CN105885842B - A kind of rare-earth photoconversion phosphor powder, the preparation method of rare-earth photoconversion phosphor powder, silica-based solar cell, solar power system - Google Patents
A kind of rare-earth photoconversion phosphor powder, the preparation method of rare-earth photoconversion phosphor powder, silica-based solar cell, solar power system Download PDFInfo
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- CN105885842B CN105885842B CN201610309953.5A CN201610309953A CN105885842B CN 105885842 B CN105885842 B CN 105885842B CN 201610309953 A CN201610309953 A CN 201610309953A CN 105885842 B CN105885842 B CN 105885842B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 35
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 35
- 239000000843 powder Substances 0.000 title claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910005228 Ga2S3 Inorganic materials 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 7
- 239000003708 ampul Substances 0.000 claims description 7
- 239000010431 corundum Substances 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- 238000004073 vulcanization Methods 0.000 claims description 7
- NVEKVESLPDZKSN-UHFFFAOYSA-N ytterbium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Yb+3].[Yb+3] NVEKVESLPDZKSN-UHFFFAOYSA-N 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 26
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052710 silicon Inorganic materials 0.000 abstract description 14
- 239000010703 silicon Substances 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000012298 atmosphere Substances 0.000 abstract description 9
- 230000001681 protective effect Effects 0.000 abstract description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 5
- 230000009466 transformation Effects 0.000 abstract description 5
- 229910052788 barium Inorganic materials 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 229910052712 strontium Inorganic materials 0.000 abstract description 4
- 229910021421 monocrystalline silicon Inorganic materials 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 4
- XXCMBPUMZXRBTN-UHFFFAOYSA-N strontium sulfide Chemical compound [Sr]=S XXCMBPUMZXRBTN-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- Y02E10/52—PV systems with concentrators
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- Chemical & Material Sciences (AREA)
- Luminescent Compositions (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention discloses a kind of rare-earth photoconversion phosphor powder, the chemical composition formula of the fluorescent material is (A1‑xYbx)Ga2S4, wherein, one or more elements in A Ca, Sr, Ba；X is molal quantity, and 0.001≤x≤0.10.Invention additionally discloses a kind of preparation method of rare-earth photoconversion phosphor powder, comprise the following steps step 101, the raw material using A sulfide as element A, with Ga2S3For the raw material of Ga elements, with Yb2S3For the raw material of Yb elements, according to chemical composition formula (A1‑xYbx)Ga2S4, weigh corresponding raw material；Step 201, after ground and mixed is uniform, under protective atmosphere, sintered 1 ~ 4 hour in 800 ~ 1000 DEG C；Step 301, attrition grinding after room temperature is cooled to, that is, sample is made.The rare earth light conversion material of the present invention has the stronger near infrared emission positioned at 975nm, the transmitting just matches with the energy gap of monocrystalline silicon, the photoelectric transformation efficiency of silicon solar cell can be effectively improved, is the potential light-converting material for being applied to silica-based solar cell.
Description
Technical field
The present invention relates to phosphor technologies field, more particularly to a kind of rare earth light suitable for silica-based solar cell to change
Fluorescent material, with and preparation method thereof.
Background technology
In recent years, with the regenerative resource such as increasingly raising, solar energy being continuously increased with environmentally friendly cry of energy demand
Increasingly it is valued by people.Solar energy tool has the advantages that cleanliness without any pollution, renewable because of it, it is considered to be substitutes traditional
A kind of new cleaning fuel of the stone energy.Solar energy photoelectric conversion technology be solve energy problem main candidate scheme it
One.According to the difference of material therefor, solar cell can be divided into：Silicon solar cell, multicomponent compound film solar cell,
Polymer multi-layer modified electrode type solar cell, nano-crystalline solar battery, organic solar batteries etc., wherein silicon solar
Battery is a kind of most ripe, the most widely used solar cell of current development, occupies staple market.
Silicon solar cell is only capable of having the near infrared light of its band gap (Eg=1.12 eV, the nm of λ ≈ 1000) nearby
Effect is converted into electric energy, and incident solar spectrum energy is mainly distributed on ultraviolet-visible area.Mismatch between this spectrum seriously limits
The further raising of monocrystaline silicon solar cell electricity conversion is made.The silicon solar cell of commercial scale at present
Photoelectric transformation efficiency is only 15% or so.To be converted to by rare earth light conversion material under the ultraviolet-visible light in solar spectrum can
Effectively absorbed by silicon solar cell ~ 1000 nm near infrared light be improve silicon solar cell photoelectric transformation efficiency one
Kind effective way.
Study what the rare earth light conversion material of more raising silicon solar cell photoelectric transformation efficiency mainly utilized at present
It is Yb3+Ion is located at nearly 1000 nm near infrared emission, and the transmitting just matches with the energy gap of monocrystalline silicon, to strengthen Yb3+
Ion usually introduces Ce in the absorption in ultraviolet-visible light area3+Ce therefore unavoidably be present as sensitizer in ion4+ -
Yb2+Metal-metal between charge transfer band caused by fluorescent quenching, the problems demand solve.
The content of the invention
One kind is provided and is applied to silica-based solar cell it is an object of the invention to overcome the deficiency of above-mentioned prior art
Rare-earth photoconversion phosphor powder and preparation method thereof, rare-earth photoconversion phosphor powder of the invention is wide using it and strong electric charge moves
Shipper pole absorbs light wave, effectively can be converted into the ultraviolet-visible light of the nm scopes of 250 nm~450 and silica-based solar cell
Nearly 1000 nm matched somebody with somebody near infrared light, it is a kind of potential light-converting material for improving silica-based solar cell efficiency.
To achieve the above object, the present invention provides a kind of rare-earth photoconversion phosphor powder suitable for silica-based solar cell,
The chemical composition formula of the fluorescent material is (A1-xYbx)Ga2S4, wherein, one or more elements in A Ca, Sr, Ba；X is to rub
That number, and 0.001≤x≤0.10.
Also a kind of preparation method of rare-earth photoconversion phosphor powder of the present invention, comprises the following steps：
Step 101, the raw material using A sulfide as element A, with Ga2S3For the raw material of Ga elements, with Yb2S3For Yb elements
Raw material, according to chemical composition formula (A1-xYbx)Ga2S4, weigh corresponding raw material；
Step 201, after ground and mixed is uniform, under protective atmosphere, sintered 1 ~ 4 hour in 800 ~ 1000 DEG C；
Step 301, attrition grinding after room temperature is cooled to, that is, sample is made.
Preferably, the protective atmosphere described in step 201 is the one or more in nitrogen, helium, argon gas.
Preferably, the sulfide of the A described in step 101 is the one or more in CaS, SrS, BaS.
Also a kind of silica-based solar cell of the present invention, it uses rare-earth photoconversion phosphor powder as claimed in claim 1.
Also a kind of solar power system of the present invention, it uses silica-based solar cell as claimed in claim 5.
Preferably, the silica-based solar cell is connected with a storage battery, and the silica-based solar cell is also by inverse
Become device to electrically connect with alternating current electrical equipment, the battery also direct current electrical equipment electrically connects.
The rare-earth photoconversion phosphor powder of the present invention can effectively absorb 250 nm -450 nm ultraviolet-visible light, and launch
Go out to be located at nearly 1000 nm stronger near infrared light, be that a kind of novel rare-earth light suitable for silicon solar cell changes material
Material.
Compared with prior art, the present invention has the advantages that：
1st, there is rare earth light conversion material of the invention wide and strong charge transfer band to absorb, can effectively absorb 250 nm-
The ultraviolet-visible light of 450 nm scopes.
2nd, rare earth light conversion material of the invention has a stronger near infrared emission positioned at 975 nm, the transmitting just with list
The energy gap matching of crystal silicon, the photoelectric transformation efficiency of silicon solar cell can be effectively improved, be potentially to be applied to silicon substrate too
The light-converting material of positive energy battery.
3rd, rare-earth photoconversion phosphor powder stability of the invention is good, and reliability is high, easy to use,
Brief description of the drawings
Fig. 1 is (Ca in one embodiment of the invention0.99Yb0.01)Ga2S4The near-infrared of rare earth light conversion material is excited and sent out
Penetrate spectrum.
The realization, functional characteristics and advantage of the object of the invention will be described further referring to the drawings in conjunction with the embodiments.
Embodiment
Embodiment 1-1：The present invention provides a kind of rare-earth photoconversion phosphor powder suitable for silica-based solar cell, the fluorescence
The chemical composition formula of powder is (A1-xYbx)Ga2S4, wherein, one or more elements in A Ca, Sr, Ba；X is molal quantity,
And 0.001≤x≤0.10.
Embodiment 1-2：Also a kind of preparation method of rare-earth photoconversion phosphor powder of the present invention, comprises the following steps：Step
101, the raw material using A sulfide as element A, with Ga2S3For the raw material of Ga elements, with Yb2S3For the raw material of Yb elements, according to
Chemical composition formula (A1-xYbx)Ga2S4, weigh corresponding raw material；Step 201, after ground and mixed is uniform, under protective atmosphere, in
800 ~ 1000 DEG C sinter 1 ~ 4 hour；Step 301, attrition grinding after room temperature is cooled to, that is, sample is made.
Electronic balance or assay balance can be used when weighing.Grinder can be used during grinding or uses mortar hand
Work is ground.When using protective atmosphere, operation is sintered in a kettle, and the partial pressure of protective atmosphere keeps constant.Powder
Pulverizer can be used to carry out for broken operation.Sample after crushing can also sieve, and the sample after crushing is reached certain mesh number.
Embodiment 1-3：Protective atmosphere described in step 201 is nitrogen, the one or more in helium, argon gas.
Embodiment 1-4：The sulfide of A described in step 101 is the one or more in CaS, SrS, BaS.
Embodiment 2：(Ca0.999Yb0.001)Ga2S4The preparation method of rare earth light conversion material
Weigh the g of calcium sulfide [CaS] 0.7207, vulcanization gallium [Ga2S3] 2.3564 g, ytterbium sulfide [Yb2S3] 0.0022
G, after being fully ground and be well mixed in agate mortar, it is fitted into corundum crucible, nitrogen (about 10 minutes) is first passed through before heating
By the air emptying in quartz ampoule, sintered 3 hours in 800 DEG C in a nitrogen atmosphere, be cooled to attrition grinding after room temperature, finally
Obtain sample.
Embodiment 3：(Sr0.999Yb0.001)Ga2S4The preparation method of rare earth light conversion material
Weigh the g of strontium sulfide [SrS] 1.1957, vulcanization gallium [Ga2S3] 2.3564 g, ytterbium sulfide [Yb2S3] 0.0022
G, after being fully ground and be well mixed in agate mortar, it is fitted into corundum crucible, argon gas (about 10 minutes) is first passed through before heating
By the air emptying in quartz ampoule, sintered 2.5 hours in 900 DEG C under an argon atmosphere, be cooled to attrition grinding after room temperature, most
Sample is obtained eventually.
Embodiment 4：(Ca0.99Yb0.01)Ga2S4The preparation method of rare earth light conversion material
Weigh the g of calcium sulfide [CaS] 0.7142, vulcanization gallium [Ga2S3] 2.3564 g, ytterbium sulfide [Yb2S3] 0.0221
G, after being fully ground and be well mixed in agate mortar, it is fitted into corundum crucible, nitrogen (about 10 minutes) is first passed through before heating
By the air emptying in quartz ampoule, sintered 2 hours in 950 DEG C under nitrogen/argon-mixed atmosphere, be cooled to attrition grinding after room temperature,
Finally give sample.
Embodiment 5：(Ca0.70Sr0.29Yb0.01)Ga2S4The preparation method of rare earth light conversion material
Weigh the g of calcium sulfide [CaS] 0.5050, the g of strontium sulfide [SrS] 0.3471, vulcanization gallium [Ga2S3] 2.3564 g,
Ytterbium sulfide [Yb2S3] 0.0221 g, after being fully ground and be well mixed in agate mortar, it is fitted into corundum crucible, before heating
Nitrogen (about 10 minutes) is first passed through by the air emptying in quartz ampoule, sinters 4 hours, is cooled in 800 DEG C under helium atmosphere
Attrition grinding after room temperature, finally gives sample.
Embodiment 6：(Ca0.50Ba0.40Yb0.10)Ga2S4The preparation method of rare earth light conversion material
Weigh the g of calcium sulfide [CaS] 0.3607, the g of barium sulphide [BaS] 0.6776, vulcanization gallium [Ga2S3] 2.3564 g,
Ytterbium sulfide [Yb2S3] 0.2211 g, after being fully ground and be well mixed in agate mortar, it is fitted into corundum crucible, before heating
Nitrogen (about 10 minutes) is first passed through by the air emptying in quartz ampoule, is sintered 1 hour in 1000 DEG C under an argon atmosphere, cooling
Attrition grinding after to room temperature, finally gives sample.
Embodiment 7：(Ba0.95Yb0.05)Ga2S4The preparation method of rare earth light conversion material
Weigh the g of barium sulphide [BaS] 1.6092, vulcanization gallium [Ga2S3] 2.3564 g, ytterbium sulfide [Yb2S3] 0.1106
G, after being fully ground and be well mixed in agate mortar, it is fitted into corundum crucible, nitrogen (about 10 minutes) is first passed through before heating
By the air emptying in quartz ampoule, sintered 3 hours in 900 DEG C in a nitrogen atmosphere, be cooled to attrition grinding after room temperature, finally
Obtain sample.
Embodiment 8：A kind of silica-based solar cell
The silica-based solar cell uses the rare earth light conversion material as prepared by any one of embodiment 2 to 7 preparation method.
The silica-based solar cell conversion efficiency is higher.
Embodiment 9：A kind of solar power system
Also a kind of solar power system of the present invention, it uses silica-based solar cell as described in Example 8.
Embodiment 9-1：
Embodiment 9 is further limited, the silica-based solar cell is connected with a storage battery, the silica-based solar
Battery is also electrically connected by inverter with alternating current electrical equipment, and the battery also direct current electrical equipment electrically connects.
In summary, the invention discloses a kind of rare-earth photoconversion phosphor powder and preparation method thereof.The fluorescent material it is basic
Chemical composition formula is：(A1-xYbx)Ga2S4, wherein A is one or more elements in Ca, Sr, Ba；X is molal quantity, and
0.001≤x≤0.10, and disclose the preparation method of the fluorescent material.Rare earth light conversion material disclosed by the invention is 250
There is stronger absorption in the range of the nm of nm~450, its near infrared emission main peak is located at 975 nm, has ultraviolet-visible light area wide
Band excites and the advantages that stronger near infrared emission, can be as potential application in the light-converting material of silica-based solar cell.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art is not departing from the principle and objective of the present invention
In the case of above-described embodiment can be changed within the scope of the invention, change, replace and modification.
Claims (3)
- A kind of 1. preparation method of rare-earth photoconversion phosphor powder, it is characterised in that：The chemical composition formula of rare-earth photoconversion phosphor powder is Ca0.999Yb0.001Ga2S4；Specific preparation process：S101, weigh calcium sulfide CaS 0.7207g, vulcanization gallium Ga2S32.3564 g, ytterbium sulfide Yb2S30.0022 g；S102, after being fully ground and be well mixed in agate mortar, is fitted into corundum crucible, and being first passed through nitrogen 10 before heating divides Clock, the air emptying in quartz ampoule sinters 3 hours in 800 DEG C in a nitrogen atmosphere；S103, attrition grinding after room temperature is cooled to, finally gives sample.
- 2. a kind of silica-based solar cell, it is characterised in that it uses rare-earth photoconversion phosphor powder as claimed in claim 1.
- 3. a kind of solar power system, it is characterised in that it uses silica-based solar cell as claimed in claim 2.
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