CN117682843B - Preparation method and application of nickel oxide target - Google Patents
Preparation method and application of nickel oxide target Download PDFInfo
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- CN117682843B CN117682843B CN202410154738.7A CN202410154738A CN117682843B CN 117682843 B CN117682843 B CN 117682843B CN 202410154738 A CN202410154738 A CN 202410154738A CN 117682843 B CN117682843 B CN 117682843B
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- nickel oxide
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- iodine
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- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 162
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims abstract description 58
- 229910001641 magnesium iodide Inorganic materials 0.000 claims abstract description 58
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 56
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011777 magnesium Substances 0.000 claims abstract description 50
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 50
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 46
- 239000011630 iodine Substances 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 45
- 239000004471 Glycine Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 150000002815 nickel Chemical class 0.000 claims abstract description 22
- 238000011049 filling Methods 0.000 claims abstract description 17
- 239000013077 target material Substances 0.000 claims abstract description 14
- 229910001868 water Inorganic materials 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 13
- 238000007873 sieving Methods 0.000 claims abstract description 13
- 238000005520 cutting process Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000005498 polishing Methods 0.000 claims abstract description 11
- 238000009966 trimming Methods 0.000 claims abstract description 11
- 238000003825 pressing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000007731 hot pressing Methods 0.000 claims abstract description 5
- 230000005525 hole transport Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 44
- 238000005245 sintering Methods 0.000 claims description 44
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 32
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- ZVHHIDVFSYXCEW-UHFFFAOYSA-L nickel(ii) nitrite Chemical compound [Ni+2].[O-]N=O.[O-]N=O ZVHHIDVFSYXCEW-UHFFFAOYSA-L 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 238000005336 cracking Methods 0.000 abstract description 17
- 238000010438 heat treatment Methods 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000000748 compression moulding Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- -1 iodide ions Chemical class 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
Classifications
-
- 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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- Physical Vapour Deposition (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The application discloses a preparation method and application of a nickel oxide target, wherein the preparation method of the nickel oxide target comprises the following steps: uniformly mixing nickel salt, magnesium iodide, water and glycine, drying to obtain xerogel, calcining the xerogel, and grinding to obtain iodine/magnesium co-doped nickel oxide; ball milling and sieving the iodine/magnesium co-doped nickel oxide to obtain powder, and filling and pressing the powder to obtain a blank; and (3) after the blank is sintered by vacuum hot pressing, demoulding, cutting, polishing and trimming to obtain the nickel oxide target. The preparation method disclosed by the application has the advantages that the operability is higher, the cracking of the nickel oxide target material can be effectively reduced, the yield of the preparation method is improved, the cost is reduced, the electrical property of the nickel oxide target material is good, the service life is long, and the preparation method can be used for preparing a hole transport layer in a perovskite solar cell.
Description
Technical Field
The invention relates to the technical field of oxide targets, in particular to a preparation method and application of a nickel oxide target.
Background
Since a perovskite solar cell has been attracting attention in recent years, researches on a nickel oxide target have been increasingly conducted by researchers. The preparation methods of nickel oxide targets are various and mainly comprise a thermal evaporation method, a molecular beam epitaxy method, a sputtering method, a chemical vapor deposition method, a casting method, a powder metallurgy method, a hot pressing method and the like. Ion doping is also used in some fabrication methods to improve the electrical properties of nickel oxide targets.
In the related art, a doping method for improving the electrical property of a nickel oxide target is disclosed, niO powder and MgO powder are mixed, ball-milled and sieved to obtain mixed powder of NiO and MgO; and (3) carrying out die filling, pre-pressing, vacuum hot pressing, demoulding treatment and machining on the mixed powder of NiO and MgO to obtain the nickel oxide target. According to the method, the magnesium element is doped in the nickel oxide target material, so that the forbidden bandwidth of the nickel oxide target material is increased, and the electrical property of the nickel oxide target material can be improved.
However, as the doping amount of magnesium increases, lattice expansion and distortion may be caused, which may cause the nickel oxide target to be easily cracked, while a small amount of magnesium doping has very limited effect on improving the electrical properties of the nickel oxide target, and these problems result in poor operability of the doping method and high cost of the prepared magnesium doped nickel oxide target.
Therefore, how to develop a preparation method capable of effectively reducing the cracking of the nickel oxide target is a problem to be solved.
Disclosure of Invention
In order to reduce cracking of a magnesium-doped nickel oxide target, the application provides a preparation method and application of the nickel oxide target.
In a first aspect, the present application provides a method for preparing a nickel oxide target, which adopts the following technical scheme:
the preparation method of the nickel oxide target comprises the following steps:
Iodine/magnesium co-doping: uniformly mixing nickel salt, magnesium iodide, water and glycine, drying to obtain xerogel, calcining the xerogel, and grinding to obtain iodine/magnesium co-doped nickel oxide;
blank manufacturing: ball milling and sieving the iodine/magnesium co-doped nickel oxide to obtain powder, and filling and pressing the powder to obtain a blank;
Firing: and (3) after the blank is sintered by vacuum hot pressing, demoulding, cutting, polishing and trimming to obtain the nickel oxide target.
By adopting the technical scheme, the iodide ions and the oxygen ions have similar chemical properties, the O-site doping can be carried out on the nickel oxide, and the structural stability of the nickel oxide is improved, so that the lattice expansion and distortion phenomena caused by magnesium ion doping are inhibited. In addition, the nickel salt and the magnesium iodide are adopted as raw materials, the nickel salt and the magnesium iodide are dissolved in water, and nickel, iodine and magnesium elements are dispersed more uniformly in a solution system, so that the nickel, the iodine and the magnesium elements in xerogel are also distributed more uniformly, the doping effect of the iodine and the magnesium on the nickel oxide is improved, the phenomena of lattice expansion and distortion are further suppressed, the sintering density of the nickel oxide target is improved, and the cracking of the target after sintering is reduced. Therefore, the preparation method provided by the application has higher operability, can effectively reduce the cracking of the nickel oxide target, improves the yield and reduces the cost.
In a specific embodiment, the molar ratio of the nickel salt to magnesium iodide in the iodine/magnesium co-doping step is 100 (5-9).
By adopting the technical scheme, the molar ratio of the nickel salt to the magnesium iodide can have an important influence on the electrical performance of the finally prepared nickel oxide target. When the molar ratio of the nickel salt to the magnesium iodide is too large, the conductivity of the nickel oxide target is lowered, and the nickel oxide target has poor working performance in a wide temperature range. When the molar ratio of the nickel salt to the magnesium iodide is too small, the nickel oxide target is liable to crack during sintering. According to the application, experiments surprisingly show that the molar ratio of the nickel salt to the magnesium iodide is adjusted to be 100 (5-9), the prepared nickel oxide target material not only has excellent conductivity, but also has good working performance in a wide temperature range, and the nickel oxide target material is not easy to crack in the preparation process, so that the molar ratio of the nickel salt to the magnesium iodide is preferably 100 (5-9).
In a specific embodiment, in the iodine/magnesium co-doping step, the nickel salt is any one of nickel nitrate, nickel nitrite or nickel hydroxide.
By adopting the technical scheme, the nickel salt can obtain better doping effect with magnesium iodide, and the prepared nickel oxide target has good electrical property and is not easy to crack in the sintering process.
In a specific embodiment, the iodine/magnesium co-doping step is as follows: adding nickel salt and magnesium iodide into water, stirring at 40-60 ℃ until the nickel salt and the magnesium iodide are completely dissolved, adding glycine, uniformly mixing, drying at 75-92 ℃ to obtain xerogel, calcining the xerogel at 480-620 ℃ for 1.5-2.5h to obtain a calcined product, and grinding the calcined product to obtain the iodine/magnesium co-doped nickel oxide.
By adopting the technical scheme, experiments show that doping is performed under the process conditions, so that the doping effect is improved, and the electrical property of the nickel oxide target is improved. This is probably because dissolution at 40-60 c accelerates dissolution of the nickel salt and magnesium iodide, and can increase its solubility, contributing to complete dissolution of the nickel salt and magnesium iodide. Drying at 75-92 ℃ can shorten the drying time, improve the uniformity of nickel element, magnesium element and iodine element in xerogel and improve the doping effect. Calcination at 480-620 ℃ is beneficial to introducing iodine into the O site of nickel oxide and introducing magnesium into the crystal lattice of nickel oxide, thereby improving doping effect.
In a specific embodiment, the blank making step is as follows: ball milling and sieving the iodine/magnesium co-doped nickel oxide to obtain powder, wherein the particle size D 50 of the powder is 21-23 mu m; and (3) after the powder is subjected to die filling, pressing and forming under the pressure of 0.2-0.5 MPa to obtain a blank.
By adopting the technical scheme, the application discovers that controlling the particle size of the powder within the range is beneficial to reducing the cracking of the nickel oxide target in the firing process. This is probably because, in this particle size range, the sintered nickel oxide target has a more dense structure. In addition, the application also discovers that the prepared nickel oxide target material has higher electrical property in the particle size range.
In a specific embodiment, the firing step is as follows: and (3) carrying out heat preservation and sintering on the green body for 5-10 hours at the sintering temperature of 700-900 ℃ and the vacuum degree of 0.08-0.1MPa, then raising the sintering temperature to 1300-1500 ℃, introducing oxygen, keeping the vacuum degree of 0.05-0.1MPa, continuing sintering for 5-12 hours to obtain a sintering product, and demoulding, cutting, polishing and trimming the sintering product to obtain the nickel oxide target.
By adopting the technical scheme, experiments show that the nickel oxide target with excellent electrical performance can be obtained by firing under the process conditions, and the cracking condition of the nickel oxide target is further reduced within the process condition range.
In a specific embodiment, the step of forming the blank further comprises zirconia, and in the step of forming the blank: mixing zirconium oxide and iodine/magnesium co-doped nickel oxide, ball milling, sieving to obtain powder, and molding and pressing the powder to obtain a blank.
By adopting the technical scheme, the application discovers that by adding zirconia, the electrical property of the nickel oxide target can be further improved, the cracking of the nickel oxide target can be further reduced, and the service life of the nickel oxide target can be prolonged. This is probably because the zirconium doping can suppress lattice distortion, maintain stability of the crystal structure, and thereby improve the electrical properties of the nickel oxide target. In addition, the doping of zirconium can effectively improve the stability, corrosion resistance and thermal stability of the nickel oxide target, improve the utilization rate of nickel electroactive substances and improve the discharge potential of a nickel electrode, thereby prolonging the service life of the nickel oxide target.
In a specific embodiment, the weight ratio of zirconia to iodine/magnesium co-doped nickel oxide is (3-6): 100.
By adopting the technical scheme, experiments show that the weight ratio of the zirconium oxide to the iodine/magnesium co-doped nickel oxide is controlled within the range, and the prepared nickel oxide target has higher electrical property and yield and longer service life.
In a second aspect, the application provides an application of a nickel oxide target, which adopts the following technical scheme:
The application of the nickel oxide target material is that the nickel oxide target material is prepared by the preparation method of the nickel oxide target material, and the nickel oxide target material is used for preparing a hole transport layer in a perovskite solar cell.
By adopting the technical scheme, the hole transport layer is manufactured by the nickel oxide target material prepared by the preparation method, so that the electrical property of the perovskite solar cell can be improved, and the service life of the perovskite solar cell can be prolonged.
In summary, the present application includes at least one of the following beneficial technical effects:
According to the preparation method, nickel salt, magnesium iodide, water and glycine are adopted as raw materials, xerogel is formed firstly, iodine/magnesium co-doped nickel oxide is formed by calcining and grinding, and then blank making and firing are carried out, so that the nickel oxide target is obtained, the operability is higher, the cracking of the nickel oxide target can be effectively reduced, the yield of the preparation method is improved, and the cost is reduced;
the application is favorable for further reducing the cracking of the nickel oxide by optimizing the reaction conditions in the process steps, and simultaneously, the electrical property of the nickel oxide target is improved;
Zirconium doping is performed by adding zirconium oxide in the blank making step, so that the cracking of nickel oxide is further reduced, the electrical property of a nickel oxide target is improved, and the service life is prolonged.
Detailed Description
The present application will be described in further detail with reference to examples.
Examples
Example 1
The embodiment provides a preparation method of a nickel oxide target, which comprises the following steps:
the raw materials are weighed as follows: 18270g of nickel nitrate, 2618.77g of magnesium iodide, 100L of deionized water and 42kg of glycine.
Adding nickel nitrate and magnesium iodide into water, stirring at 50 ℃ until the nickel nitrate and the magnesium iodide are completely dissolved, adding glycine, and continuously stirring at constant temperature until the nickel nitrate and the magnesium iodide are uniformly mixed to obtain a mixed solution. Then, the mixed solution was placed in an oven and dried under vacuum at 88 ℃ to obtain xerogel. And then placing the xerogel into a calciner, heating to 550 ℃ at a speed of 3 ℃/min, calcining for 2 hours at a constant temperature, ending the calcining, naturally cooling to obtain a calcined product, and grinding the calcined product to obtain the iodine/magnesium co-doped nickel oxide.
Sequentially ball-milling and sieving the iodine/magnesium co-doped nickel oxide to obtain powder with the particle diameter D 50 of 22 mu m, then filling the powder into a mold, and then pressing and forming under the pressure of 0.35MPa to obtain a blank body.
Then placing the green body into a furnace, preserving heat and sintering for 8 hours at the sintering temperature of 800 ℃ and the vacuum degree of 0.08MPa, then heating to 1400 ℃ at the heating rate of 1 ℃/min, introducing oxygen, controlling the vacuum degree in the furnace within the range of 0.05-0.1MPa, continuing sintering for 8 hours, stopping sintering, naturally cooling to obtain a sintering product, and sequentially demoulding, cutting, polishing and trimming the sintering product to obtain the nickel oxide target.
Example 2
The present embodiment provides a method for preparing a nickel oxide target, which is different from embodiment 1 only in that the raw materials are weighed as follows: 18270g of nickel nitrate, 1870.55g of magnesium iodide, 100L of deionized water and 42kg of glycine.
Example 3
The present embodiment provides a method for preparing a nickel oxide target, which is different from embodiment 1 only in that the raw materials are weighed as follows: 18270g of nickel nitrate, 3366.99g of magnesium iodide, 100L of deionized water and 42kg of glycine.
Example 4
The present embodiment provides a method for preparing a nickel oxide target, which is different from embodiment 1 only in that the raw materials are weighed as follows: 18270g of nickel nitrate, 1496.44g of magnesium iodide, 100L of deionized water and 42kg of glycine.
Example 5
The present embodiment provides a method for preparing a nickel oxide target, which is different from embodiment 1 only in that the raw materials are weighed as follows: 18270g of nickel nitrate, 3741.1g of magnesium iodide, 100L of deionized water and 42kg of glycine.
Example 6
The present embodiment provides a method for preparing a nickel oxide target, which is different from embodiment 1 only in that the raw materials are weighed as follows: 15070.44g of nickel nitrite, 3741.1g of magnesium iodide, 100L of deionized water and 42kg of glycine. Adding nickel nitrite and magnesium iodide into water, stirring at 50 ℃ until the nickel nitrite and the magnesium iodide are completely dissolved, adding glycine, and continuously stirring at constant temperature until the nickel nitrite and the magnesium iodide are uniformly mixed to obtain a mixed solution.
Example 7
The present embodiment provides a method for preparing a nickel oxide target, which is different from embodiment 1 only in that the raw materials are weighed as follows: 9270.8g of nickel hydroxide, 3741.1g of magnesium iodide, 100L of deionized water and 42kg of glycine. Adding nickel hydroxide and magnesium iodide into water, stirring at 50deg.C until completely dissolved, adding glycine, and stirring at constant temperature until uniformly mixed to obtain mixed solution.
Example 8
The present example provides a method for preparing a nickel oxide target, which is different from example 1 only in that nickel nitrate and magnesium iodide are added into water, stirred at 40 ℃ until the nickel nitrate and magnesium iodide are completely dissolved, glycine is added, and stirring at constant temperature is continued until the nickel nitrate and magnesium iodide are uniformly mixed, so as to obtain a mixed solution. Then, the mixed solution was placed in an oven and dried under vacuum at 75 ℃ to obtain xerogel. And then placing the xerogel into a calciner, heating to 480 ℃ at a speed of 3 ℃/min, calcining for 2.5 hours at a constant temperature, ending the calcining, naturally cooling to obtain a calcined product, and grinding the calcined product to obtain the iodine/magnesium co-doped nickel oxide.
Example 9
The present example provides a method for preparing a nickel oxide target, which is different from example 1 only in that nickel nitrate and magnesium iodide are added into water, stirred at 60 ℃ until the nickel nitrate and magnesium iodide are completely dissolved, glycine is then added, and stirring at constant temperature is continued until the nickel nitrate and magnesium iodide are uniformly mixed, thus obtaining a mixed solution. Then, the mixed solution was placed in an oven and dried under vacuum at 92 ℃ to obtain xerogel. And then placing the xerogel into a calciner, heating to 620 ℃ at a speed of 3 ℃/min, calcining for 1.5 hours at a constant temperature, ending the calcining, naturally cooling to obtain a calcined product, and grinding the calcined product to obtain the iodine/magnesium co-doped nickel oxide.
Example 10
The present example provides a method for preparing a nickel oxide target, which is different from example 1 only in that nickel nitrate and magnesium iodide are added into water, stirred at 35 ℃ until the nickel nitrate and magnesium iodide are completely dissolved, glycine is added, and stirring at constant temperature is continued until the nickel nitrate and magnesium iodide are uniformly mixed, so as to obtain a mixed solution. Then, the mixed solution was placed in an oven and dried under vacuum at 72 ℃ to obtain xerogel. And then placing the xerogel into a calciner, heating to 460 ℃ at a speed of 3 ℃/min, calcining for 2.8 hours at a constant temperature, ending the calcining, naturally cooling to obtain a calcined product, and grinding the calcined product to obtain the iodine/magnesium co-doped nickel oxide.
Example 11
The present example provides a method for preparing a nickel oxide target, which is different from example 1 only in that nickel nitrate and magnesium iodide are added into water, stirred at 65 ℃ until the nickel nitrate and magnesium iodide are completely dissolved, glycine is then added, and stirring at constant temperature is continued until the nickel nitrate and magnesium iodide are uniformly mixed, thus obtaining a mixed solution. Then, the mixed solution was placed in an oven and dried under vacuum at 95℃to obtain xerogel. And then placing the xerogel into a calciner, heating to 640 ℃ at a speed of 3 ℃/min, calcining for 1.3 hours at a constant temperature, ending the calcining, naturally cooling to obtain a calcined product, and grinding the calcined product to obtain the iodine/magnesium co-doped nickel oxide.
Example 12
The present example provides a method for preparing a nickel oxide target, which differs from example 1 only in that the iodine/magnesium co-doped nickel oxide is sequentially ball-milled and sieved to obtain powder with a particle size D 50 of 21 μm, and then the powder is subjected to die filling and press molding under 0.35MPa to obtain a green body.
Example 13
The present example provides a method for preparing a nickel oxide target, which differs from example 1 only in that the iodine/magnesium co-doped nickel oxide is sequentially ball-milled and sieved to obtain powder with a particle size D 50 of 23 μm, and then the powder is subjected to die filling and press molding under 0.35MPa to obtain a green body.
Example 14
The present example provides a method for preparing a nickel oxide target, which differs from example 1 only in that the iodine/magnesium co-doped nickel oxide is sequentially ball-milled and sieved to obtain powder with a particle size D 50 of 20 μm, and then the powder is subjected to die filling and press molding under 0.35MPa to obtain a green body.
Example 15
The present example provides a method for preparing a nickel oxide target, which differs from example 1 only in that the iodine/magnesium co-doped nickel oxide is sequentially ball-milled and sieved to obtain powder with a particle size D 50 of 24 μm, and then the powder is subjected to die filling and press molding under 0.35MPa to obtain a green body.
Example 16
The present example provides a method for preparing a nickel oxide target, which differs from example 1 only in that the iodine/magnesium co-doped nickel oxide is sequentially ball-milled and sieved to obtain powder with a particle size D 50 of 22 μm, and then the powder is subjected to die filling and press molding under 0.2MPa to obtain a green body.
Example 17
The present example provides a method for preparing a nickel oxide target, which differs from example 1 only in that the iodine/magnesium co-doped nickel oxide is sequentially ball-milled and sieved to obtain powder with a particle size D 50 of 22 μm, and then the powder is subjected to die filling and press molding under 0.5MPa to obtain a green body.
Example 18
The embodiment provides a preparation method of a nickel oxide target, which is different from embodiment 1 only in that a green body is placed into a furnace, the green body is subjected to heat preservation and sintering for 10 hours at the sintering temperature of 700 ℃ and the vacuum degree of 0.1MPa, then the temperature is raised to 1300 ℃ at the heating rate of 1 ℃/min, oxygen is introduced, the vacuum degree in the furnace is controlled within the range of 0.05-0.1MPa, sintering is continued for 12 hours, sintering is stopped, a sintered product is obtained after natural cooling, and the sintered product is sequentially subjected to demoulding, cutting, polishing and trimming to obtain the nickel oxide target.
Example 19
The embodiment provides a preparation method of a nickel oxide target, which is different from embodiment 1 only in that a green body is placed into a furnace, the green body is subjected to heat preservation and sintering for 5 hours at the sintering temperature of 900 ℃ and the vacuum degree of 0.08MPa, then the temperature is raised to 1500 ℃ at the heating rate of 1 ℃/min, oxygen is introduced, the vacuum degree in the furnace is controlled within the range of 0.05-0.1MPa, sintering is continued for 5 hours, sintering is stopped, a sintered product is obtained after natural cooling, and the sintered product is sequentially subjected to demoulding, cutting, polishing and trimming to obtain the nickel oxide target.
Example 20
The embodiment provides a preparation method of a nickel oxide target, which is different from embodiment 1 only in that a green body is placed into a furnace, the green body is subjected to heat preservation and sintering for 12 hours at the sintering temperature of 600 ℃ and the vacuum degree of 0.11MPa, then the temperature is raised to 1200 ℃ at the heating rate of 1 ℃/min, oxygen is introduced, the vacuum degree in the furnace is controlled within the range of 0.1-0.12MPa, sintering is continued for 14 hours, sintering is stopped, a sintered product is obtained after natural cooling, and the sintered product is sequentially subjected to demoulding, cutting, polishing and trimming to obtain the nickel oxide target.
Example 21
The embodiment provides a preparation method of a nickel oxide target, which is different from embodiment 1 only in that a green body is placed into a furnace, the green body is subjected to heat preservation and sintering for 4 hours at the sintering temperature of 1000 ℃ and the vacuum degree of 0.06MPa, then the temperature is raised to 1600 ℃ at the heating rate of 1 ℃/min, oxygen is introduced, the vacuum degree in the furnace is controlled within the range of 0.01-0.4MPa, sintering is continued for 4 hours, sintering is stopped, a sintered product is obtained after natural cooling, and the sintered product is sequentially subjected to demoulding, cutting, polishing and trimming to obtain the nickel oxide target.
Example 22
The embodiment provides a preparation method of a nickel oxide target, which comprises the following steps:
The raw materials are weighed as follows: 18270g of nickel nitrate, 2618.77g of magnesium iodide, 100L of deionized water, 42kg of glycine and 45g of zirconia.
Adding nickel nitrate and magnesium iodide into water, stirring at 50 ℃ until the nickel nitrate and the magnesium iodide are completely dissolved, adding glycine, and continuously stirring at constant temperature until the nickel nitrate and the magnesium iodide are uniformly mixed to obtain a mixed solution. Then, the mixed solution was placed in an oven and dried under vacuum at 88 ℃ to obtain xerogel. And then placing the xerogel into a calciner, heating to 550 ℃ at a speed of 3 ℃/min, calcining for 2 hours at a constant temperature, ending the calcining, naturally cooling to obtain a calcined product, and grinding the calcined product to obtain the iodine/magnesium co-doped nickel oxide.
Mixing 45g of zirconia and 1000g of iodine/magnesium co-doped nickel oxide, sequentially performing ball milling and sieving to obtain powder with the particle size D 50 of 22 mu m, filling the powder into a mold, and performing compression molding under the pressure of 0.35MPa to obtain a blank body.
Then placing the green body into a furnace, preserving heat and sintering for 8 hours at the sintering temperature of 800 ℃ and the vacuum degree of 0.08MPa, then heating to 1400 ℃ at the heating rate of 1 ℃/min, introducing oxygen, controlling the vacuum degree in the furnace within the range of 0.05-0.1MPa, continuing sintering for 8 hours, stopping sintering, naturally cooling to obtain a sintering product, and sequentially demoulding, cutting, polishing and trimming the sintering product to obtain the nickel oxide target.
Example 23
The present embodiment provides a method for preparing a nickel oxide target, which is different from embodiment 22 only in that the raw materials are weighed as follows: 18270g of nickel nitrate, 2618.77g of magnesium iodide, 100L of deionized water, 42kg of glycine and 30g of zirconia.
Mixing 30g of zirconia and 1000g of iodine/magnesium co-doped nickel oxide, sequentially performing ball milling and sieving to obtain powder with the particle size D 50 of 22 mu m, filling the powder into a mold, and performing compression molding under the pressure of 0.35MPa to obtain a blank body.
Example 24
The present embodiment provides a method for preparing a nickel oxide target, which is different from embodiment 22 only in that the raw materials are weighed as follows: 18270g of nickel nitrate, 2618.77g of magnesium iodide, 100L of deionized water, 42kg of glycine and 60g of zirconia.
Mixing 60g of zirconia and 1000g of iodine/magnesium co-doped nickel oxide, sequentially performing ball milling and sieving to obtain powder with the particle size D 50 of 22 mu m, filling the powder into a mold, and performing compression molding under the pressure of 0.35MPa to obtain a blank body.
Example 25
The present embodiment provides a method for preparing a nickel oxide target, which is different from embodiment 22 only in that the raw materials are weighed as follows: 18270g of nickel nitrate, 2618.77g of magnesium iodide, 100L of deionized water, 42kg of glycine and 25g of zirconia.
Mixing 25g of zirconia and 1000g of iodine/magnesium co-doped nickel oxide, sequentially performing ball milling and sieving to obtain powder with the particle size D 50 of 22 mu m, filling the powder into a mold, and performing compression molding under the pressure of 0.35MPa to obtain a blank body.
Example 26
The present embodiment provides a method for preparing a nickel oxide target, which is different from embodiment 22 only in that the raw materials are weighed as follows: 18270g of nickel nitrate, 2618.77g of magnesium iodide, 100L of deionized water, 42kg of glycine and 65g of zirconia.
Mixing 65g of zirconia and 1000g of iodine/magnesium co-doped nickel oxide, sequentially performing ball milling and sieving to obtain powder with the particle size D 50 of 22 mu m, filling the powder into a mold, and performing compression molding under the pressure of 0.35MPa to obtain a blank body.
Comparative example
Comparative example 1
This comparative example provides a method for producing a nickel oxide target, which differs from example 1 only in that magnesium iodide is not contained.
Comparative example 2
This comparative example provides a method for preparing a nickel oxide target, which differs from example 1 only in that glycine is not included.
Comparative example 3
The comparative example provides a preparation method of a nickel oxide target, which is different from example 1 only in that nickel nitrate and magnesium iodide are uniformly mixed, then the mixture is directly put into a calciner, the temperature is raised to 550 ℃ at 3 ℃/min, the calcination is performed for 2 hours at constant temperature, the calcination is finished, the natural cooling is performed, a calcination product is obtained, and the calcination product is ground to obtain the iodine/magnesium co-doped nickel oxide.
Performance test
For the nickel oxide targets provided in examples 1-26 and comparative examples 1-3, the following performance tests were performed:
Resistivity: the resistivity of the nickel oxide target was measured according to GB/T40007-2021.
Relative density: the relative density of the nickel oxide target was determined using archimedes method.
Yield rate: each of the examples and comparative examples was prepared with 50 nickel oxide target samples, and whether the surface of each nickel oxide target sample was cracked or not was observed, and no cracking was good, and the yield = good number ≡50×100%.
The above test results are shown in Table 1.
TABLE 1
As can be seen from the combination of examples 1 and comparative examples 1 to 3 and table 1, the nickel oxide target of example 1 has lower resistivity, significantly higher relative density and yield than those of comparative examples 1 to 2, which means that the nickel oxide target having better conductivity and less prone to cracking can be obtained in the presence of magnesium iodide and glycine at the same time and under the process conditions of example 1. This demonstrates that there is a synergy between magnesium iodide, glycine and process conditions, by which the present application achieves the effects of improving the electrical conductivity of the nickel oxide target and reducing cracking of the nickel oxide target.
As can be seen from examples 1-5 in combination with table 1, the nickel oxide targets of examples 1,2 and 4 have progressively increasing resistivity but progressively decreasing relative density and yield, the resistivity of example 3 is less than that of example 1, but the yield of example 3 becomes smaller, the resistivity of example 5 is greater than that of example 3 but less than that of example 1, and the yield of example 5 is less than that of example 3. This means that when the molar ratio of nickel oxide to magnesium iodide is in the range of (5-9), the nickel oxide target prepared has both excellent electrical conductivity and high yield, and in the case of an embodiment outside this molar ratio range, at least one of the electrical conductivity and yield of the nickel oxide target is lowered.
As can be seen from examples 1 and examples 6 to 7, and from table 1, the resistivity, the relative density, and the yield of examples 6 to 7 were less changed than that of example 1, which suggests that nickel oxide targets excellent in conductivity and yield can be obtained by using any of nickel nitrate, nickel nitrite, and nickel hydroxide as the nickel salt.
As can be seen from the combination of examples 1 and examples 8 to 11 and table 1, the resistivity of examples 1 and examples 8 to 11 is less variable, but the yield of example 11 is lower, which indicates that the process conditions of examples 1 and examples 8 to 9 are used to help reduce the cracking of the nickel oxide target.
As can be seen from the combination of examples 1, 12-17 and Table 1, the resistivity and the relative density of examples 12-13 and examples 16-17 are small, the yield is over 96%, the resistivity of examples 14-15 is large, and the yield is 94% or less, which means that the nickel oxide target cracking is reduced under the process conditions that the particle diameter D 50 of the powder is 21-23 μm and 0.2-0.5 MPa.
As can be seen from the combination of examples 1 and examples 18 to 21 and the combination of Table 1, the resistivity and the relative density of examples 18 to 21 are less varied, but the yields of examples 18 to 19 are 96% or more and the yields of examples 20 to 21 are 90% or less, which means that the firing process conditions of examples 18 to 19 are conducive to improving the conductivity of the nickel oxide target and reducing the cracking of the nickel oxide target.
As can be seen from the combination of the embodiment 1 and the embodiments 22 to 26 and the table 1, the resistivities of the embodiments 22 to 26 are all significantly reduced, the relative densities are all significantly increased, the yields of the embodiments 22 to 24 reach 100%, but the yields of the embodiments 25 to 26 are all 98, which means that the conductivity of the nickel oxide target is improved when zirconia is added, and the addition ratio of the zirconia is controlled within the range of the embodiments 22 to 24, which is helpful for further improving the yields of the nickel oxide target.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (4)
1. The preparation method of the nickel oxide target is characterized by comprising the following steps:
Iodine/magnesium co-doping: adding nickel salt and magnesium iodide into water, stirring at 40-60 ℃ until the nickel salt and the magnesium iodide are completely dissolved, adding glycine, uniformly mixing, drying at 75-92 ℃ to obtain xerogel, calcining the xerogel at 480-620 ℃ for 1.5-2.5h to obtain a calcined product, and grinding the calcined product to obtain iodine/magnesium co-doped nickel oxide;
blank manufacturing: ball milling and sieving the iodine/magnesium co-doped nickel oxide to obtain powder, and filling and pressing the powder to obtain a blank;
Firing: after the blank is sintered by vacuum hot pressing, demoulding, cutting, polishing and trimming are carried out to obtain a nickel oxide target material; in the iodine/magnesium co-doping step, the molar ratio of the nickel salt to the magnesium iodide is 100 (5-9); in the iodine/magnesium co-doping step, the nickel salt is any one of nickel nitrate, nickel nitrite or nickel hydroxide; the blank making step comprises the following steps: ball milling and sieving the iodine/magnesium co-doped nickel oxide to obtain powder, wherein the particle size D 50 of the powder is 21-23 mu m; after the powder is die-filled, the powder is pressed and molded under the pressure of 0.2MPa to 0.5MPa to obtain a blank; the firing steps are as follows: and (3) carrying out heat preservation and sintering on the green body for 5-10 hours at the sintering temperature of 700-900 ℃ and the vacuum degree of 0.08-0.1MPa, then raising the sintering temperature to 1300-1500 ℃, introducing oxygen, keeping the vacuum degree of 0.05-0.1MPa, continuing sintering for 5-12 hours to obtain a sintering product, and demoulding, cutting, polishing and trimming the sintering product to obtain the nickel oxide target.
2. The method for producing a nickel oxide target according to claim 1, wherein the step of producing a blank further comprises zirconia, and wherein in the step of producing a blank: mixing zirconium oxide and iodine/magnesium co-doped nickel oxide, ball milling, sieving to obtain powder, and molding and pressing the powder to obtain a blank.
3. The method for preparing a nickel oxide target according to claim 2, wherein the weight ratio of the zirconium oxide to the iodine/magnesium co-doped nickel oxide is (3-6): 100.
4. Use of a nickel oxide target, characterized in that the nickel oxide target is produced by the method for producing a nickel oxide target according to any one of claims 1-3, for producing a hole transport layer in a perovskite solar cell.
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