CN102126708B - Preparation method of Cu-In-Ga-Se-S nano powder material - Google Patents

Preparation method of Cu-In-Ga-Se-S nano powder material Download PDF

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CN102126708B
CN102126708B CN 201010028148 CN201010028148A CN102126708B CN 102126708 B CN102126708 B CN 102126708B CN 201010028148 CN201010028148 CN 201010028148 CN 201010028148 A CN201010028148 A CN 201010028148A CN 102126708 B CN102126708 B CN 102126708B
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powder material
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CN102126708A (en
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吴孟强
张树人
张其翼
刘文龙
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Sichuan University
University of Electronic Science and Technology of China
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Abstract

The invention provides a preparation method of a Cu-In-Ga-Se-S nano powder material, belonging to the technical field of inorganic chemical materials. The preparation method comprises the following steps: based on alkanolamine with a boiling point large than or equal to 180 DEG C as a solvent, dissolving Cu, In and Ga compounds into the alkanolamine in a mole ratio of Cu: (In+Ga) of 1: (1-1.5); then dissolving Se and S in the alkanolamine, wherein the sum of molar weights of Se and S is twice as heavy as molar weight of Cu; and subsequently, mixing two solutions, stirring under the protective condition of inert gas, heating to 200-280 DEG C for refluxing, maintaining the reaction for 4-10 hours and then stopping heating and stirring, cooling to room temperature, centrifuging, washing and drying the black powder on the lower layer, so as to obtain the Cu-In-Ga-Se-S nano powder material. By using the preparation method in the invention, the Cu-In-Ga-Se-S nano powder material which is in a nano grade and has uniform scale, good dispersibility and high phase purity can be prepared, the whole preparation process is high in efficiency and low in cost, and operation is simple and is easy to control. The Cu-In-Ga-Se-S nano powder material prepared by the method in the invention can be used in a solar battery as an absorption layer material.

Description

A kind of preparation method of Cu-In-Ga-Se-S nano-powder material
Technical field
The invention belongs to the inolrganic chemicals technical field, relate to the preparation method of Cu-In-Ga-Se-S compound nano powdered material.
Background technology
CuInSe 2, CuInS 2, CuGaSe 2, CuGaS 2, Cu (In xGa 1-x) Se 2(CIGS), Cu (In xGa 1-x) S 2And Cu (In xGa 1-x) (Se yS 2-y) etc. be referred to as the compound of Cu-In-Ga-Se-S.Because having good absorbing properties, high stability and unique structure and electric property, it becomes very promising photovoltaic material.Particularly, the solar cell transformation efficiency take copper-indium-galliun-selenium as absorption layer surpasses 20%, has already become this area research focus, is subject to the extensive concern of scientific research, exploitation and industrial community.
Existing preparation method about the Cu-In-Ga-Se-S powdered material mainly concentrates on liquid phase thermal synthesis aspect.Such as: (the Grisaru H such as Grisaru, Palchik O, Gedanken A, Palchik V, Slifkin MA, Weiss AM.2003.Inorganic Chemistry42:7148-55) reported a kind of with CuCl, simple substance In, Se as precursor, adopt microwave-assisted to process to produce CuInSe 2The method of nanometer powder.Although the method for microwave-assisted has advantages of that the reaction times is short, the powder shape that obtains and big or small lack of homogeneity, particle is easily reunited, and has a small amount of Cu 2The Se by product.Li etc. (Li B, Xie Y, Huang JX, Qian YT.1999.Advanced Materials 11:1456-9) have reported employing CuCl 2, InCl 3With simple substance Se as reactant, the synthetic CuInSe take quadrol or diethylamine as solvent 2Solvent thermal process, can obtain the chalcopyrite CuInSe of single-phase 2, particle dispersion is better, however above-mentioned solvent thermal building-up reactions must in an airtight high temperature and high pressure kettle, carry out, and the reaction needed at least just can finish in 15 hours even several days.This is owing to solvent for use, as: quadrol or diethylamine, the boiling point under normal pressure are respectively 118 ℃ and 55 ℃, all have very high vapour pressure under the synthesis temperature of solvent thermal, therefore need high-tension unit, thereby are unfavorable for business-like scale production.(the Malik MA such as Malik, O ' Brien P, Revaprasadu is Materials11:1441-4 N.1999.Advanced) proposed in tri-n-octyl phosphine (TOP) and trioctyl-phosphine oxide (TOPO) solution, to adopt " hot notes method " to synthesize CuInSe 2Method.The synthesis step of this method is: first with CuCl and InCl 3TOP solution under 100 ℃, be injected among the TOPO, then be heated to 330 ℃, again Se-TOP solution is injected hybrid reaction.Can synthesize the CuInSe that granular size is 4.5nm by this method 2Powder, but regrettably, by product Cu is arranged in the product 2Se and In 2O 3Generate.Castro etc. (Castro SL, Bailey SG, Raffaelle RP, Banger KK, Hepp AF.2003.Chemistry of Materials 15:3142-7) have reported employing (PPh 3) 2CuIn (SePh) 4As precursor, having synthesized the high mean particle size of purity with spray pyrolysis method is the CuInSe of 3-30nm 2Powder, but its precursor is difficult to preparation and cost is high.(the Qijie Guo such as Guo, Suk Jun Kim, Mahaprasad Kar, WilliamN.Shafarman, Robert W.Birkmire, Eric A.Stach, Rakesh Agrawal, and Hugh W.Hillhouse.2008.Nano Letters 8 (9): 2982-7) reported, adopt simple substance Cu, In, Ga, Se, S as reactant, alkylamine adopts " hot notes method " to synthesize fast metallic selenium sulfide nanometer powders two-dimentional, three peacekeeping multidimensional under not too high temperature and normal pressure as solvent.In addition, in recent years, the Cu-In-Ga-Se-S compound nano powder has been synthesized in people's active adoption similarly " hot notes method ".For example, (Jiang Tang, Sean Hinds, Shana O.Kelley, the and Edward H.Sargent.2008.Chemistry ofMaterials 20 (22): 6907-12) synthesized CuGaSe such as Tang 2And Cu (InGa) Se 2Nanometer powder, (the Matthew G.Panthani such as Panthani, Vahid Akhavan, Brian Goodfellow, Johanna P.Schmidtke, Lawrence Dunn, AnanthDodabalapur, Paul F.Barbara, and Brian A.Korgel.2008.Journal of the American ChemicalSociety 130:16770-7) synthesized CuInS 2And Cu (In xGa 1-x) Se 2Nanometer powder, (the Chet Steinhagen such as Steinhagen, Matthew G.Panthani, Vahid Akhavan, Brian Goodfellow, Bonil Koo, and Brian A.Korgel.2009.Journal of the American Chemical Society 131:12554-5) synthesized Cu 2ZnSnS 4Nanometer powder.Yet the solvent that adopts in above-mentioned " hot notes method " is all expensive oleyl amine, and need to add CHCl at last stage reaction 3Come termination reaction, in order to stop the generation of by product, also need add simultaneously the CuInSe that dispersion agent and flocculation agent make black in addition 2Powder is constantly separated out, and has increased complicacy and the cost of technological operation.
Summary of the invention
The invention provides a kind of fast preparation method of synthetic Cu-In-Ga-Se-S nano-powder material effective and with low cost, prepared Cu-In-Ga-Se-S nano-powder material have yardstick evenly, good dispersity and high characteristics of purity mutually.Whole preparation technology's efficient is high, cost is low, and simple to operate, be easy to control.
Technical solution of the present invention is as follows:
A kind of preparation method of Cu-In-Ga-Se-S nano-powder material as shown in Figure 1, may further comprise the steps:
Step 1: selecting Cu, the In of the alkyl alcoholamine that can be dissolved in boiling point 〉=180 ℃ and the compound of Ga is raw material; according to Cu: (In+Ga)=1: the mol ratio of (1～1.5) joins in the alkyl alcoholamine; under the protection of inert gas condition, stir, be heated to 110～180 ℃; so that the compound of Cu, In and Ga dissolves fully, obtain reaction system A.
Step 2: simple substance Se and simple substance S are joined in the alkyl alcoholamine, under constantly stirring, be heated to 200～280 ℃ of backflows, so that Se and S dissolve fully, obtain reaction system B.The molar weight sum of the Se that adds and S is the twice of the molar weight of Cu in the step 1.
Step 3: reaction system A and reaction system B are mixed, obtain reaction system C.
Step 4: reaction system C is heated to 200～280 ℃ of backflows under constantly stirring, keep reaction stopped heating stirring after 4～10 hours, be cooled to room temperature, carry out centrifugation, washing and drying treatment, obtain Cu-In-Ga-Se-S black nano powdered material, i.e. Cu (In xGa 1-x) (Se yS 2-y) nanometer powder, wherein 0≤x≤1,0≤y≤2.
Need to prove:
1, the compound of the Cu that selects in the step 1, In and Ga can be hydrochloride, vitriol, nitrate, acetate or acetylacetonate.
2, the alkyl alcoholamine of boiling point described in the step 1 〉=180 ℃ can be trolamine, diethanolamine, diglycolamine, dimethylethanolamine, N, N-dimethylethanolamine or dimethyl hydramine.
3, the centrifugation rate that adopts during centrifugal treating in the step 4 〉=8000～10000 rev/mins; The washing composition that adopts during carrying out washing treatment can be the organic solvents such as water, ethanol, acetone, chloroform or normal hexane; The drying temperature that adopts during drying treatment is 20～60 ℃.
4, adopting the purpose of protection of inert gas in the step 1 is to prevent Cu +Be oxidized to Cu 2+
Reaction mechanism of the present invention can be described as: after the compound of Cu, In and Ga joins alkyl alcoholamine, and Cu +, In 3+, Ga 3+Respectively with alkyl alcoholamine in hydroxyl and amido produce complex reaction, generate metal-alkyl alcoholamine complexing ion; And simple substance Se and S at first are reduced into respectively Se in alkyl alcoholamine 2-And S 2-, then generate Cu with metal-alkyl alcoholamine complexing ion reaction 2Se, Cu 2S, Ga 2Se 3, Ga 2S 3, In 2Se 3And In 2S 3Last Cu 2Se, Cu 2S, Ga 2Se 3, Ga 2S 3, In 2Se 3And In 2S 3These six kinds of materials react in the alkyl alcoholamine solvent and generate Cu (In xGa 1-x) (Se yS 2-y), i.e. Cu-In-Ga-Se-S nano-powder material.In the whole reaction process, theoretic reaction mol ratio Cu: (In+Ga): (Se+S)=1: 1: 2, but because the stability constant of the alkyl alcoholamine complexing ion of In or Ga is higher than the stability constant of the alkyl alcoholamine complexing ion of Cu, at metal-alkyl alcoholamine complexing ion and Se 2-And S 2-Reaction process in, Cu 2Se and Cu 2S can generate fast, and Ga 2Se 3, Ga 2S 3, In 2Se 3And In 2S 3Then generation is slower, so, in the real reaction process, can adopt the suitable excessive mode of molar weight of In or Ga, to reduce the whole reaction times.But, too many if the molar weight of In or Ga surpasses the molar weight of Cu, then may cause the loss of In or Ga and make whole preparation method lose cost advantage.Experiment showed, mol ratio Cu: (In+Ga)=1: (1～1.5) is suitable.
Advantage of the present invention and high-lighting effect are:
(1) solvent for use is alkyl alcoholamine, nontoxic, non-volatility and low cost;
(2) whole reaction was finished in several hours, and required time is short, fast, effectively;
(3) will directly join the alkyl alcoholamine solvent according to certain mol ratio for the raw material of reaction, and can accurately control the chemical composition of final compound, and guarantee to obtain highly purified copper-indium-galliun-selenium sulphur compound, productive rate is more than 95%;
(4) the copper-indium-galliun-selenium sulphur compound of preparation is that yardstick is even, the ball shaped nano powder of good dispersity;
(5) adopt common reflux, simple to operate, naturally cool to room temperature, no coupling product generates;
(6) powder of black sinks to rapidly the bottom, filters the supernatant liquid energy recycle of collecting, and is conducive to reduce cost;
(7) whole reaction is carried out under normal pressure, safety, environmental protection.
Description of drawings
Fig. 1 is schematic flow sheet of the present invention.
Fig. 2 is the XRD figure of the Cu-In-Ga-Se-S nanometer powder that adopts the method for the invention and make, and wherein, ordinate zou is absorption intensity (Intensity), and X-coordinate is diffraction angle (2 θ), is CuInSe (a) and (b) 2XRD figure, be respectively Cu (InGa) Se (c) and (d) 2And CuGaSe 2XRD figure.
Cu (InGa) Se of Fig. 3 for adopting the method for the invention to make 2SEM figure.
The CuGaSe of Fig. 4 for adopting the method for the invention to make 2SEM figure.
The CuInSe of Fig. 5 for adopting the method for the invention to make 2The TEM figure of nanometer powder.
The CuInSe of Fig. 6 for adopting the method for the invention to make 2The HR-TEM figure of nanometer powder.
Fig. 7 is the ultraviolet of the Cu-In-Ga-Se-S nanometer powder that adopts the method for the invention and make-near-infrared absorption spectrum figure.Wherein, curve 1 is the CuInSe that the present invention prepares 2Ultraviolet-the near-infrared absorption spectrum of nanometer powder; Curve 2 is Cu (InGa) Se that the present invention prepares 2Ultraviolet-near-infrared absorption spectrum; Curve 3 is CuGaSe that the present invention prepares 2Ultraviolet-the near-infrared absorption spectrum of nanometer powder.
Fig. 8 is the absorbancy of the Cu-In-Ga-Se-S nanometer powder that adopts the method for the invention and make-bandwidth figure.Wherein, curve 1 is the CuInSe that the present invention prepares 2The absorbancy of nanometer powder-energy bandwidth relationship curve; Curve 2 is Cu (InGa) Se that the present invention prepares 2The absorbancy of nanometer powder-energy bandwidth relationship curve; Curve 3 is CuGaSe that the present invention prepares 2The absorbancy of nanometer powder-energy bandwidth relationship curve.
Embodiment
Embodiment 1:
At synthetic CuInSe 2In the process of nanometer powder, adopt trolamine to make solvent.In reaction process, trolamine participates in reaction as complexing agent, is reduced to again at last trolamine.CuCl, InCl 34H 2O and Se have generated CuInSe 220 ℃ of lower atmospheric pressure reflux in triethanolamine solution 2Nanometer powder.
Take by weighing 2.5mmolCuCl and 2.5mmolInCl 34H 2O stirs under the protection of inert gas condition, stopped heating when oil bath is heated to 160 ℃ in the 100mL there-necked flask that the 50mL trolamine is housed, and solution colour becomes sorrel again by the light blue mazarine that becomes, and counts solution A.Take by weighing the adding of 5mmol Se powder and be equipped with in the 100mL there-necked flask of 50mL trolamine, slowly be warming up to 240 ℃, solution becomes brown immediately, counts solution B.Solution A and solution B are mixed; stirring, oil bath are heated to 240 ℃ under the protection of inert gas condition; reflux 7 hours until react completely; stop to stir, after temperature is reduced to room temperature, pour out supernatant liquid; the lower black pressed powder was descended centrifugal 30 minutes at 10000 rev/mins; then water or ethanol clean, and recentrifuge got CuInSe with centrifugal product in 12 hours 50 ℃ of lower vacuum-dryings 2Nanometer powder.
Embodiment 2
At synthetic CuInSe 2In the process of nanometer powder, make solvent with reacted upper strata liquid.In reaction process, trolamine participates in reaction as complexing agent, is reduced to again at last trolamine.CuCl, InCl 34H 2O and Se have generated CuInSe 220 ℃ of lower atmospheric pressure reflux in triethanolamine solution 2Nanometer powder.
Take by weighing 2mmolCuCl and 2mmolInCl 34H 2In the 100mL there-necked flask of the triethanolamine solution that O reclaims after 50mL reaction is housed, under the protection of inert gas condition, stir, stopped heating when oil bath is heated to 180 ℃, solution colour becomes sorrel again by the light blue mazarine that becomes, and counts solution A.Take by weighing 4mmol Se powder and join in the 100mL there-necked flask that the triethanolamine solution that reclaims after the 50mL reaction is housed, slowly be warming up to 230 ℃, solution becomes brown immediately, counts solution B.Solution A and solution B are mixed; stirring, oil bath are heated to 230 ℃ under the protection of inert gas condition; reflux 8 hours until react completely; stop to stir, after temperature is reduced to room temperature, pour out supernatant liquid; the lower black pressed powder was descended centrifugal 30 minutes at 10000 rev/mins; then water or ethanol clean, and recentrifuge got CuInSe with centrifugal product in 12 hours 50 ℃ of lower vacuum-dryings 2Powder.
Embodiment 3
In the process of synthetic CuInGaSe nanometer powder, still make solvent with trolamine.
Take by weighing 1mmolCuCl, 0.6mmolInCl 34H 2O, 0.6mmolGaCl 3In the 100mL there-necked flask that the 25mL triethanolamine solution is housed, heated and stirred in oil bath under 200 ℃, all is dissolved in these solid particulates in the solvent under the protection of rare gas element, is designated as A.In another 100mL there-necked flask, add 25mL trolamine 2mmolSe powder, be heated to 200 ℃, the complete complexing of Se powder, solution becomes sorrel, is designated as B.A is heated to temperature of reaction, then rapidly B is injected, there are a large amount of gray solid particles to generate, 4h again refluxes, stop stirring and be cooled to room temperature, pour out supernatant liquid, the lower black pressed powder was descended centrifugal 30 minutes at 10000 rev/mins, then with normal hexane clean, centrifugal 3 times, with centrifugal product 40 ℃ of lower vacuum-dryings 4 hours Cu (In 0.5Ga 0.5) Se 2Nanometer powder.
Embodiment 4
In the process of synthetic CuInGaS nanometer powder, make solvent with diglycolamine.
In a 50mL there-necked flask, add 10mL diglycolamine and 0.5mmol S powder, under agitation be heated to 150 ℃ and treat that the S powder dissolves fully, is designated as B.Take by weighing in addition 0.5mmol acetylacetonate copper, 0.7mmolInCl 3, 0.7mmol acetylacetonate gallium and 10mL diglycolamine solution in the 50mL there-necked flask, in oil bath, be heated to 180 ℃ of stirrings solid particulate all be dissolved in the diglycolamine uniformly, be designated as A, whole process is carried out in the protection of rare gas element.Continuation is heated to temperature of reaction with A, then rapidly B is injected, have a large amount of gray solid particles to generate, solution becomes black immediately, 6h again refluxes, stop stirring and be cooled to room temperature, add dehydrated alcohol, make black solid particle natural subsidence, then outwell supernatant liquid, with the lower black pressed powder 10000 rev/mins lower centrifugal 5 minutes, then with dehydrated alcohol or chloroform clean, centrifugal 3 times, with at normal temperatures vacuum-drying of centrifugal product 4 hours Cu (In 0.5Ga 0.5) S 2Nanometer powder.
The prepared Cu-In-Ga-Se-S nano-powder material of above-mentioned four embodiment is made respectively XRD, SEM, TEM and HR-TEM analyze, extremely shown in Figure 6 such as Fig. 2.Wherein Fig. 2 is the XRD figure of the Cu-In-Ga-Se-S nano-powder material that adopts the method for the invention and make, and wherein, ordinate zou is absorption intensity (Intensity), and X-coordinate is diffraction angle (2 θ), is CuInSe (a) and (b) 2XRD figure, be respectively Cu (InGa) Se (c) and (d) 2And CuGaSe 2XRD figure.As shown in Figure 2, adopt the prepared Cu-In-Ga-Se-S nano-powder material of the present invention to have very high phase purity.Cu (InGa) Se of Fig. 3 for adopting the method for the invention to make 2SEM figure.As shown in Figure 3, adopt prepared Cu (InGa) Se of the present invention 2Powdered material has the nano level yardstick, and granularity is very even.The CuGaSe of Fig. 4 for adopting the method for the invention to make 2SEM figure.As shown in Figure 4, adopt the prepared CuGaSe of the present invention 2Have the nano level yardstick, and granularity is very even.The CuInSe of Fig. 5 for adopting the method for the invention to make 2The TEM figure of nanoparticle.The CuInSe that Fig. 6 adopts the method for the invention to make 2The HR-TEM figure of nanoparticle.Fig. 7 is the ultraviolet of the Cu-In-Ga-Se-S nano-powder material that makes with the method for the invention-near-infrared absorption spectrum figure.Wherein, curve 1 is the CuInSe that the present invention prepares 2Ultraviolet-the near-infrared absorption spectrum of nanoparticle; Curve 2 is Cu (InGa) Se that the present invention prepares 2Ultraviolet-near-infrared absorption spectrum; Curve 3 is CuGaSe that the present invention prepares 2Ultraviolet-near-infrared absorption spectrum.Fig. 8 is the absorbancy of the Cu-In-Ga-Se-S nano-powder material that makes with the method for the invention-bandwidth figure.Wherein, curve 1 is the CuInSe that the present invention prepares 2The absorbancy of nanoparticle-energy bandwidth relationship curve; Curve 2 is Cu (InGa) Se that the present invention prepares 2Absorbancy-energy bandwidth relationship curve; Curve 3 is CuGaSe that the present invention prepares 2Absorbancy-energy bandwidth relationship curve.As can be seen from Figure 8, the CuInSe of the present invention's preparation 2, Cu (InGa) Se 2, CuGaSe 2Bandwidth be respectively 1.04eV, 1.35eV, 1.74eV, consistent with the conclusion of bibliographical information.

Claims (3)

1. the preparation method of a Cu-In-Ga-Se-S nano-powder material may further comprise the steps:
Step 1: select that can be dissolved in boiling point be raw material more than or equal to Cu, the In of 180 ℃ alkyl alcoholamine and the compound of Ga, according to Cu: (In+Ga)=1: the mol ratio of (1～1.5) joins in the alkyl alcoholamine, under the protection of inert gas condition, stir, be heated to 110～180 ℃, so that the compound of Cu, In and Ga dissolves fully, obtain reaction system A; Described boiling point is trolamine, diethanolamine or diglycolamine more than or equal to 180 ℃ alkyl alcoholamine;
Step 2: simple substance Se and simple substance S are joined in the alkyl alcoholamine, be heated to 200～280 ℃ of backflows under stirring, so that the compound of Se and S dissolves fully, obtain reaction system B; The molar weight sum of the Se that adds and S is the twice of the molar weight of Cu in the step 1;
Step 3: reaction system A and reaction system B are mixed, obtain reaction system C;
Step 4: will be heated to 200～280 ℃ of backflows under the reaction system C stirring, keep reaction after 4～10 hours, stopped heating stirs, be cooled to room temperature, take off layer black powder and carry out centrifugal, washing and drying treatment, obtain the Cu-In-Ga-Se-S nano-powder material, i.e. Cu (In xGa 1-x) (Se yS 2-y) nanometer powder, wherein 0＜x＜1,0＜y＜2.
2. the preparation method of Cu-In-Ga-Se-S nano-powder material according to claim 1 is characterized in that, the compound of described Cu, In and Ga is hydrochloride, vitriol, nitrate, acetate or acetylacetonate.
3. the preparation method of Cu-In-Ga-Se-S nano-powder material according to claim 1 is characterized in that, the centrifugation rate that adopts during centrifugal treating in the step 4 is 8000～10000 rev/mins; The washing composition that adopts during carrying out washing treatment is ethanol, acetone, chloroform or normal hexane organic solvent; The drying temperature that adopts during drying treatment is 20～60 ℃.
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CN104979428B (en) * 2015-05-31 2017-03-08 厦门大学 A kind of nanocrystalline synthetic method of copper indium gallium sulphur selenium

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CN101234779A (en) * 2008-03-06 2008-08-06 中国科学院化学研究所 Method for preparing copper-indium-sulfur semi-conductor nano particles

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Title
Matthew G. Panthani et al..Synthesis of CuInS2, CuInSe2, and Cu(InxGa1-x)Se2 (CIGS) Nanocrystal Inks for Printable Photovoltaics.《J. Am. Chem. Soc.》.2008,第130卷(第49期),16770-16777. *

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