CN101826599B - Polymer solar battery with high open-circuit voltage - Google Patents
Polymer solar battery with high open-circuit voltage Download PDFInfo
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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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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Abstract
The invention discloses a polymer solar battery with a high open-circuit voltage, which comprises a substrate, an anode, an anode modifying layer, an active layer, a cathode modifying layer and a cathode, wherein the active layer is a composite membrane of a polymer P(BDT-PhI) and PCBM of benzo-bithiophene and imide. By using the characteristics of an ultra-low HOMO energy level, a wide absorption spectrum, high mobility and the like of the P(BDT-PhI), the polymer solar battery prepared by the invention has a very high open-circuit voltage (0.93V), a widened spectral response range and high energy conversion efficiency. Besides, the very low HOMO energy level of the P(BDT-PhI) is also helpful for prolonging the service life of the polymer solar battery.
Description
Technical field
The present invention relates to solar cell, relate in particular to a kind of polymer solar battery of high open circuit voltage.
Background technology
Solar energy is human inexhaustible, nexhaustible regenerative resource.Therefore, sharp rising in oil price, the mineral resources a large amount of dischargings of exhaustion and greenhouse gas today of causing the climate warming phenomenon to be on the rise day by day, is that the solar cell of electric energy receives increasing attention based on photovoltaic effect with solar energy converting.Yet present commercial solar cell all is that to adopt silicon or inorganic compound semiconductor be the inorganic solar cell of active layer material, and complicated process of preparation, cost is high, weight is big, frangible, has seriously restricted the large-scale promotion application of solar cell.In this respect, with conjugated polymer and fullerene derivate (like PCBM, C
71-PCBM etc.) laminated film is that the polymer solar battery of active layer has special advantages: its cost is low, can adopt methods processing such as easy solution spin coating, inkjet printing, obtain the large area flexible device easily; Cause the great interest of various countries scientist and each major company, formed research boom rapidly.
Yet at present the photovoltaic energy conversion efficient of polymer solar battery is also lower, as being active layer with the compound system of PCBM (P3HT) with the most frequently used gathering (3-hexyl thiophene); Efficient is no more than 5% (Nature Materials; 2005,4,864); Than low 1 one magnitude of inorganic solar cell, become one of main bottleneck that hinders its industrialization.For this reason; People design the conjugated polymer that has synthesized a series of narrow band gaps; The absorption spectrum of conjugated polymer is expanded to the near infrared region, strengthening, thereby effectively improved the energy conversion efficiency of polymer solar battery the absorbing of energy photons in the solar spectrum.For example; The people such as M ü hlbacher of U.S. Konarka company Austria branch company design and have synthesized a kind of Optical Properties of Novel Conjugated---the copolymer (PCPDTBT) of cyclopenta and two thiophene and diazosulfide; Its band gap is 1.40eV, and the energy of absorption edge red shift is to 890nm (Advanced Materials, 2006; 18,2884); The people such as Peet in California, USA university St Babara branch school are with PCPDTBT and C
71-PCBM is compound, and through adding thiol treatment, the efficient of battery is brought up to 5.5% (Nature Materials, 2007,6,497).The people such as Hou Jianhui of U.S. Solarmer company design the copolymer (PBDTTT-C) that has synthesized two thiophene of benzo and thienyl (3,4-also) thiophene, and its band gap is 1.61eV, and energy of absorption edge is 770nm, with PBDTTT-C and C
71-PCBM blend is as the active layer of polymer solar battery, and efficient is 6.58% (Journalof the American ChemicalSociety, 2009,131,15586) when best.Recently, they further carry out chemical modification to this polymer, obtain the substituted polymer P BDTTT-CF of fluorine atom; Thereby realized the photovoltaic energy conversion efficient that present polymer solar battery is the highest---7.73% (Nature Photonicss; 2009,3,649).
Polymer solar battery will be realized practicability, except will significantly improving its energy conversion efficiency high open circuit voltage (V
OC) also be the index of a key.At present, the V of most polymer solar batteries
OCAll between 0.6～0.7V, this just means that when practical application the intimate consistent element cell of electricity index that need a plurality of processes be carefully chosen, various (like efficient, internal resistance, life-span etc.) is together in series and is assembled into battery pack, the V of element cell
OCLow more, the battery number that needs is just many more, and packaging technology is more complicated, and cost is also just high more.Research shows, the V of polymer solar battery
OCBy the decision of the energy level difference between the lumo energy of the HOMO energy level of polymer donor material and acceptor material.In present stage, the best acceptor material of performance that can be applied to polymer solar battery all is the derivative of fullerene.When the lumo energy of acceptor material (4.3eV) confirm after, obtain high V
OC, have only the HOMO energy level (Advanced Materials, 2006,18,789) that reduces conjugated polymer as much as possible.But; Reduce the HOMO energy level of polymer through chemical modification after, make other photoelectric properties deteriorations of polymer probably, as band gap broaden, degradation under the mobility; Cause photon absorption efficiency and charge transfer efficiency variation, the integral energy conversion efficiency of polymer solar battery descends very lowly.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, providing a kind of can keep and even optimize under the situation of spectral absorption scope and mobility the polymer solar battery with high open circuit voltage.
The polymer solar battery of high open circuit voltage comprises substrate, anode, anode modification layer, active layer, cathodic modification layer and negative electrode, and said active layer is the two thiophene of benzo and the copolymer of benzoylimino and the composite membrane of PCBM.
The copolymer of two thiophene of described benzo and benzoylimino is P (BDT-PhI), and chemical structural formula is:
Wherein R is the 2-ethylhexyl.
P in the described active layer (BDT-PhI) is 1: 4～4: 1 with the weight ratio of PCBM, and the thickness of active layer is 50～150nm.
Described substrate is glass or polyester film; Described anode is ITO; Described anode modification layer is the composite membrane of PEDOT and PSS; Described cathodic modification layer is LiF; Described negative electrode is an aluminium.
The invention has the advantages that and adopt the donor material of P (BDT-PhI) as polymer solar battery.In the molecular structure of P (BDT-PhI), the two thiophene units of benzo have the rigid planar structure of height conjugation, help the orderly accumulation of polymer molecule in film, make active layer have high mobility.In addition, the benzoylimino unit of electrophilic property replace keyed jointing with the two thiophene units of the benzo of giving electronics property and forms main polymer chain, makes electron cloud that track generation coupling between skew and unit take place; Improved the delocalization property of pi-electron, reduced the band gap of polymer, (band gap of P (BDT-PhI) is 2.15eV; And the band gap of the homopolymers PBDT of the two thiophene of benzo is 2.20eV, sees document Chemistry of Materials, 2006; 18,3237).The more important thing is; The introducing of electrophilic property benzoylimino unit, the HOMO energy level that has reduced polymer significantly is (5.51eV), far below the HOMO energy level of P3HT (5.0eV); Is the polymer solar battery of active layer with P (BDT-PhI) with the PCBM composite membrane, and open circuit voltage is up to 0.93V.Simultaneously, low HOMO energy level also can effectively delay the oxidizing process of polymer, thereby improves the life-span of polymer solar battery.
Description of drawings
The weight ratio of P in Fig. 1 active layer (BDT-PhI) and PCBM be 1: 1, active layer thickness be 87nm polymer solar battery in the dark with illumination under electric current-voltage curve;
The weight ratio of P in Fig. 2 active layer (BDT-PhI) and PCBM is that 1: 1, active layer thickness are the external quantum efficiency-wavelength curve of the polymer solar battery of 87nm.
Embodiment
Utilize 2, two (tin trimethyl)-4 of 6-, two (the 2-ethylhexyl oxygen) benzos [1 of 8-; 2-b:4; 5-b '] two thiophene (be called for short: BDT) with N-(2-ethylhexyl)-3,6-dibromobenzene acid imide (be called for short: Stille coupling reaction PhI) is synthesized P (BDT-PhI), and reaction equation is:
R represents the 2-ethylhexyl in the formula.Wherein BDT is with document Journal of the American ChemicalSociety, 2009,131; 15586 reported method are synthetic, and PhI is with document Journal of the AmericanChemical Society, 2009; 131,7206 reported method are synthetic.The synthesis step of P (BDT-PhI) is:
20ml toluene, 0.772g BDT (1.0mmol) and 0.417g PhI (1.0mmol) join in the 50ml round bottom three-necked bottle, stir BDT and PhI are dissolved in the toluene, and solution after 10 minutes, adds 30mg Pd (PPh with nitrogen bubble
3)
4As catalyst, used nitrogen bubble again 20 minutes.Reaction system is warming up to 110 ℃, and reaction is 48 hours under nitrogen.After reaction system reduces to room temperature, solution is precipitated collecting precipitation thing, oven dry to 100ml methyl alcohol.Sediment is put into cable-styled extractor, use methyl alcohol, acetone and n-hexane extracting (3 * 24 hours) successively, to remove unreacted raw material and oligomer; Use the chloroform extracting again, the polymer that reaction is obtained all is dissolved in the chloroform, and chloroformic solution is revolved steaming; Remove solvent; In 80 ℃ of vacuum drying ovens dry 24 hours at last, obtain the polymer P (BDT-PhI) (orange powder, productive rate 41.5%) behind the 0.291g purifying.
Record the number-average molecular weight (M of P (BDT-PhI) with gel permeation chromatography (GPC)
n) be 20.7K, weight average molecular weight (M
w) be 40.2K; The HOMO energy level that records P (BDT-PhI) with cyclic voltammetric (CV) method is-5.51eV; The optical band gap that records P under the filminess (BDT-PhI) with absorption spectrum is 2.15eV; The hole mobility that use efficient transistor (FET) method records P (BDT-PhI) is 0.012cm
2/ (Vs).
After the transparent conducting glass that surface etch is had a strip ITO (anode) cleaned with the liquid detergent aqueous solution, deionized water, acetone and isopropyl alcohol sonic oscillation successively, oven dry was used oxygen plasma treatment 10 minutes again; The aqueous solution of spin coating PEDOT and PSS mixture on conductive glass surface then, rotating speed is 2000r/min, 150 ℃ of dryings 15 minutes obtain the composite membrane (anode modification layer) of thick PEDOT of one deck 30nm and PSS; Then, the mixed solution of spin coating P (BDT-PhI) and PCBM above that, rotating speed is 1500r/min; The total concentration of solution is 20mg/ml, and solvent is a chlorobenzene, and P (BDT-PhI) is 1: 1 with the weight ratio of PCBM; The spin coating time is 60 seconds, and spin coating is lower than 1 * 10 at pressure after finishing
-4Drying at room temperature is 2 hours under the vacuum of Pa, obtains the composite membrane (active layer) of P that a layer thickness is 87nm (BDT-PhI) and PCBM; The LiF (cathodic modification layer) that vacuum evaporation last layer 0.5nm is thick on active layer then; At last, the aluminium that vacuum evaporation last layer 40nm is thick on the cathodic modification layer is as negative electrode, thereby obtained a complete polymer solar battery antetype device.
In intensity of illumination is 100mW/cm
2AM1.5 simulated solar rayed under, test the electric current-voltage curve of this device, therefrom obtaining open circuit voltage is 0.93V, short-circuit current density is 1.35mA/cm
2, fill factor, curve factor is 0.42, photovoltaic energy conversion efficient is 0.53%.
It is 100mW/cm with intensity of illumination in the dark that Fig. 1 has provided this device
2AM1.5 simulated solar rayed under electric current-voltage curve; Fig. 2 provides the external quantum efficiency-wavelength curve of this device of son, explains that the spectral response range of this device has been expanded to more than the 600nm.
After the transparent conducting glass that surface etch is had a strip ITO (anode) cleaned with the liquid detergent aqueous solution, deionized water, acetone and isopropyl alcohol sonic oscillation successively, oven dry was used oxygen plasma treatment 10 minutes again; The aqueous solution of spin coating PEDOT and PSS mixture on conductive glass surface then, rotating speed is 2000r/min, 150 ℃ of dryings 15 minutes obtain the composite membrane (anode modification layer) of thick PEDOT of one deck 30nm and PSS; Then, the mixed solution of spin coating P (BDT-PhI) and PCBM above that, rotating speed is 1000r/min; The total concentration of solution is 20mg/ml, and solvent is a chlorobenzene, and P (BDT-PhI) is 1: 1 with the weight ratio of PCBM; The spin coating time is 60 seconds, and spin coating is lower than 1 * 10 at pressure after finishing
-4Drying at room temperature is 2 hours under the vacuum of Pa, obtains the composite membrane (active layer) of P that a layer thickness is 100nm (BDT-PhI) and PCBM; The LiF (cathodic modification layer) that vacuum evaporation last layer 0.5nm is thick on active layer then; At last, the aluminium that vacuum evaporation last layer 40nm is thick on the cathodic modification layer is as negative electrode, thereby obtained a complete polymer solar battery antetype device.
In intensity of illumination is 100mW/cm
2AM1.5 simulated solar rayed under, test the electric current-voltage curve of this device, therefrom obtaining open circuit voltage is 0.87V, short-circuit current density is 0.76mA/cm
2, fill factor, curve factor is 0.36, photovoltaic energy conversion efficient is 0.24%.
After the transparent conducting glass that surface etch is had a strip ITO (anode) cleaned with the liquid detergent aqueous solution, deionized water, acetone and isopropyl alcohol sonic oscillation successively, oven dry was used oxygen plasma treatment 10 minutes again; The aqueous solution of spin coating PEDOT and PSS mixture on conductive glass surface then, rotating speed is 2000r/min, 150 ℃ of dryings 15 minutes obtain the composite membrane (anode modification layer) of thick PEDOT of one deck 30nm and PSS; Then, the mixed solution of spin coating P (BDT-PhI) and PCBM above that, rotating speed is 600r/min; The total concentration of solution is 20mg/ml, and solvent is a chlorobenzene, and P (BDT-PhI) is 1: 1 with the weight ratio of PCBM; The spin coating time is 60 seconds, and spin coating is lower than 1 * 10 at pressure after finishing
-4Drying at room temperature is 2 hours under the vacuum of Pa, obtains the composite membrane (active layer) of P that a layer thickness is 130nm (BDT-PhI) and PCBM; The LiF (cathodic modification layer) that vacuum evaporation last layer 0.5nm is thick on active layer then; At last, the aluminium that vacuum evaporation last layer 40nm is thick on the cathodic modification layer is as negative electrode, thereby obtained a complete polymer solar battery antetype device.
In intensity of illumination is 100mW/cm
2AM1.5 simulated solar rayed under, test the electric current-voltage curve of this device, therefrom obtaining open circuit voltage is 0.93V, short-circuit current density is 0.67mA/cm
2, fill factor, curve factor is 0.37, photovoltaic energy conversion efficient is 0.23%.
After the transparent conducting glass that surface etch is had a strip ITO (anode) cleaned with the liquid detergent aqueous solution, deionized water, acetone and isopropyl alcohol sonic oscillation successively, oven dry was used oxygen plasma treatment 10 minutes again; The aqueous solution of spin coating PEDOT and PSS mixture on conductive glass surface then, rotating speed is 2000r/min, 150 ℃ of dryings 15 minutes obtain the composite membrane (anode modification layer) of thick PEDOT of one deck 30nm and PSS; Then, the mixed solution of spin coating P (BDT-PhI) and PCBM above that, rotating speed is 2000r/min; The total concentration of solution is 20mg/ml, and solvent is a chlorobenzene, and P (BDT-PhI) is 1: 1 with the weight ratio of PCBM; The spin coating time is 60 seconds, and spin coating is lower than 1 * 10 at pressure after finishing
-4Drying at room temperature is 2 hours under the vacuum of Pa, obtains the composite membrane (active layer) of P that a layer thickness is 65nm (BDT-PhI) and PCBM; The LiF (cathodic modification layer) that vacuum evaporation last layer 0.5nm is thick on active layer then; At last, the aluminium that vacuum evaporation last layer 40nm is thick on the cathodic modification layer is as negative electrode, thereby obtained a complete polymer solar battery antetype device.
In intensity of illumination is 100mW/cm
2AM1.5 simulated solar rayed under, test the electric current-voltage curve of this device, therefrom obtaining open circuit voltage is 0.85V, short-circuit current density is 1.10mA/cm
2, fill factor, curve factor is 0.40, photovoltaic energy conversion efficient is 0.37%.
Embodiment 6
After the transparent conducting glass that surface etch is had a strip ITO (anode) cleaned with the liquid detergent aqueous solution, deionized water, acetone and isopropyl alcohol sonic oscillation successively, oven dry was used oxygen plasma treatment 10 minutes again; The aqueous solution of spin coating PEDOT and PSS mixture on conductive glass surface then, rotating speed is 2000r/min, 150 ℃ of dryings 15 minutes obtain the composite membrane (anode modification layer) of thick PEDOT of one deck 30nm and PSS; Then, the mixed solution of spin coating P (BDT-PhI) and PCBM above that, rotating speed is 1000r/min; The total concentration of solution is 20mg/ml, and solvent is a chlorobenzene, and P (BDT-PhI) is 2: 1 with the weight ratio of PCBM; The spin coating time is 60 seconds, and spin coating is lower than 1 * 10 at pressure after finishing
-4Drying at room temperature is 2 hours under the vacuum of Pa, obtains the composite membrane (active layer) of P that a layer thickness is 143nm (BDT-PhI) and PCBM; The LiF (cathodic modification layer) that vacuum evaporation last layer 0.5nm is thick on active layer then; At last, the aluminium that vacuum evaporation last layer 40nm is thick on the cathodic modification layer is as negative electrode, thereby obtained a complete polymer solar battery antetype device.
In intensity of illumination is 100mW/cm
2AM1.5 simulated solar rayed under, test the electric current-voltage curve of this device, therefrom obtaining open circuit voltage is 0.91V, short-circuit current density is 0.65mA/cm
2, fill factor, curve factor is 0.35, photovoltaic energy conversion efficient is 0.21%.
Embodiment 7
After the transparent conducting glass that surface etch is had a strip ITO (anode) cleaned with the liquid detergent aqueous solution, deionized water, acetone and isopropyl alcohol sonic oscillation successively, oven dry was used oxygen plasma treatment 10 minutes again; The aqueous solution of spin coating PEDOT and PSS mixture on conductive glass surface then, rotating speed is 2000r/min, 150 ℃ of dryings 15 minutes obtain the composite membrane (anode modification layer) of thick PEDOT of one deck 30nm and PSS; Then, the mixed solution of spin coating P (BDT-PhI) and PCBM above that, rotating speed is 1000r/min; The total concentration of solution is 20mg/ml, and solvent is a chlorobenzene, and P (BDT-PhI) is 1: 2 with the weight ratio of PCBM; The spin coating time is 60 seconds, and spin coating is lower than 1 * 10 at pressure after finishing
-4Drying at room temperature is 2 hours under the vacuum of Pa, obtains the composite membrane (active layer) of P that a layer thickness is 81nm (BDT-PhI) and PCBM; The LiF (cathodic modification layer) that vacuum evaporation last layer 0.5nm is thick on active layer then; At last, the aluminium that vacuum evaporation last layer 40nm is thick on the cathodic modification layer is as negative electrode, thereby obtained a complete polymer solar battery antetype device.
In intensity of illumination is 100mW/cm
2AM1.5 simulated solar rayed under, test the electric current-voltage curve of this device, therefrom obtaining open circuit voltage is 0.89V, short-circuit current density is 0.92mA/cm
2, fill factor, curve factor is 0.40, photovoltaic energy conversion efficient is 0.33%.
Embodiment 8
After the transparent conducting glass that surface etch is had a strip ITO (anode) cleaned with the liquid detergent aqueous solution, deionized water, acetone and isopropyl alcohol sonic oscillation successively, oven dry was used oxygen plasma treatment 10 minutes again; The aqueous solution of spin coating PEDOT and PSS mixture on conductive glass surface then, rotating speed is 2000r/min, 150 ℃ of dryings 15 minutes obtain the composite membrane (anode modification layer) of thick PEDOT of one deck 30nm and PSS; Then, the mixed solution of spin coating P (BDT-PhI) and PCBM above that, rotating speed is 1000r/min; The total concentration of solution is 20mg/ml, and solvent is a chlorobenzene, and P (BDT-PhI) is 1: 3 with the weight ratio of PCBM; The spin coating time is 60 seconds, and spin coating is lower than 1 * 10 at pressure after finishing
-4Drying at room temperature is 2 hours under the vacuum of Pa, obtains the composite membrane (active layer) of P that a layer thickness is 74nm (BDT-PhI) and PCBM; The LiF (cathodic modification layer) that vacuum evaporation last layer 0.5nm is thick on active layer then; At last, the aluminium that vacuum evaporation last layer 40nm is thick on the cathodic modification layer is as negative electrode, thereby obtained a complete polymer solar battery antetype device.
In intensity of illumination is 100mW/cm
2AM1.5 simulated solar rayed under, test the electric current-voltage curve of this device, therefrom obtaining open circuit voltage is 0.89V, short-circuit current density is 0.87mA/cm
2, fill factor, curve factor is 0.42, photovoltaic energy conversion efficient is 0.32%.
Embodiment 9
After the transparent conducting glass that surface etch is had a strip ITO (anode) cleaned with the liquid detergent aqueous solution, deionized water, acetone and isopropyl alcohol sonic oscillation successively, oven dry was used oxygen plasma treatment 10 minutes again; The aqueous solution of spin coating PEDOT and PSS mixture on conductive glass surface then, rotating speed is 2000r/min, 150 ℃ of dryings 15 minutes obtain the composite membrane (anode modification layer) of thick PEDOT of one deck 30nm and PSS; Then, the mixed solution of spin coating P (BDT-PhI) and PCBM above that, rotating speed is 1000r/min; The total concentration of solution is 20mg/ml, and solvent is a chlorobenzene, and P (BDT-PhI) is 1: 4 with the weight ratio of PCBM; The spin coating time is 60 seconds, and spin coating is lower than 1 * 10 at pressure after finishing
-4Drying at room temperature is 2 hours under the vacuum of Pa, obtains the composite membrane (active layer) of P that a layer thickness is 58nm (BDT-PhI) and PCBM; The LiF (cathodic modification layer) that vacuum evaporation last layer 0.5nm is thick on active layer then; At last, the aluminium that vacuum evaporation last layer 40nm is thick on the cathodic modification layer is as negative electrode, thereby obtained a complete polymer solar battery antetype device.
In intensity of illumination is 100mW/cm
2AM1.5 simulated solar rayed under, test the electric current-voltage curve of this device, therefrom obtaining open circuit voltage is 0.85V, short-circuit current density is 0.67mA/cm
2, fill factor, curve factor is 0.38, photovoltaic energy conversion efficient is 0.22%.
Claims (3)
1. the polymer solar battery of a high open circuit voltage comprises substrate, anode, anode modification layer, active layer, cathodic modification layer and negative electrode, it is characterized in that active layer is the two thiophene of benzo and the copolymer of benzoylimino and the composite membrane of PCBM; The copolymer of two thiophene of described benzo and benzoylimino is P (BDT-PhI), and chemical structural formula is:
Wherein R is the 2-ethylhexyl.
2. the polymer solar battery of a kind of high open circuit voltage according to claim 1 is characterized in that P in the described active layer (BDT-PhI) and the weight ratio of PCBM are 1: 4～4: 1, and the thickness of active layer is 50～150nm.
3. the polymer solar battery of a kind of high open circuit voltage according to claim 1, it is characterized in that: described substrate is glass or polyester film; Described anode is ITO; Described anode modification layer is the composite membrane of PEDOT and PSS; Described cathodic modification layer is LiF; Described negative electrode is an aluminium.
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| CN101355139A (en) * | 2008-09-09 | 2009-01-28 | 吉林大学 | Novel method for preparing mutual-leakage type polymer solar battery |
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| CN101355139A (en) * | 2008-09-09 | 2009-01-28 | 吉林大学 | Novel method for preparing mutual-leakage type polymer solar battery |
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| 姜鸿基等.基于富勒烯和噻吩聚合物的本体异质结太阳电池.<<化学进展>>.2008,第20卷(第9期),1361-1373. * |
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