymer P (DMS-CO-EO) and the mass ratio of oxirane are 3:7 ~ 7:3.
The number-average molecular weight of dimethyl siloxane of the present invention-ethylene oxide copolymer P (DMS-CO-EO) is 5 × 10
5~ 1 × 10
6.
Dimethyl siloxane of the present invention-ethylene oxide copolymer P (DMS-CO-EO) is 6 ~ 25:1 with the mass ratio of O atom in lithium salts and Li atom, and described nanometer inorganic filler accounts for 5 ~ 10% of lithium salts and dimethyl siloxane-ethylene oxide copolymer gross mass.
Lithium salts of the present invention is the multiple of a kind of or arbitrary proportion in lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, lithium perchlorate, trifluoromethyl sulfonic acid lithium, perfluoro butyl Sulfonic Lithium, lithium aluminate, chlorine lithium aluminate, fluoro sulfimide lithium, lithium chloride and lithium iodide.
Above-mentioned lithium salts is preferably two kinds of the one or any ratio mixing in lithium perchlorate and fluoro sulfimide lithium.
Nanometer inorganic filler of the present invention is: titanium oxide (TiO
2), zirconia (ZrO
2), alundum (Al2O3) (Al
2o
3) and magnesium oxide (MgO) in a kind of or arbitrary proportion multiple.
The particle diameter of above-mentioned inorganic filler is 30 ~ 70nm.
A kind of preparation method of compound all-solid polymer electrolyte battery, processing step comprises conventional anode sizing agent and cathode size preparation, positive pole and negative pole preparation, compound all-solid polymer electrolyte preparation, heat treatment, heat-sealing, once changes into, secondary heat treatment and partial volume, it is characterized in that: described compound all-solid polymer electrolyte is prepared and is specially:
A, lithium salts is joined in acetonitrile solvent, be stirred to dissolving; (arbitrary proportion)
B, nanometer inorganic filler is joined in steps A solution, stir after ultrasonic disperse and form slurry;
C, in the slurry prepared by step B, add dimethyl siloxane-ethylene oxide copolymer P (DMS-CO-EO), stir, form suspension;
D, by the suspension in step C anode surface, battery cathode is surperficial or be placed in Teflon mould, is directly clipped between battery plus-negative plate, evaporative removal solvent, obtains compound all-solid polymer electrolyte.
Being stirred to is in step dissolved as stirred at ambient temperature 10 ~ 30min.
The ultrasonic disperse time described is in stepb 10 ~ 60min.
In the stirring described in step C for stir 30min ~ 2h at 60 ~ 90 DEG C.
Evaporative removal solvent described is in step D at 60 DEG C, and vacuum degree is dry 16 ~ 24h under-85KPa.
Described in step D suspension is placed in Teflon mould, is directly clipped between battery plus-negative plate as at 0.1 ~ 2MPa, at 60 ~ 120 DEG C, makes battery plus-negative plate bond with the Teflon mould that suspension is housed.
Beneficial effect of the present invention is as follows:
1, compared with existing composite solid polymer electrolyte, the composite solid polymer electrolyte basis material that the present invention adopts is dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) because the regularity of polymer segment declines, the degree of crystallinity of its polymer of surface declines, and therefore has higher ionic conductivity under normal temperature;
2, composite solid polymer electrolyte of the present invention contains nano sized inorganic fillers, owing to having higher specific area, can improve the mechanical property of full solid state polymer electrolyte significantly and improve its ionic conductivity;
4, the lithium ion battery prepared by the present invention is adopted to have higher fail safe.
5, the dimethyl siloxane in dimethyl siloxane of the present invention-ethylene oxide copolymer P (DMS-CO-EO) and the mass ratio of oxirane are 3:7 ~ 7:3, adopt this proportion can increase the randomness of polymer molecular chain, also mean the degree of crystallinity that can reduce polymer, improve the ionic conductivity of polymer itself.
6, nanometer inorganic filler of the present invention accounts for 5 ~ 10% of lithium salts and dimethyl siloxane-ethylene oxide copolymer gross mass, the particle diameter of inorganic filler is 30 ~ 70nm, adopt this parameter area can take into account the raising of ionic conductivity, take into account the raising of mechanical property simultaneously.
7, lithium salts of the present invention is two kinds of the one or any ratio mixing in lithium perchlorate and fluoro sulfimide lithium, can significantly improve conductivity.
8, in prior art, nano inorganic particle stirs together with polymer, the defect existed is after polymer joins, the viscosity of whole suspension can sharply increase, and nano particle is difficult to be disperseed in a full-bodied environment, and in preparation method of the present invention, nano inorganic particle is independent dispersion, therefore dispersed better and efficiency is higher and Inventive polymers dissolves and completes at 60 ~ 90 DEG C, and such dissolved efficiency is high, cost-saving, improve production efficiency.
Embodiment
embodiment 1
A kind of compound all-solid polymer electrolyte lithium ion battery, comprise battery case and pole piece, described pole piece sealing is contained in battery case, described pole piece comprises positive pole, negative pole and the compound all-solid polymer electrolyte between positive pole and negative pole, it is characterized in that: described compound all-solid polymer electrolyte comprises dimethyl siloxane-ethylene oxide copolymer, lithium salts and nanometer inorganic filler.
Compared with existing composite solid polymer electrolyte, the composite solid polymer electrolyte basis material that the present invention adopts is dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) because the regularity of polymer segment declines, the degree of crystallinity of its polymer of surface declines, and therefore has higher ionic conductivity under normal temperature.
embodiment 2
A kind of compound all-solid polymer electrolyte lithium ion battery, comprise battery case and pole piece, described pole piece sealing is contained in battery case, described pole piece comprises positive pole, negative pole and the compound all-solid polymer electrolyte between positive pole and negative pole, it is characterized in that: described compound all-solid polymer electrolyte comprises dimethyl siloxane-ethylene oxide copolymer, lithium salts and nanometer inorganic filler.
Dimethyl siloxane in described dimethyl siloxane-ethylene oxide copolymer and the mass ratio of oxirane are 7:3.
In described dimethyl siloxane-ethylene oxide copolymer and lithium salts, the mass ratio of O atom and Li atom is 6:1, and described nanometer inorganic filler accounts for 5% of lithium salts and dimethyl siloxane-ethylene oxide copolymer gross mass.
Described lithium salts is two kinds of the one or any ratio mixing in lithium perchlorate and fluoro sulfimide lithium.
The particle diameter of described inorganic filler is 30nm.
embodiment 3
A kind of compound all-solid polymer electrolyte lithium ion battery, comprise battery case and pole piece, described pole piece sealing is contained in battery case, described pole piece comprises positive pole, negative pole and the compound all-solid polymer electrolyte between positive pole and negative pole, it is characterized in that: described compound all-solid polymer electrolyte comprises dimethyl siloxane-ethylene oxide copolymer, lithium salts and nanometer inorganic filler.
Dimethyl siloxane in described dimethyl siloxane-ethylene oxide copolymer and the mass ratio of oxirane are 3:7.
In described dimethyl siloxane-ethylene oxide copolymer and lithium salts, the mass ratio of O atom and Li atom is 25:1, and described nanometer inorganic filler accounts for 10% of lithium salts and dimethyl siloxane-ethylene oxide copolymer gross mass.
Described lithium salts is two kinds of the one or any ratio mixing in lithium perchlorate and fluoro sulfimide lithium.
The particle diameter of described inorganic filler is 70nm.
embodiment 4
A kind of compound all-solid polymer electrolyte lithium ion battery, comprise battery case and pole piece, described pole piece sealing is contained in battery case, described pole piece comprises positive pole, negative pole and the compound all-solid polymer electrolyte between positive pole and negative pole, it is characterized in that: described compound all-solid polymer electrolyte comprises dimethyl siloxane-ethylene oxide copolymer, lithium salts and nanometer inorganic filler.
Dimethyl siloxane in described dimethyl siloxane-ethylene oxide copolymer and the mass ratio of oxirane are 21:29.
In described dimethyl siloxane-ethylene oxide copolymer and lithium salts, the mass ratio of O atom and Li atom is 15.5:1, and described nanometer inorganic filler accounts for 7.5% of lithium salts and dimethyl siloxane-ethylene oxide copolymer gross mass.
Described lithium salts is two kinds of the one or any ratio mixing in lithium perchlorate and fluoro sulfimide lithium.
The particle diameter of described inorganic filler is 50nm.
embodiment 5
A kind of compound all-solid polymer electrolyte lithium ion battery, comprise battery case and pole piece, described pole piece sealing is contained in battery case, described pole piece comprises positive pole, negative pole and the compound all-solid polymer electrolyte between positive pole and negative pole, it is characterized in that: described compound all-solid polymer electrolyte comprises dimethyl siloxane-ethylene oxide copolymer, lithium salts and nanometer inorganic filler.
Dimethyl siloxane in described dimethyl siloxane-ethylene oxide copolymer and the mass ratio of oxirane are 3:4.
In described dimethyl siloxane-ethylene oxide copolymer and lithium salts, the mass ratio of O atom and Li atom is 20:1, and described nanometer inorganic filler accounts for 8.5% of lithium salts and dimethyl siloxane-ethylene oxide copolymer gross mass.
Described lithium salts is two kinds of the one or any ratio mixing in lithium perchlorate and fluoro sulfimide lithium.
The particle diameter of described inorganic filler is 42nm.
embodiment 6
A kind of preparation method of compound all-solid polymer electrolyte battery, processing step comprises anode sizing agent and cathode size preparation, positive pole and negative pole preparation, compound all-solid polymer electrolyte preparation, heat treatment, heat-sealing, once changes into, secondary heat treatment and partial volume, and described compound all-solid polymer electrolyte is prepared and is specially:
A, lithium salts is joined in acetonitrile solvent, be stirred to dissolving;
B, nanometer inorganic filler is joined in steps A solution, stir after ultrasonic disperse and form slurry;
C, in the slurry prepared by step B, add dimethyl siloxane-ethylene oxide copolymer, stir, form suspension;
D, by the suspension in step C anode surface, battery cathode is surperficial or be placed in Teflon mould, is directly clipped between battery plus-negative plate, evaporative removal solvent, obtains compound all-solid polymer electrolyte.
embodiment 7
A kind of preparation method of compound all-solid polymer electrolyte battery, processing step comprises anode sizing agent and cathode size preparation, positive pole and negative pole preparation, compound all-solid polymer electrolyte preparation, heat treatment, heat-sealing, once changes into, secondary heat treatment and partial volume, and described compound all-solid polymer electrolyte is prepared and is specially:
A, lithium salts is joined in acetonitrile solvent, be stirred to dissolving;
B, nanometer inorganic filler is joined in steps A solution, stir after ultrasonic disperse and form slurry;
C, in the slurry prepared by step B, add dimethyl siloxane-ethylene oxide copolymer, stir, form suspension;
D, by the suspension in step C anode surface, battery cathode is surperficial or be placed in Teflon mould, is directly clipped between battery plus-negative plate, evaporative removal solvent, obtains compound all-solid polymer electrolyte.
Being stirred to is in step dissolved as stirred at ambient temperature 10min.
The ultrasonic disperse time described is in stepb 10min.
In the stirring described in step C for stir 30min at 60 DEG C.
Evaporative removal solvent described is in step D at 60 DEG C, and vacuum degree is dry 16h under-85KPa.
embodiment 8
A kind of preparation method of compound all-solid polymer electrolyte battery, processing step comprises anode sizing agent and cathode size preparation, positive pole and negative pole preparation, compound all-solid polymer electrolyte preparation, heat treatment, heat-sealing, once changes into, secondary heat treatment and partial volume, and described compound all-solid polymer electrolyte is prepared and is specially:
A, lithium salts is joined in acetonitrile solvent, be stirred to dissolving;
B, nanometer inorganic filler is joined in steps A solution, stir after ultrasonic disperse and form slurry;
C, in the slurry prepared by step B, add dimethyl siloxane-ethylene oxide copolymer, stir, form suspension;
D, by the suspension in step C anode surface, battery cathode is surperficial or be placed in Teflon mould, is directly clipped between battery plus-negative plate, evaporative removal solvent, obtains compound all-solid polymer electrolyte.
Being stirred to is in step dissolved as stirred at ambient temperature 30min.
The ultrasonic disperse time described is in stepb 60min.
In the stirring described in step C for stir 2h at 90 DEG C.
Evaporative removal solvent described is in step D at 60 DEG C, and vacuum degree is dry 24h under-85KPa.
embodiment 9
A kind of preparation method of compound all-solid polymer electrolyte battery, processing step comprises anode sizing agent and cathode size preparation, positive pole and negative pole preparation, compound all-solid polymer electrolyte preparation, heat treatment, heat-sealing, once changes into, secondary heat treatment and partial volume, and described compound all-solid polymer electrolyte is prepared and is specially:
A, lithium salts is joined in acetonitrile solvent, be stirred to dissolving;
B, nanometer inorganic filler is joined in steps A solution, stir after ultrasonic disperse and form slurry;
C, in the slurry prepared by step B, add dimethyl siloxane-ethylene oxide copolymer, stir, form suspension;
D, by the suspension in step C anode surface, battery cathode is surperficial or be placed in Teflon mould, is directly clipped between battery plus-negative plate, evaporative removal solvent, obtains compound all-solid polymer electrolyte.
Being stirred to is in step dissolved as stirred at ambient temperature 20min.
The ultrasonic disperse time described is in stepb 35min.
In the stirring described in step C for stir 1.25h at 75 DEG C.
Evaporative removal solvent described is in step D at 60 DEG C, and vacuum degree is dry 20h under-85KPa.
embodiment 10
A kind of preparation method of compound all-solid polymer electrolyte battery, processing step comprises anode sizing agent and cathode size preparation, positive pole and negative pole preparation, compound all-solid polymer electrolyte preparation, heat treatment, heat-sealing, once changes into, secondary heat treatment and partial volume, and described compound all-solid polymer electrolyte is prepared and is specially:
A, lithium salts is joined in acetonitrile solvent, be stirred to dissolving;
B, nanometer inorganic filler is joined in steps A solution, stir after ultrasonic disperse and form slurry;
C, in the slurry prepared by step B, add dimethyl siloxane-ethylene oxide copolymer, stir, form suspension;
D, by the suspension in step C anode surface, battery cathode is surperficial or be placed in Teflon mould, is directly clipped between battery plus-negative plate, evaporative removal solvent, obtains compound all-solid polymer electrolyte.
Being stirred to is in step dissolved as stirred at ambient temperature 26min.
The ultrasonic disperse time described is in stepb 18min.
In the stirring described in step C for stir 1.6h at 81 DEG C.
Evaporative removal solvent described is in step D at 60 DEG C, and vacuum degree is dry 21h under-85KPa.
embodiment 11
First, according to (O/Li)=6 take a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and lithium perchlorate, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 1 × 10
5, the mass ratio of dimethyl siloxane and oxirane is 1: 9; Next mass percent taking lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is the nano titanium oxide (TiO of 0.5%
2), wherein the particle diameter of titanium dioxide is 10nm;
Dissolve lithium salts: join in acetonitrile solution by the lithium salts after weighing, at room temperature stir 30min;
Dispersed inorganic filler: by the lithium salts nano titanium oxide (TiO after weighing
2) add ultrasonic wave dispersion 10min in above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after weighing is joined in above-mentioned suspension, stirring at room temperature 30min;
Dry: to water in Teflon mould by above-mentioned solution, dry 16h in 60 DEG C of vacuum environments with-85kpa, obtain compound all-solid polymer electrolyte, prepared Electrolyte film thickness is 120 microns.The ionic conductivity at 60 DEG C of then testing sample is 5.3 × 10
-4s/cm.
embodiment 12
First, according to (O/Li)=25 take a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and lithium perchlorate, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 2 × 10
6, the mass ratio of dimethyl siloxane and oxirane is 9: 1; Next mass percent taking lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is the nano titanium oxide (TiO of 20%
2), wherein the particle diameter of titanium dioxide is 100nm;
Dissolve lithium salts: join in acetonitrile solution by the lithium salts after weighing, at room temperature stir 30min;
Dispersed inorganic filler: by the lithium salts nano titanium oxide (TiO after weighing
2) add ultrasonic wave dispersion 60min in above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after weighing is joined in above-mentioned suspension, stirring at room temperature 2h;
Dry: to water in Teflon mould by above-mentioned solution, dry 24h in 60 DEG C of vacuum environments with-85kpa, obtain compound all-solid polymer electrolyte, prepared Electrolyte film thickness is 120 microns.The ionic conductivity at 60 DEG C of then testing sample is 6.7 × 10
-4s/cm.
embodiment 13
First, according to (O/Li)=16 take a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and lithium perchlorate, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 2 × 10
6, the mass ratio of dimethyl siloxane and oxirane is 3: 7; Next mass percent taking lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is the nano titanium oxide (TiO of 10%
2), wherein the particle diameter of titanium dioxide is 50nm;
Dissolve lithium salts: join in acetonitrile solution by the lithium salts after weighing, at room temperature stir 30min;
Dispersed inorganic filler: by the lithium salts nano titanium oxide (TiO after weighing
2) add ultrasonic wave dispersion 30min in above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after weighing is joined in above-mentioned suspension, stirring at room temperature 1h;
Dry: to water in Teflon mould by above-mentioned solution, dry 18h in 60 DEG C of vacuum environments with-85kpa, obtain compound all-solid polymer electrolyte, prepared Electrolyte film thickness is 120 microns.The ionic conductivity at 60 DEG C of then testing sample is 9.1 × 10
-4s/cm.
embodiment 14
First, according to (O/Li)=16 take a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and trifluoromethyl sulfonic acid lithium, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 5 × 10
5, the mass ratio of dimethyl siloxane and oxirane is 7: 3; Next mass percent taking lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is the nano-aluminium oxide (Al of 8%
2o
3), wherein the particle diameter of alundum (Al2O3) is 30nm;
Dissolve lithium salts: join in acetonitrile solution by the lithium salts after weighing, at room temperature stir 30min;
Dispersed inorganic filler: by the lithium salts nano-aluminium oxide (Al after weighing
2o
3) add ultrasonic wave dispersion 30min in above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after weighing is joined in above-mentioned suspension, stirring at room temperature 1h;
Dry: to water in Teflon mould by above-mentioned solution, dry 18h in 60 DEG C of vacuum environments with-85kpa, obtain compound all-solid polymer electrolyte, prepared Electrolyte film thickness is 120 microns.The ionic conductivity at 60 DEG C of then testing sample is 1.2 × 10
-3s/cm.
embodiment 15
First, according to (O/Li)=12 take a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and trifluoromethyl sulfonic acid lithium, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 5 × 10
5, the mass ratio of dimethyl siloxane and oxirane is 5: 5; Next mass percent taking lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is the nano magnesia (MgO) of 8%, and wherein magnesian particle diameter is 40nm;
Dissolve lithium salts: join in acetonitrile solution by the lithium salts after weighing, at room temperature stir 30min;
Dispersed inorganic filler: the lithium salts nano magnesia (MgO) after weighing is added ultrasonic wave dispersion 10min in above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after weighing is joined in above-mentioned suspension, stirring at room temperature 1.5h;
Dry: to water in Teflon mould by above-mentioned solution, dry 18h in 60 DEG C of vacuum environments with-85kpa, obtain compound all-solid polymer electrolyte, prepared Electrolyte film thickness is 120 microns.The ionic conductivity at 60 DEG C of then testing sample is 9.9 × 10
-4s/cm.
embodiment 16
First, according to (O/Li)=12 take a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and trifluoromethyl sulfonic acid lithium, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 1 × 10
6, the mass ratio of dimethyl siloxane and oxirane is 5: 5; Next mass percent taking lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is the nano zircite (ZrO of 5%
2), wherein zirconic particle diameter is 20nm;
Dissolve lithium salts: join in acetonitrile solution by the lithium salts after weighing, at room temperature stir 30min;
Dispersed inorganic filler: by the lithium salts nano zircite (ZrO after weighing
2) add ultrasonic wave dispersion 30min in above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after weighing is joined in above-mentioned suspension, stirring at room temperature 1h;
Dry: to water in Teflon mould by above-mentioned solution, dry 18h in 60 DEG C of vacuum environments with-85kpa, obtain compound all-solid polymer electrolyte, prepared Electrolyte film thickness is 120 microns.The ionic conductivity at 60 DEG C of then testing sample is 2.1 × 10
-3s/cm.
embodiment 17
First, according to (O/Li)=16 take a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and trifluoromethyl sulfonic acid lithium, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 1 × 10
6, the mass ratio of dimethyl siloxane and oxirane is 4: 6; Next mass percent taking lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is the nano zircite (ZrO of 5%
2), wherein zirconic particle diameter is 20nm;
Dissolve lithium salts: join in acetonitrile solution by the lithium salts after weighing, at room temperature stir 30min;
Dispersed inorganic filler: by the lithium salts nano zircite (ZrO after weighing
2) add ultrasonic wave dispersion 30min in above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after weighing is joined in above-mentioned suspension, stirring at room temperature 1h;
Dry: to water in Teflon mould by above-mentioned solution, dry 18h in 60 DEG C of vacuum environments with-85kpa, obtain compound all-solid polymer electrolyte, prepared Electrolyte film thickness is 120 microns.The ionic conductivity at 60 DEG C of then testing sample is 2.7 × 10
-3s/cm.
embodiment 18
First, according to (O/Li)=16 take a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and trifluoromethyl sulfonic acid lithium, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 1 × 10
6, the mass ratio of dimethyl siloxane and oxirane is 6: 4; Next mass percent taking lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is the nano zircite (ZrO of 5%
2), wherein zirconic particle diameter is 20nm;
Dissolve lithium salts: join in acetonitrile solution by the lithium salts after weighing, at room temperature stir 30min;
Dispersed inorganic filler: by the lithium salts nano zircite (ZrO after weighing
2) add ultrasonic wave dispersion 30min in above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after weighing is joined in above-mentioned suspension, stirring at room temperature 1h;
Dry: to water in Teflon mould by above-mentioned solution, dry 18h in 60 DEG C of vacuum environments with-85kpa, obtain compound all-solid polymer electrolyte, prepared Electrolyte film thickness is 120 microns.The ionic conductivity at 60 DEG C of then testing sample is 3.1 × 10
-3s/cm.
embodiment 19
A kind of lithium ion battery, comprise battery case and pole piece, described pole piece sealing is contained in battery case, described pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, the full solid state polymer electrolyte of described full solid state polymer electrolyte prepared by the method for embodiment 1 ~ 18.
The preparation method of lithium rechargeable battery is following processing step:
The preparation of A, anode sizing agent: according to those skilled in the art's technology in common knowledge by LiCoO
2,acetylene black PVDF and NMP mixes;
The preparation of B, cathode size: graphite, acetylene black, PVDF and NMP mix by the technology in common knowledge according to those skilled in the art;
The preparation of C, positive pole: the anode sizing agent prepared by steps A is evenly coated in collection liquid surface by the technology in common knowledge according to those skilled in the art, coating thickness 50 microns;
The preparation of D, negative pole: the anode sizing agent prepared by step B is evenly coated in collection liquid surface by the technology in common knowledge according to those skilled in the art, coating thickness 50 microns;
The preparation of E, full solid state polymer electrolyte suspension: prepare all solid state polyeletrolyte suspension according to the method for embodiment 1 ~ 18;
F, full solid state polymer electrolyte: the full solid state polymer electrolyte uniform suspension prepared by step e is coated in positive electrode surface or negative terminal surface;
H, drying: by dry 16h under vacuum condition at step F full solid state polymer electrolyte 60 DEG C, described vacuum degree is-85kpa;
I, heat treatment: after the positive pole containing full solid state polymer electrolyte and negative pole are replaced lamination, at pressure 0.2MPa, under temperature 60 C, hot pressing 1min, makes pole piece;
J, heat-sealing: adopt method known in those skilled in the art, put into aluminum plastic film bag by the pole piece in step C and seal, being prepared into battery core;
K, once to change into: adopt method known in those skilled in the art, adopt 0.05C electric current that above-mentioned battery core is charged to 70%SOC state;
L, secondary heat treatment: be 0.2MPa at pressure by the battery core after once changing into, temperature is pressurization baking 3h at 60 DEG C, obtains lithium rechargeable battery.
M, partial volume: the method adopting those skilled in the art to know altogether tests out the capacity (rated capacity is 50mAh) of battery.
Comparative example 1
Adopting and prepare lithium ion battery with the method that embodiment 19 is identical, is business-like liquid electrolyte unlike electrolyte.
embodiment 20
A kind of lithium ion battery, comprise battery case and pole piece, described pole piece sealing is contained in battery case, described pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, the full solid state polymer electrolyte of described full solid state polymer electrolyte prepared by the method for embodiment 1 ~ 18.
The manufacture craft process of battery is identical with embodiment 19, and difference is: in step (H), drying time is 24h, and temperature is 100 DEG C; Thermal pressure 1.0MPa in step (I), hot pressing time is 10min; Thermal pressure 1.0MPa in step (L), hot pressing time is 12h, and temperature is 100 DEG C.
Comparative example 2
Adopting and prepare lithium ion battery with the method that embodiment 20 is identical, is business-like liquid electrolyte unlike electrolyte.
embodiment 21
A kind of lithium ion battery, comprise battery case and pole piece, described pole piece sealing is contained in battery case, described pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, the full solid state polymer electrolyte of described full solid state polymer electrolyte prepared by the method for embodiment 1 ~ 18.
The manufacture craft process of battery is identical with embodiment 19, and difference is: in step (H), drying time is 24h, and temperature is 75 DEG C; Thermal pressure 0.4MPa in step (I), hot pressing time is 3min; Thermal pressure 0.4MPa in step (L), hot pressing time is 4h, and temperature is 75 DEG C.
Comparative example 3
Adopting and prepare lithium ion battery with the method that embodiment 21 is identical, is business-like liquid electrolyte unlike electrolyte.
embodiment 22
A kind of lithium ion battery, comprise battery case and pole piece, described pole piece sealing is contained in battery case, described pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, the full solid state polymer electrolyte of described full solid state polymer electrolyte prepared by the method for embodiment 1 ~ 18.
The manufacture craft process of battery is identical with embodiment 19, and difference is: in step (H), drying time is 24h, and temperature is 85 DEG C; Thermal pressure 0.6MPa in step (I), hot pressing time is 5min; Thermal pressure 0.6MPa in step (L), hot pressing time is 8h, and temperature is 85 DEG C.
Comparative example 4
Adopting and prepare lithium ion battery with the method that embodiment 22 is identical, is business-like liquid electrolyte unlike electrolyte.
embodiment 23
A kind of lithium ion battery, comprise battery case and pole piece, described pole piece sealing is contained in battery case, described pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, the full solid state polymer electrolyte of described full solid state polymer electrolyte prepared by the method for embodiment 1 ~ 18.
The manufacture craft process of battery is identical with embodiment 19, and difference is: in step (H), drying time is 24h, and temperature is 85 DEG C; Thermal pressure 0.6MPa in step (I), hot pressing time is 5min; Thermal pressure 0.6MPa in step (L), hot pressing time is 8h, and temperature is 85 DEG C.
Comparative example 5
Adopting and prepare lithium ion battery with the method that embodiment 23 is identical, is business-like liquid electrolyte unlike electrolyte.
embodiment 24
A kind of lithium ion battery, comprise battery case and pole piece, described pole piece sealing is contained in battery case, described pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, the full solid state polymer electrolyte of described full solid state polymer electrolyte prepared by the method for embodiment 1 ~ 18.
The manufacture craft process of battery is identical with embodiment 19, and difference is: in step (H), drying time is 24h, and temperature is 85 DEG C; Thermal pressure 0.6MPa in step (I), hot pressing time is 5min; Thermal pressure 0.6MPa in step (L), hot pressing time is 8h, and temperature is 85 DEG C.
Comparative example 6
Adopting and prepare lithium ion battery with the method that embodiment 24 is identical, is business-like liquid electrolyte unlike electrolyte.
embodiment 25
A kind of lithium ion battery, comprise battery case and pole piece, described pole piece sealing is contained in battery case, described pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, the full solid state polymer electrolyte of described full solid state polymer electrolyte prepared by the method for embodiment 1 ~ 18.
The manufacture craft process of battery is identical with embodiment 19, and difference is: in step (H), drying time is 24h, and temperature is 85 DEG C; Thermal pressure 0.6MPa in step (I), hot pressing time is 5min; Thermal pressure 0.6MPa in step (L), hot pressing time is 8h, and temperature is 85 DEG C.
Comparative example 7
Adopting and prepare lithium ion battery with the method that embodiment 25 is identical, is business-like liquid electrolyte unlike electrolyte.
embodiment 26
A kind of lithium ion battery, comprise battery case and pole piece, described pole piece sealing is contained in battery case, described pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, the full solid state polymer electrolyte of described full solid state polymer electrolyte prepared by the method for embodiment 1 ~ 18.
The manufacture craft process of battery is identical with embodiment 19, and difference is: in step (H), drying time is 24h, and temperature is 85 DEG C; Thermal pressure 0.6MPa in step (I), hot pressing time is 5min; Thermal pressure 0.6MPa in step (L), hot pressing time is 8h, and temperature is 85 DEG C.
Comparative example 8
Adopting and prepare lithium ion battery with the method that embodiment 26 is identical, is business-like liquid electrolyte unlike electrolyte.
embodiment 27
Security performance is tested
Embodiment 19 ~ 26 and the battery capacity prepared by comparative example 1 ~ 8 are 50mAh(0.1C).Under room temperature, respectively select the lithium ion battery that 6 embodiments 19 ~ 26 and comparative example 1 ~ 8 obtain, and charged with 0.1mAh/cm2 by battery, upper voltage limit 4.2V, cut-off current is 0.05C, does acupuncture, 150 DEG C of furnace temperature (1h) and impact test after being full of electricity respectively.Testing standard with reference to U.S. UL standard, by standard for not on fire, do not explode (×: represent and do not pass through; Zero: represent and pass through).As shown in table 1.
Table 1
As can be seen from embodiment 11 ~ 18, the ionic conductivity of the full solid state polymer electrolyte prepared by the present invention reaches 10
-3more than S/cm, close to the level of the ionic conductivity of liquid electrolyte; Can find out from embodiment 19 ~ 26 and comparative example 1 ~ 8 in addition adopts the fail safe of this full solid state polymer electrolyte apparently higher than liquid state electrolyte battery.
embodiment 28
Positive pole of the present invention refers to and is evenly applied on a current collector by anode sizing agent, thickness is 10 ~ 50 microns, the preparation method of slurry is technology known in those skilled in the art, by positive active material, conductive agent, binding agent and solvent evenly.
Positive active material of the present invention is: a kind of or arbitrary proportion in LiCoO2, LiFePO4, LiNiO2, LiNiCoAlO2, LiMn2O4 and LiNiMnCoO2 several, preferred LiFePO4 or LiMn2O4.
Conductive agent of the present invention is: a kind of or arbitrary proportion in carbon black, acetylene black, carbon fiber, flake graphite several, containing flake graphite under preferable case.
Binding agent of the present invention is: one or more in polyvinylidene fluoride and copolymer (PVDF) thereof, hexafluoropropylene-vinylidene (HFP-PVDF), polyacrylonitrile (PAN), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate (PMMA).
Solvent of the present invention is nitrogen methyl pyrrolidone (NMP).
Negative pole of the present invention refers to and is evenly applied on a current collector by cathode size, thickness is 10 ~ 50 microns, the preparation method of slurry is technology known in those skilled in the art, by negative electrode active material, conductive agent, binding agent and solvent evenly.
Negative electrode active material of the present invention is: a kind of or arbitrary proportion in Delanium, native graphite, agraphitic carbon, hard carbon or lithium titanate several.
Conductive agent of the present invention is: a kind of or arbitrary proportion in carbon black, acetylene black, carbon fiber, flake graphite several, containing flake graphite under preferable case.
Binding agent of the present invention is: one or more in polyvinylidene fluoride and copolymer (PVDF) thereof, hexafluoropropylene-vinylidene (HFP-PVDF), polyacrylonitrile (PAN), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate (PMMA);
Solvent of the present invention is nitrogen methyl pyrrolidone (NMP).
In addition, negative pole of the present invention also can be metal lithium sheet.
The preparation method of above-mentioned a kind of lithium rechargeable battery, is characterized in that: comprise following processing step:
The preparation of A, anode sizing agent: positive active material and composition mix by the technology in common knowledge according to those skilled in the art;
The preparation of B, cathode size: negative electrode active material and composition mix by the technology in common knowledge according to those skilled in the art;
The preparation of C, positive pole: the anode sizing agent prepared by steps A is evenly coated in collection liquid surface by the technology in common knowledge according to those skilled in the art, coating thickness 50 ~ 150 microns;
The preparation of D, negative pole: the anode sizing agent prepared by step B is evenly coated in collection liquid surface by the technology in common knowledge according to those skilled in the art, coating thickness 50 ~ 150 microns;
The preparation of E, full solid state polymer electrolyte suspension: the method to specifications prepares all solid state polyeletrolyte suspension;
F, full solid state polymer electrolyte: the full solid state polymer electrolyte uniform suspension prepared by step e is coated in positive electrode surface or negative terminal surface;
H, drying: by 16 ~ 24h dry under vacuum condition at step F full solid state polymer electrolyte 60 DEG C, described vacuum degree is-85kpa;
I, heat treatment: after the positive pole containing full solid state polymer electrolyte and negative pole are replaced lamination, at pressure 0.2 ~ 1.0MPa(preferably 0.4 ~ 0.6 MPa), hot pressing 1min ~ 10min(preferably 3 ~ 5min at temperature 60 ~ 100 DEG C (preferably 75 ~ 85 DEG C)), make pole piece;
J, heat-sealing: adopt method known in those skilled in the art, put into aluminum plastic film bag by the pole piece in step C and seal, being prepared into battery core;
K, once to change into: adopt method known in those skilled in the art, adopt 0.05C electric current that above-mentioned battery core is charged to 70%SOC state;
L, secondary heat treatment: be 0.2 ~ 1.0MPa(preferably 0.4 ~ 0.6 MPa at pressure by the battery core after once changing into), temperature is pressurize baking 3 ~ 12h(under 60 ~ 100 DEG C (preferably 75 ~ 85 DEG C) preferably 4 ~ 8 h), obtains lithium rechargeable battery.
M, partial volume: the method adopting those skilled in the art to know altogether tests out the capacity of battery.
Need further illustrate, if negative pole is metal lithium sheet, the preparation method of above-mentioned a kind of lithium rechargeable battery, its feature does not comprise step B and step D.
Claims (1)
1. a compound all-solid polymer electrolyte lithium ion battery, comprise battery case and pole piece, described pole piece sealing is contained in battery case, described pole piece comprises positive pole, negative pole and the compound all-solid polymer electrolyte between positive pole and negative pole, it is characterized in that: described compound all-solid polymer electrolyte comprises dimethyl siloxane-ethylene oxide copolymer, lithium salts and nanometer inorganic filler; Dimethyl siloxane in described dimethyl siloxane-ethylene oxide copolymer and the mass ratio of oxirane are 3:7 ~ 7:3; In described dimethyl siloxane-ethylene oxide copolymer and lithium salts, the mass ratio of O atom and Li atom is 6 ~ 25:1, and described nanometer inorganic filler accounts for 5 ~ 10% of lithium salts and dimethyl siloxane-ethylene oxide copolymer gross mass; The particle diameter of described inorganic filler is 30 ~ 70nm; Described lithium salts is fluoro sulfimide lithium;
Described compound all-solid polymer electrolyte lithium ion battery is obtained by following methods:
Anode sizing agent and cathode size preparation, positive pole and negative pole preparation, compound all-solid polymer electrolyte preparation, heat treatment, heat-sealing, once change into, secondary heat treatment and partial volume, described compound all-solid polymer electrolyte is prepared and is specially:
A, join in acetonitrile solvent by lithium salts, stirred at ambient temperature 10 ~ 30min is to dissolving;
B, nanometer inorganic filler is joined in steps A solution, stir after ultrasonic disperse 10 ~ 60min and form slurry;
C, in the slurry prepared by step B, add dimethyl siloxane-ethylene oxide copolymer, at 60 ~ 90 DEG C, stir 30min ~ 2h, form suspension;
D, by the suspension in step C anode surface, battery cathode is surperficial or be placed in Teflon mould, directly be clipped between battery plus-negative plate, at 60 DEG C, vacuum degree is dry 16 ~ 24h evaporative removal solvent under-85KPa, obtains compound all-solid polymer electrolyte.
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| CN107978792A (en) * | 2013-05-24 | 2018-05-01 | 苏州宝时得电动工具有限公司 | Lithium secondary battery |
| CN103647107B (en) * | 2013-11-28 | 2016-02-03 | 中国东方电气集团有限公司 | For the dielectric film and preparation method thereof of all-solid lithium-ion battery |
| CN103700886B (en) * | 2013-12-24 | 2016-05-04 | 江苏华东锂电技术研究院有限公司 | The preparation method of polymer Li-ion battery |
| CN105742713B (en) * | 2014-12-12 | 2020-08-28 | 东莞新能源科技有限公司 | All-solid-state polymer lithium battery |
| CN104993139B (en) * | 2015-06-17 | 2018-11-09 | 北京大学深圳研究生院 | A kind of composition silicate all-solid-state battery and preparation method thereof |
| CN106941189A (en) * | 2017-03-15 | 2017-07-11 | 东北师范大学 | A kind of method that all solid state electrolyte is prepared based on original position |
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| CN108155410A (en) * | 2017-12-19 | 2018-06-12 | 成都亦道科技合伙企业（有限合伙） | Solid electrolyte structure and preparation method thereof, lithium battery |
| CN108232318B (en) * | 2018-01-30 | 2020-07-17 | 陕西煤业化工技术研究院有限责任公司 | Manufacturing method of all-solid-state power lithium ion battery |
| US11476498B2 (en) | 2018-03-27 | 2022-10-18 | Lg Energy Solution, Ltd. | Complex solid electrolyte membrane for all-solid-state battery and all-solid-state battery including same |
| CN110224180A (en) * | 2019-04-30 | 2019-09-10 | 河北神州巨电新能源科技开发有限公司 | A kind of extraction process of new polymers lithium battery |
| CN110212241A (en) * | 2019-06-12 | 2019-09-06 | 哈尔滨工业大学 | A kind of solid electrolyte membrane and its preparation process and application |
| CN111883823B (en) * | 2020-06-10 | 2021-10-26 | 华南理工大学 | Composite polymer solid electrolyte material and preparation method and application thereof |
| CN111682258B (en) * | 2020-07-09 | 2021-09-03 | 常州赛得能源科技有限公司 | Dielectric electrolyte, lithium ion battery and preparation method thereof |
| CN113258172A (en) * | 2021-04-19 | 2021-08-13 | 中国科学院青岛生物能源与过程研究所 | Solid electrolyte suitable for room-temperature all-solid-state zinc-air battery and preparation method thereof |
| CN118994586A (en) * | 2023-05-17 | 2024-11-22 | 中国科学院化学研究所 | Photocurable polysiloxane, preparation method thereof and application of photocuring polysiloxane as polymer solid electrolyte |
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