CN116189799A - Nickel tin oxide solid ion storage layer and preparation method and application thereof - Google Patents
Nickel tin oxide solid ion storage layer and preparation method and application thereof Download PDFInfo
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- ZAJDUICOHISPCL-UHFFFAOYSA-N nickel;oxotin Chemical compound [Ni].[Sn]=O ZAJDUICOHISPCL-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000007787 solid Substances 0.000 title claims abstract description 69
- 238000003860 storage Methods 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 22
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 12
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 238000004544 sputter deposition Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 9
- 239000010405 anode material Substances 0.000 abstract description 7
- 230000004044 response Effects 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 229910002640 NiOOH Inorganic materials 0.000 description 7
- 239000011521 glass Substances 0.000 description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- 238000001420 photoelectron spectroscopy Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910005887 NiSn Inorganic materials 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 229910018661 Ni(OH) Inorganic materials 0.000 description 2
- -1 NiO and Ni 2 O 3 Chemical class 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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Abstract
The invention belongs to the technical field of electrochromic devices, and discloses a nickel tin oxide solid ion storage layer, a preparation method and application thereof. The invention provides a method for preparing the solid ion storage layer in the electrochromic device by combining magnetron sputtering and alkali treatment, which improves the electrochemical capacity and visible light transmittance of the solid ion storage layer. The solid ion storage layer film obtained by the invention has the characteristics of high stability, strong adhesive force, large change range of transmittance, high color change response speed and the like. The resulting solid ion storage layer film is useful as an anode material for all-solid electrochromic devices, resulting in significant improvements in device performance such as cycle durability, optical dimming amplitude, and response time.
Description
Technical Field
The invention relates to the technical field of electrochromic devices, in particular to a nickel tin oxide solid ion storage layer, a preparation method and application thereof.
Background
Electrochromic refers to the optical properties of a material, such as transmittance, that changes reversibly in color under low voltage driving, changing in appearance as a reversible change between blue and transparent states. Electrochromic has excellent sunlight adjusting function as a hot spot for research at present and has wide application field. The electrochromic device and the technology are mainly applied to the fields of automobile anti-dazzle rearview mirrors, energy-saving building glass, other moving body windows, display screens, electronic paper, camouflage and the like. The solid ion storage layer is a film material which assists the electrochromic layer to generate oxidation-reduction reaction in the ion migration or migration process, the electrochemical capacity of the transition metal oxide film prepared directly by magnetron sputtering is low, the valence state control of the reactive sputtering is difficult, the color change amplitude is weak, the contribution rate to electrochromic devices is low, and the solid ion storage layer is mainly inorganic transition metal oxides such as Cr2O3, co2O3, mnO2, tiO2, ir2O3 and NiO. Wherein, the nickel oxide is 3d transition metal oxide, the structure of the nickel oxide is mainly NaCl which belongs to a close-packed face-centered cubic structure, and the nickel oxide has good electrochromic property. The function of the device is that ions migrate in or out under the drive of voltage to cause reversible oxidation-reduction reaction of the ion storage layer, and the ion storage layer and the electrochromic layer are paired to form reversible change between a color state and a transparent state in appearance.
The nickel oxide film is obtained by the methods of heating the substrate, cold treatment of the substrate, post-oxidation treatment and the like in the film deposition process, and the obtained film has low transmittance and can be converted into transparent nickel oxide by complex post-treatment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the nickel tin oxide solid ion storage layer, the preparation method and the application thereof, and the obtained nickel tin oxide solid ion storage layer has the characteristics of higher transparency, higher color changing efficiency and better electrochemical capacity.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a nickel tin oxide solid ion storage layer, which comprises the following steps: preparing a nickel tin oxide film on a substrate by direct current pulse magnetron sputtering, and performing alkali treatment to obtain a nickel tin oxide solid ion storage layer loaded on the substrate;
the substrate is ITO, FTO or AZO deposited on the transparent substrate.
Preferably, when the nickel tin oxide film is prepared by the direct current pulse magnetron sputtering, the temperature of the substrate is between-20 and 400 ℃; background vacuum degree of 1×10 -5 ～5×10 -4 Pa; the coating time is 20-60 min, and the working air pressure is 0.5-5 Pa.
Preferably, when the nickel tin oxide film is prepared by the direct current pulse magnetron sputtering, the sputtering working atmosphere is a mixed gas of oxygen and argon, and the oxygen ratio in the mixed gas is 5-100%; the power density of sputtering is 0.5-5W/cm 2 。
Preferably, the specific steps of the alkali treatment are as follows: and (3) placing the material prepared by the direct current pulse magnetron sputtering in a sodium hydroxide solution, and treating to obtain the nickel tin oxide solid ion storage layer.
Preferably, the concentration of the sodium hydroxide solution is 0.2 to 2M.
Preferably, the alkali treatment is performed under a direct-current voltage of ±1 to ±10v.
Preferably, the alkali treatment is performed for 20 to 180 seconds.
Preferably, the thickness of the nickel tin oxide solid ion storage layer in the nickel tin oxide solid ion storage layer loaded on the substrate is 30-500 nm.
The invention also provides the nickel tin oxide solid ion storage layer loaded on the substrate, which is prepared by the preparation method of the nickel tin oxide solid ion storage layer.
The invention also provides application of the nickel tin oxide solid ion storage layer loaded on the substrate in an all-solid-state electrochromic device.
Compared with the prior art, the invention has the following beneficial effects:
(1) The nickel tin oxide solid ion storage layer obtained by the method has the characteristics of higher transparency, higher color changing efficiency and better electrochemical capacity;
(2) The full-solid electrochromic device prepared by the nickel tin oxide solid ion storage layer loaded on the substrate has the advantages of improved transmittance, faster response speed and greatly improved cycle durability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the transmittance of the nickel tin oxide solid ion storage layer supported on a substrate and the nickel tin oxide solid ion storage layer supported on a substrate without alkali treatment obtained in example 1;
FIG. 2 is a graph showing the transmittance and reflectance of an anode material of an all-solid electrochromic device using the nickel tin oxide solid ion storage layer supported on a substrate obtained in example 1;
FIG. 3 is a photoelectron spectroscopy (XPS) spectrum of the anode material of the all-solid electrochromic device obtained from the nickel tin oxide solid ion storage layer supported on the substrate obtained in example 1;
FIG. 4 is a photoelectron spectroscopy (XPS) spectrum of the anode material of the all-solid electrochromic device obtained from the nickel tin oxide solid ion storage layer supported on the substrate obtained in example 2;
FIG. 5 is a cyclic voltammetry graph of the nickel tin oxide solid state ion storage layer supported on a substrate obtained in example 1;
FIG. 6 is a cyclic voltammetry graph of a nickel tin oxide solid state ion storage layer supported on a substrate obtained in example 3;
fig. 7 is a graph of transmittance versus response time for an all-solid state electrochromic device using the nickel tin oxide solid state ion storage layer supported on a substrate obtained in example 1.
Detailed Description
The invention provides a preparation method of a nickel tin oxide solid ion storage layer, which comprises the following steps: preparing a nickel tin oxide film on a substrate by direct current pulse magnetron sputtering, and performing alkali treatment to obtain the nickel tin oxide solid ion storage layer loaded on the substrate.
In the present invention, the base is preferably ITO, FTO, or AZO deposited on a transparent substrate, and more preferably ITO deposited on a transparent substrate.
In the invention, when the nickel tin oxide film is prepared by the direct current pulse magnetron sputtering, the temperature of the substrate is preferably-20-400 ℃, and more preferably 20-250 ℃; the background vacuum is preferably 1X 10 -5 ～5×10 -4 Pa, more preferably 1X 10 -5 ～2×10 -5 Pa; the coating time is preferably 20 to 60 minutes, more preferably 30 to 40 minutes; the working air pressure is preferably 0.5 to 5Pa, more preferably 1 to 2Pa.
In the invention, when the direct current pulse magnetron sputtering is used for preparing the nickel tin oxide film, the target material is NiSn x Or NiSn x O, wherein x is preferably in the range of 0 to 0.5, more preferably 0.1 to 0.4.
In the invention, when the nickel tin oxide film is prepared by direct current pulse magnetron sputtering, the sputtering working atmosphere is a mixed gas of oxygen and argon, and the ratio of oxygen in the mixed gas is preferably 5-100%, more preferably 20-80%, and even more preferably 40-60%; the power density of sputtering is preferably 0.5 to 5W/cm 2 More preferably 1 to 4W/cm 2 More preferably 2 to 3W/cm 2 。
In the invention, the specific steps of the alkali treatment are as follows: and (3) placing the material prepared by the direct current pulse magnetron sputtering in a sodium hydroxide solution, and treating to obtain the nickel tin oxide solid ion storage layer.
In the present invention, the concentration of the sodium hydroxide solution is preferably 0.2 to 2M, more preferably 0.5 to 1.0M.
In the present invention, the alkali treatment is performed under a direct-current voltage of preferably.+ -. 1 to.+ -. 10V, more preferably 1 to 3V.
In the present invention, the temperature of the alkali treatment is preferably from room temperature to 80 ℃, and more preferably from room temperature; the alkali treatment time is preferably 20 to 180 seconds, more preferably 30 to 60 seconds.
In the present invention, the thickness of the nickel tin oxide solid ion storage layer in the nickel tin oxide solid ion storage layer supported on the substrate is preferably 30 to 500nm, more preferably 200 to 300nm.
The film obtained by magnetron sputtering deposition is further treated by alkali solution to obtain a film material with higher transparency, and the valence state in the film is more consistent, the film becomes transparent when negative voltage is added, and the divalent component is more in the transparent state, such as NiO or Ni (OH) 2 The film turns brown when positive voltage is applied, and the component is Ni with trivalent 2 O 3 ，NiOOH。
The nickel oxide or nickel tin oxide film obtained by utilizing magnetron sputtering deposition has obviously improved electrochemical capacity after negative voltage treatment is applied to an alkali solution, and after the nickel oxide or nickel tin oxide film is used as an anode material of an electrochromic device, the transmittance is improved, the response speed is increased, and the cycle durability is also improved.
The invention also provides the nickel tin oxide solid ion storage layer loaded on the substrate, which is prepared by the preparation method of the nickel tin oxide solid ion storage layer.
The invention also provides application of the nickel tin oxide solid ion storage layer loaded on the substrate in an all-solid-state electrochromic device.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Cleaning a glass substrate: sequentially using 1M sodium hydroxide standard solution, water, absolute ethyl alcohol and water to ultrasonically clean for 10min, and drying;
preparation of nickel tin oxide film by DC pulse magnetron sputtering: placing the cleaned glass substrate into a magnetron sputtering chamber, and vacuumizing to a vacuum degree of 4×10 -5 Pa; forming a transparent conductive layer ITO on a glass substrate by using an ITO target material through a magnetron sputtering preparation method, wherein the parameters are specifically set as follows: background vacuum degree of 1×10 -5 Pa; the substrate temperature was 25 ℃; the coating time is 40min; the working air pressure is 0.1Pa; the sputtering working atmosphere is a mixed gas of argon and oxygen, and the oxygen accounts for 10 percent; the sputtering power density was 0.5W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Forming a nickel tin oxide film on the transparent conductive layer, wherein the parameters are specifically set as follows: targets made of nickel-tin alloy (NiSn) 0.5 ) Preparing a nickel tin oxide film by a magnetron sputtering method; background vacuum degree of 1×10 -5 Pa; the substrate temperature was 200 ℃; the coating time is 20min; the working air pressure is 5Pa; the sputtering working atmosphere is a mixed gas of argon and oxygen, and the oxygen accounts for 60 percent; the sputtering power density was 5W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Obtaining a nickel tin oxide solid ion storage layer loaded on a substrate, wherein the thickness of the nickel tin oxide solid ion storage layer is 100nm;
alkali treatment: and placing the nickel tin oxide solid ion storage layer loaded on the substrate in a sodium hydroxide solution with the concentration of 2M, taking a platinum electrode as an anode, taking a substrate conducting layer as a cathode, changing the color of the nickel tin oxide solid ion storage layer from brown to transparent under the drive of low voltage of 2V, drying at 250 ℃, and finally aging in air for 60min to obtain the transparent nickel tin oxide solid ion storage layer loaded on the substrate.
The whole of the transparent nickel tin oxide solid ion storage layer loaded on the substrate obtained in the embodiment is used as an anode material of an all-solid-state electrochromic device for photoelectron spectroscopy analysis, and the obtained result is shown in fig. 3.
As can be seen from fig. 3, the nickel oxide film contains divalent nickel ions and trivalent nickel ions. The method is favorable for efficiently completing electrochromic reaction, and further can improve the response time of the all-solid-state electrochromic device. The binding energy peak positions of divalent and trivalent nickel are obviously different, and the binding energy peak is wide, which indicates that the obtained transparent nickel oxide film contains various compounds, such as NiO and Ni 2 O 3 、Ni(OH) 2 NiOOH, etc.
The alkali treatment step was cycled several times to obtain a cyclic voltammetry chart of the nickel tin oxide solid ion storage layer supported on the substrate, and the obtained results are shown in fig. 5.
As can be seen from fig. 5, there are two peaks illustrated: 0.43V and 0.34-0.24V respectively. Wherein the 0.46V peak is Ni 3+ →Ni 2 + 。Ni 3+ Can be Ni 2 O 3 Or NiOOH can be a mixture of two of different proportions, and Ni is the same 2+ Can be NiO or Ni (OH) 2 Or a mixture of the two with different proportions. 0.34-0.24V peak is Ni 2+ →Ni 3+ . The peak change at 0.24V is large and the migration process can be seen as a result of indirect alkali treatment. Ni (Ni) 2+ Can be NiO or Ni (OH) 2 Or a mixture of the two materials with different proportions, and Ni is the same 3+ Can be Ni 2 O 3 Or the NiOOH can be a mixture of the two in different proportions.
Example 2
The differences from example 1 are: forming a transparent conductive layer on a glass substrate, wherein parameters are specifically set as follows: background vacuum degree is 2×10 -5 Pa; the substrate temperature was 20 ℃; the coating time is 120min; the working air pressure is 3Pa; the sputtering working atmosphere is a mixed gas of argon and oxygen, and the oxygen accounts for 20 percent; the sputtering power density was 3W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Otherwise, the same as in example 1 was conducted.
The entire transparent nickel tin oxide solid ion storage layer loaded on the substrate obtained in this example was used as the anode material of the all-solid electrochromic device for photoelectron spectroscopy, and the obtained results are shown in fig. 4.
As can be seen from fig. 4, the nickel oxide film contains divalent nickel ions and trivalent nickel ions. The method is favorable for efficiently completing electrochromic reaction, and further can improve the response time of the all-solid-state electrochromic device. The binding energy peak positions of divalent and trivalent nickel are obviously different, and the binding energy peak is wide, which indicates that the obtained transparent nickel oxide film contains various compounds, such as NiO and Ni 2 O 3 、Ni(OH) 2 NiOOH, etc.
Example 3
The differences from example 1 are: the alkali treatment comprises the following steps: placing a nickel tin oxide solid ion storage layer loaded on a substrate in a sodium hydroxide solution with the concentration of 1M, taking a platinum electrode as a counter electrode, taking ITO coated with a nickel tin oxide film as a working electrode, and taking a silver-silver chloride (Ag/AgCl) electrode as a reference electrode to reversibly circulate for a plurality of times within a voltage range of +/-1.2V, so that the color of the nickel tin oxide film is changed from brown to transparent; otherwise, the same as in example 1 was conducted.
The alkali treatment step was repeated several times to obtain a cyclic voltammetry chart of the nickel tin oxide solid ion storage layer supported on the substrate, and the obtained results are shown in fig. 6.
As can be seen from fig. 6, there are two peaks illustrated: 0.40V and 0.21-0.16V, respectively. Wherein the 0.40V peak is Ni 3+ →Ni 2 + 。Ni 3+ Can be Ni 2 O 3 Or NiOOH can be a mixture of two of different proportions, and Ni is the same 2+ Can be NiO or Ni (OH) 2 Or a mixture of the two with different proportions. 0.21-0.16V peak is Ni 2+ →Ni 3+ 。Ni 2+ Can be NiO or Ni (OH) 2 Or a mixture of the two materials with different proportions, and Ni is the same 3+ Can be Ni 2 O 3 Or the NiOOH can be a mixture of the two in different proportions.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the nickel tin oxide solid ion storage layer is characterized by comprising the following steps: preparing a nickel tin oxide film on a substrate by direct current pulse magnetron sputtering, and performing alkali treatment to obtain a nickel tin oxide solid ion storage layer loaded on the substrate;
the substrate is ITO, FTO or AZO deposited on the transparent substrate.
2. The nickel oxide according to claim 1The preparation method of the tin solid ion storage layer is characterized in that when the nickel tin oxide film is prepared by direct current pulse magnetron sputtering, the temperature of the substrate is-20-400 ℃; background vacuum degree of 1×10 -5 ～5×10 -4 Pa; the coating time is 20-60 min, and the working air pressure is 0.5-5 Pa.
3. The method for preparing the nickel tin oxide solid ion storage layer according to claim 2, wherein when the direct current pulse magnetron sputtering is used for preparing the nickel tin oxide film, the sputtering working atmosphere is a mixed gas of oxygen and argon, and the ratio of oxygen in the mixed gas is 5-100%; the power density of sputtering is 0.5-5W/cm 2 。
4. A method for preparing a nickel tin oxide solid state ion storage layer according to any one of claims 1 to 3, wherein the specific steps of the alkali treatment are: and (3) placing the material prepared by the direct current pulse magnetron sputtering in a sodium hydroxide solution, and treating to obtain the nickel tin oxide solid ion storage layer.
5. The method of claim 4, wherein the concentration of the sodium hydroxide solution is 0.2-2M.
6. The method for preparing a nickel tin oxide solid ion storage layer according to claim 5, wherein the alkali treatment is performed under a direct current voltage of + -1 to + -10V.
7. The method for preparing a solid ion storage layer of nickel tin oxide according to claim 6, wherein the alkali treatment time is 20-180 s.
8. The method according to claim 1, wherein the thickness of the nickel tin oxide solid ion storage layer in the nickel tin oxide solid ion storage layer supported on the substrate is 30 to 500nm.
9. The nickel tin oxide solid ion storage layer supported on a substrate prepared by the method for preparing the nickel tin oxide solid ion storage layer according to any one of claims 1 to 8.
10. Use of a nickel tin oxide solid state ion storage layer supported on a substrate as claimed in claim 9 in an all solid state electrochromic device.
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