CN102299378A - Composite polymer electrolyte for lithium ion secondary battery and preparation method thereof - Google Patents

Composite polymer electrolyte for lithium ion secondary battery and preparation method thereof Download PDF

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Publication number
CN102299378A
CN102299378A CN2011102059792A CN201110205979A CN102299378A CN 102299378 A CN102299378 A CN 102299378A CN 2011102059792 A CN2011102059792 A CN 2011102059792A CN 201110205979 A CN201110205979 A CN 201110205979A CN 102299378 A CN102299378 A CN 102299378A
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polymer electrolyte
lithium
composite polymer
oxide
nano
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张鼎
其鲁
李卫
闫慧
朱智
王健
郎宇琪
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HOHHOT RUOZI NEW ENERGY CO Ltd
Peking University
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HOHHOT RUOZI NEW ENERGY CO Ltd
Peking University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a composite polymer electrolyte for lithium ion secondary battery and a preparation method thereof. The preparation method comprises the following steps: using lithium bis(oxalate)borate as a main lithium salt, introducing the main lithium salt in a polymer system of ether-oxygen containing groups comprising oxirene-vinylidene fluoride, and introducing nano metallic oxide; dispersing the three ingredients uniformly to a single organic solution or mixed solution, concentrating and then volatilizing the solution to obtain the membrane. The obtained composite polymer electrolyte has excellent combination properties comprising that: the composite polymer electrolyte can stably work for commonly used anode materials of 4 or more V lithium ion batteries, and keep compatibility with the lithium metal cathode material; the composite polymer electrolyte contains no inflammable constituent and has good thermal stability; and the composite polymer electrolyte has low realization cost and can be widely used in the field of lithium ion secondary battery that has special requirements of safety and thermal stability of batteries.

Description

A kind of composite polymer electrolyte that is used for lithium secondary battery and preparation method thereof
Technical field
The present invention relates to a kind of composite polymer electrolyte and preparation method thereof, belong to lithium secondary battery critical material and technical field category.
Background technology
Excellent specific properties such as lithium secondary battery has operating voltage height, energy density height, has extended cycle life, self-discharge rate is little, low pollution, memory-less effect, portable type electronic products such as mobile phone, video camera, notebook computer have been widely used in, simultaneously, as the core component of electric automobile, the R﹠D work of lithium secondary electrokinetic cell is like a raging fire.The development of battery proposes higher requirement for the performance of its important component part one electrolyte.Traditional electrolyte based on liquid organic solvent, because the volatility of solvent, inflammability, electrolytic salt lithium hexafluoro phosphate (LiPF 6) unsteadiness under higher temperature, limited the raising of lithium secondary electrokinetic cell thermal stability and fail safe.Based on the compound polymer dielectric of polymer and novel lithium salts, because the polymer that has used high heat stability has unique advantage as the lithium salts dispersion with respect to traditional electrolyte.
In numerous polymeric systems, poly-oxireme (PEO) is because have very strong solvability and for the compatibility of lithium metal negative pole, obtain researcher's extensive concern lithium salts.For the polymer dielectric of PEO and the compound gained of lithium salts, the key point of its performance equally mainly is ionic conductivity, lithium ion transference number and electrochemical stability.About 2000, and people such as Croce (Croce E Appetecchi G B, Persi L, et al.Nature, 1998,394:456) with nanometer materials TiO 2And Al 2O 3Be incorporated in the PEO-lithium salts system, improved the conductivity at room temperature of material on largely, simultaneously to certain lifting being arranged with material lithium ion transport number and interface performance.Wieczorek and his partner (Mazor H since research in 2004, Goodnitsky D, Peled E, et al.Journal of Power Sources, 2008,178 (2): 736) in PEO-lithium salts system, introduce anion ligand material and nano-powder, prepared composite polymer electrolyte with higher conductivity at room temperature and transference number of ions performance.These researchs have all promoted the performance of composite polymer electrolyte in some aspects, remain shortcoming but its combination property especially reaches the more support of the positive electrode of high working voltage for 4 volts (V) level than high working voltage.In 15 years, typical work is that Scrosai and its partner (B.Scrosati, F.Croce, S.Panero, Journal of Power Sources, 100 (2001) 93-100.) will consist of PEO in the past 20-LiSO 3CF 3-10wt%Al 2O 3Be applied to 3V rank positive electrode LiMn 3O 6And LiFePO 4In go.
People are still waiting further investigation to the electrochemical stability of polymer dielectric, are applicable to 4V and the above rank positive electrode such as the LiCoO of extensive use 2, LiMn 2O 4, LiNi 1/3Co 1/3Mn 1/3O 2Perhaps LiNi 0.5Mn 1.5O 2Composite polymer electrolyte still do not see open report.These positive electrodes are respectively 3.9V with respect to the operating voltage of lithium metal, 4.1V, and 3.75V, therefore 4.7V has proposed very high requirement for electrolyte electrochemical stability.
Summary of the invention
The objective of the invention is to develop a kind of polymer dielectric that has higher stability with respect to high voltage, can support the working voltage platform steady operation of anode material for lithium-ion batteries more than 3.75V.
We are based on the deep understanding for traditional polymeric matrix PEO chemical characteristic, have studied to have the more polymer matrices of superior function; Novel lithium salts biethyl diacid lithium borate (LiBOB) has been done on a large amount of numerical simulation work and the research basis for nano material and polymer phase capacitive, fully optimize it and form, finally obtain a kind of composite polymer electrolyte with excellent comprehensive performance.This novel composite polymer electrolyte has obtained for above positive electrode of 4V rank such as LiCoO on the basis that guarantees for lithium metal negative pole and other traditional negative pole material compatibilities 2, LiMn 2O 4, LiNi 1/3Co 1/3Mn 1/3O 2And LiNi 0.5Mn 1.5O 2Electrochemical stability, simultaneously material has good thermal stability and interface ion conductivity.
Concrete, technical scheme of the present invention is as follows:
A kind of composite polymer electrolyte comprises the polymeric matrix that contains the ether oxygen groups, and is dispersed in lithium salts and nano-metal-oxide in the polymeric matrix, and wherein, ether oxygen groups in the polymer and lithium salts mol ratio are 8 to 40; The quality of nano-metal-oxide is 1% to 15% with respect to the quality sum of polymer and lithium salts; Described polymer is selected from one or more in the following polymers: the polycondensation product of oxireme-vinylidene fluoride copolymers, oxireme-acrylonitrile copolymer, oxireme-methylmethacrylate copolymer and oxireme and boric acid; The main component of described lithium salts is a biethyl diacid lithium borate, and it accounts for 60%～100% of whole lithium salts moles.
The present invention adopts and contains the dispersion of the polymer of ether oxygen groups as lithium salts, oxireme-vinylidene fluoride copolymers (P (EO-VDF)), oxireme-acrylonitrile copolymer (P (EO-AN)), oxireme-methylmethacrylate copolymer (P (EO-MMA)), and the polycondensation product of oxireme and boric acid (molecular weight that preferred end has a hydroxyl is 400 polyvinyl alcohol (PEG) and the polycondensation product of boric acid, is designated as BO (PEG-400) 3) in one or more mixture of polymers all can use and adding and the polymer ergasia that has the nano-metal-oxide of excellent compatibility to constitute.Nano-metal-oxide refers to nano cupric oxide (CuO), magnesium oxide (MgO), zinc oxide (ZnO), aluminium oxide lithium (LiAlO 2) in waiting one or more, particle size range is 15nm～500nm.
Except biethyl diacid lithium borate (LiBOB), account for other lithium salts such as the trifluoromethyl sulfonic acid lithium (LiSO of described lithium salts mole 0～40% 3CF 3, LiTf), two (trifluoromethane sulfonic acid) imines lithium (LiN (CF 3SO 3) 2, LiTFSI), lithium perchlorate (LiClO 4), lithium hexafluoro phosphate (LiPF 6) and LiBF4 (LIBF 4) in one or more mixture.
The preparation method of composite polymer electrolyte of the present invention evenly spreads to three kinds of compositions (polymer, lithium salts and nano-metal-oxide) in single organic solvent or the mixed solvent, concentrates back solvent flashing film forming.Employed organic solvent comprises in oxolane, ether, acetone, acetonitrile, glycol dimethyl ether, dimethyl carbonate, diethyl carbonate, dimethyl sulfoxide (DMSO) and the ethylene carbonate any one or multiple mixture.
The composite polymer electrolyte of the present invention preparation has excellent comprehensive performances: can both steady operation for normally used 4 volts and above rank anode material for lithium-ion batteries, keep simultaneously and the compatibility of lithium metal negative material; Do not contain inflammable constituent, Heat stability is good; Realize that cost is lower, can be widely applied to the lithium secondary battery field that specific (special) requirements is arranged for battery security and thermal stability.
Description of drawings
Fig. 1 is the prepared composite polymer electrolyte P (EO-VDF) of embodiment 1 10The ionic conductivity temperature curve of-LiBOB-5wt%CuO.
Fig. 2 is the prepared composite polymer electrolyte P (EO-VDF) of embodiment 1 10The interface impedance of-LiBOB-5wt%CuO is change curve in time.
Fig. 3 has shown the compound polymer dielectric P (EO-MMA) that embodiment 2 is prepared 10-LiBOB-10wt%LiAlO 2The electrochemical window performance.
Fig. 4 is the prepared compound polymer dielectric P (EO-MMA) of embodiment 2 10-LiBOB-10wt%LiAlO 2Lithium symmetry battery overpotential curve.
Fig. 5 is the thermogravimetric curve of prepared composite polymer electrolyte P (the EO-AN)-LiBOB-LiTFSI-3wt%ZnO of embodiment 3.
Fig. 6 is that embodiment 3 prepared composite polymer electrolyte P (EO-AN)-LiBOB-LiTFSI-3wt%ZnO are applied to LiCoO 2The cycle performance of battery curve of material.
Fig. 7 is the prepared composite polymer electrolyte BO (PEG-400) of embodiment 4 3)-LiBOB-7%wt MgO-CuO uses LiNi 1/3Co 1/3Mn 1/3O 2The cycle performance of battery curve of material.
Fig. 8 is the prepared composite polymer electrolyte P (EO-PO) of Comparative Examples 2 20-LiBOB-5wt%ZrO 2Be applied to LiCoO 2The cycle performance of battery curve of material.
Embodiment
Further specify the present invention with example below, but protection scope of the present invention is not limited to embodiment.
Embodiment 1
Prepare composite polymer electrolyte P (EO-VDF) according to following method 10-LiBOB-5wt%CuO:
1) with 100 ℃ of dry 48h of LiBOB salt of 1.97g; 10.8g oxireme-vinylidene fluoride copolymers (weight average molecular weight 300,000) through 60 ℃ of vacuumize 48h; 0.638g 300 ℃ of dry 24h of nano cupric oxide (average grain diameter 20nm);
2) with dried above-mentioned three kinds of substance transfer in the 800ml acetonitrile, more than the strong agitation 8h, afterwards solvent evaporation is fallen 2/3, be transferred to natural casting film-forming on the polyfluortetraethylene plate, the translucent self-supported membrane P (EO-VDF) of the about 50 μ m of thickness 10-LiBOB-5wt%CuO (mol ratio of ether oxygen groups (EO) and Li in the subscript 10 expression polymer in the formula, down with),
Prepared composite polymer electrolyte P (EO-VDF) 10-LiBOB-5wt%CuO oxidation transformation current potential in the time of 100 ℃ is 4.9V; Ionic conductivity 1 * 10 in the time of 80 ℃ -3S/Cm, transference number of ions 0.33.
Composite polymer electrolyte P (EO-VDF) 10The ionic conductivity temperature curve of-LiBOB-5wt%CuO as shown in Figure 1.For the electrolyte of using in lithium ion battery, high ionic conductivity is beneficial to the fast transferring of lithium ion.The conductivity that promotes under the room temperature has positive effect for expanding the battery applications temperature range simultaneously.
Composite polymer electrolyte P (EO-VDF) 10The interface impedance of-LiBOB-5wt%CuO in time change curve as shown in Figure 2, lower and stable interface impedance helps guaranteeing the reversible of lithium ion battery.
Embodiment 2
Prepare compound polymer dielectric P (EO-MMA) according to following method 10-LiBOB-10wt%LiAlO 2:
1) with 100 ℃ of dry 48h of LiBOB salt of 2g; 14.4g poly-oxireme-methyl methacrylate (P (EO-MMA), weight average molecular weight 50,000) through 100 ℃ of vacuumize 48h; 1.64g 500 ℃ of dry 24h of nano aluminium oxide lithium (average grain diameter 25nm);
2) with dried above-mentioned three kinds of substance transfer in 1: 1 mixed solvent of 600ml acetonitrile-diethyl carbonate volume ratio, more than the strong agitation 10h, afterwards solvent evaporation is fallen 2/3, be transferred to natural casting film-forming on the polyfluortetraethylene plate, obtain the white self-supported membrane P (EO-MMA) of the about 80 μ m of thickness 10-LiBOB-10wt%LiAlO 2
Prepared composite polymer electrolyte P (EO-MMA) 10-LiBOB-10wt%LiAlO 2The oxidation transformation current potential is 5.0V in the time of 100 ℃, ionic conductivity 2 * 10 -3S/Cm, transference number of ions 0.45.
Prepared compound polymer dielectric P (EO-MMA) 10-LiBOB-10wt%LiAlO 2The electrochemical window performance as shown in Figure 3.The reflection of electrochemical window performance is the criterion of electrochemical stability from the size (for the electrode of appointment) of the electrolyte exchanging electric current that id reaction causes in the certain voltage interval.Because temperature is high more, electrolyte is unstable more.Be unified in 100 ℃ of test polymer electrolyte electrochemical stability among the present invention.Scanning of comprehensive negative electrode for the first time and the negative electrode scanning curve second time, this electrolyte just has violent oxidative decomposition to take place more than 5.0V.The decomposition that electrolyte begins at the low voltage place during negative electrode scanning first is owing to the effect of trace impurity.In addition, this electrolyte is tested the electrode exchanging electric current that obtains in 3.0 to 5.0V interval all very little, also confirmed the stability of this electrolyte height.
Prepared compound polymer dielectric P (EO-MMA) 10-LiBOB-10wt%LiAlO 2Lithium symmetry battery overpotential curve as shown in Figure 4.The overpotential curve has reflected the invertibity of the deposition of lithium ion in electrolyte/peel off, and has the electrolytical overpotential curve shape of excellent compatibility level and smooth with metal lithium electrode, and it is stable that the overpotential value also can keep.Test finds that this electrolyte still can keep good invertibity in 3500 circulations, confirms that this electrolyte and metal lithium electrode have good compatibility.
Embodiment 3
Prepare compound polymer dielectric P (EO-AN)-LiBOB-LiTFSI-3wt%ZnO according to following method:
1) LiBOB salt and the 1.276g LiTFSI salt with 1.18g places 100 ℃ of dry 48h together; 9.8g oxireme-acrylonitrile copolymer (weight average molecular weight 40,000) through 60 ℃ of vacuumize 48h; 0.368g 300 ℃ of dry 4h of nano zine oxide (average grain diameter 25nm);
2) above-mentioned substance of drying is transferred in the 800ml acetonitrile, more than the strong agitation 24h, afterwards solvent evaporation is fallen 2/3, be transferred to natural casting film-forming on the polyfluortetraethylene plate, get translucent self-supported membrane P (EO-AN)-LiBOB-LiTFSI-3wt%ZnO of the about 50 μ m of thickness.
Prepared composite polymer electrolyte P (EO-AN)-LiBOB-LiTFSI-3wt%ZnO oxidation transformation current potential in the time of 100 ℃ is 5.3V, ionic conductivity 2 * 10 -3S/Cm, transference number of ions 0.42.
The thermogravimetric curve of prepared composite polymer electrolyte P (EO-AN)-LiBOB-LiTFSI-3wt%ZnO as shown in Figure 5.Thermogravimetric curve reflection resulting polymers electrolyte just begins to take place tangible decomposition at certain more than the temperature.This electrolyte is keeping stable below 240 ℃.
Prepared composite polymer electrolyte P (EO-AN)-LiBOB-LiTFSI-3wt%ZnO uses LiCoO 2The cycle performance of battery curve of material as shown in Figure 6, this electrolyte meter reveals high efficiency for charge-discharge and capacity and keeps performance.
Embodiment 4
Prepare compound polymer dielectric BO (PEG-400) according to following method 3)-LiBOB-7%wt MgO-CuO:
1) with 100 ℃ of dry 48h of LiBOB salt of 1.97g; The oxireme of 5g-boric acid condensation polymer (weight average molecular weight 1,200) is through 80 ℃ of vacuumize 48h; 0.5g 200 ℃ of dry 5h of nano magnesia and nano oxidized copper mixture (mass ratio 1: 1, magnesium oxide average grain diameter 20nm, nano cupric oxide average grain diameter 50nm);
2) above-mentioned substance of drying is transferred in the 500ml glycol dinitrate ether solvents, more than the strong agitation 10h,, got the composite polymer electrolyte BO (PEG-400) of thick liquid nano afterwards with solvent evaporation 3)-LiBOB-7%wtMgO-CuO.
Prepared composite polymer electrolyte BO (PEG-400) 3)-LiBOB-7%wt MgO-CuO utilizes PP barrier film commonly used in the lithium secondary battery to soak into back assembling simulated battery and tests its chemical property, and the oxidation transformation current potential is 5.0V in the time of 40 ℃, ionic conductivity 1 * 10 -4S/Cm, transference number of ions 0.40.
Prepared composite polymer electrolyte BO (PEG-400) 3)-LiBOB-7%wt MgO-CuO uses LiNi 1/3Co 1/3Mn 1/3O 2The cycle performance of battery curve of material as shown in Figure 7.
Comparative Examples 1
Prepare composite polymer electrolyte PEO according to following method 10-LiClO 4-5wt%MgO:
1) with the LiClO of 1.06g 4100 ℃ of dry 48h of salt; 4.4g poly-oxireme (weight average molecular weight 600,000) through 60 ℃ of vacuumize 48h; 0.318g 200 ℃ of dry 4h of nano cupric oxide (average grain diameter 50nm);
2) with above-mentioned three kinds of substance transfer of drying in the 800ml acetonitrile, more than the strong agitation 8h, afterwards solvent evaporation is fallen 2/3, be transferred to natural casting film-forming on the polyfluortetraethylene plate, the translucent self-supported membrane PEO of the about 50 μ m of thickness 10-LiClO 4-5wt%MgO.
Prepared composite polymer electrolyte PEO 10-LiClO 4-5wt%MgO oxidation transformation voltage in the time of 100 ℃ only is 4.0V, ionic conductivity 2 * 10 -3S/Cm, transference number of ions 0.42.This composite polymer electrolyte is for common LiFePO 4 material (LiFePO 4) better support can be provided, but for LiNi 1/3Co 1/3Mn 1/3O 2The 4V positive electrode of beginning, promptly near the workbench of positive electrode, battery capacity decays the electrolyte oxidation voltage fast, cisco unity malfunction.
Comparative Examples 2
Prepare composite polymer electrolyte P (EO-PO) according to following method 20-LiBOB-5wt%ZrO 2:
1) with 100 ℃ of dry 48h of LiBOB salt of 1.93g; 10.2g oxireme-propylene oxide copolymer (weight average molecular weight 100,000) through 80 ℃ of vacuumize 48h; 0.318g 150 ℃ of dry 12h of nano zircite (average grain diameter 40nm);
2) with above-mentioned three kinds of substance transfer of drying in the 800ml oxolane, more than the strong agitation 8h, afterwards solvent evaporation is fallen 2/3, be transferred to natural casting film-forming on the polyfluortetraethylene plate, the translucent self-supported membrane P (EO-PO) of the about 60 μ m of thickness 20-LiBOB-5wt%ZrO 2
Prepared composite polymer electrolyte P (EO-PO) 20-LiBOB-5wt%ZrO 2Oxidation transformation voltage only is 3.9V in the time of 100 ℃, ionic conductivity 1.5 * 10 -3S/Cm, transference number of ions 0.30.This electrolyte is for common LiFePO 4 material (LiFePO 4) better support can be provided, simultaneously for LiNi 1/3Co 1/3Mn 1/3O 2Certain support can be provided.But for LiCoO 2And has a more LiMn of high working voltage platform 2O 4Deng, it is very unstable that electrolyte begins to become.Fig. 8 is that this electrolyte is applied to LiCoO 2The cycle performance of battery curve of material.Under same test condition, based on this electrolytical LiCoO 2Battery capacity decay is about every circulation 0.9mAh/g, the 0.1-0.2mAh/g that can reach much larger than the present invention.Show that this electrolytical performance will be inferior to the present invention.
This shows, for utilizing the polymeric matrix reported application, and other lithium salts and nano-oxide to be used as component be the polymer dielectric that can not obtain having high electrochemical stability.The present invention has remarkable improvement on technical merit.

Claims (7)

1. a composite polymer electrolyte comprises the polymeric matrix that contains the ether oxygen groups, and is dispersed in lithium salts and nano-metal-oxide in the polymeric matrix, and wherein, ether oxygen groups in the polymer and lithium salts mol ratio are 8～40; The quality of nano-metal-oxide is 1%～15% with respect to the quality sum of polymer and lithium salts; Described polymer is selected from one or more in the following polymers: the polycondensation product of oxireme-vinylidene fluoride copolymers, oxireme-acrylonitrile copolymer, oxireme-methylmethacrylate copolymer and oxireme and boric acid; The main component of described lithium salts is a biethyl diacid lithium borate, and it accounts for 60%～100% of whole lithium salts moles.
2. composite polymer electrolyte as claimed in claim 1 is characterized in that, the polycondensation product of described oxireme and boric acid is meant that molecular weight that end has a hydroxyl is 400 the polyvinyl alcohol and the polycondensation product of boric acid.
3. composite polymer electrolyte as claimed in claim 1 is characterized in that, described nano-metal-oxide is selected from one or more in nano cupric oxide, magnesium oxide, zinc oxide, the aluminium oxide lithium.
4. composite polymer electrolyte as claimed in claim 1 is characterized in that, the particle size range of described nano-metal-oxide is 15nm～500nm.
5. composite polymer electrolyte as claimed in claim 1, it is characterized in that, except that biethyl diacid lithium borate, described composite polymer electrolyte also contains one or more in the following lithium salts: trifluoromethyl sulfonic acid lithium, two (trifluoromethane sulfonic acid) imines lithium, lithium perchlorate, lithium hexafluoro phosphate and LiBF4.
6. the preparation method of the arbitrary described composite polymer electrolyte of claim 1～5 evenly spreads to described polymer, lithium salts and the nano-metal-oxide of drying in single organic solvent or the mixed solvent, concentrates back solvent flashing film forming.
7. preparation method as claimed in claim 6, it is characterized in that described solvent is selected from one or more the mixture in oxolane, ether, acetone, acetonitrile, glycol dimethyl ether, dimethyl carbonate, diethyl carbonate, dimethyl sulfoxide (DMSO) and the ethylene carbonate.
CN2011102059792A 2011-07-21 2011-07-21 Composite polymer electrolyte for lithium ion secondary battery and preparation method thereof Pending CN102299378A (en)

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Cited By (3)

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CN104937748A (en) * 2013-02-27 2015-09-23 大曹株式会社 Positive electrode and nonaqueous electrolyte secondary battery
CN113267803A (en) * 2021-06-19 2021-08-17 衡阳师范学院 Device and method for measuring ionization rate of water vapor molecules in air
CN113484897A (en) * 2021-07-27 2021-10-08 衡阳师范学院 Device and method for measuring Po-218 mobility and neutralization rate by electrostatic collection method

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CN104937748A (en) * 2013-02-27 2015-09-23 大曹株式会社 Positive electrode and nonaqueous electrolyte secondary battery
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CN113267803A (en) * 2021-06-19 2021-08-17 衡阳师范学院 Device and method for measuring ionization rate of water vapor molecules in air
CN113484897A (en) * 2021-07-27 2021-10-08 衡阳师范学院 Device and method for measuring Po-218 mobility and neutralization rate by electrostatic collection method

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Application publication date: 20111228