CN108530053B - PH value sensitive color-changing inorganic material and preparation method thereof - Google Patents
PH value sensitive color-changing inorganic material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011147 inorganic material Substances 0.000 title claims abstract description 17
- 229910010272 inorganic material Inorganic materials 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 58
- 238000000498 ball milling Methods 0.000 claims abstract description 40
- 239000000919 ceramic Substances 0.000 claims abstract description 29
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000668 LiMnPO4 Inorganic materials 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 10
- 238000007873 sieving Methods 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000839 emulsion Substances 0.000 claims abstract description 8
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 8
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 8
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- 238000005469 granulation Methods 0.000 claims abstract description 3
- 230000003179 granulation Effects 0.000 claims abstract description 3
- 238000005360 mashing Methods 0.000 claims abstract description 3
- 239000011812 mixed powder Substances 0.000 claims abstract 8
- 238000000034 method Methods 0.000 claims description 16
- 230000008859 change Effects 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910006209 Li1+xAlxTi2−x Inorganic materials 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052609 olivine Inorganic materials 0.000 claims description 5
- 239000010450 olivine Substances 0.000 claims description 5
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- 238000003825 pressing Methods 0.000 claims description 3
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract 1
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000010936 titanium Substances 0.000 description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- 125000003158 alcohol group Chemical group 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
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- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
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- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000001980 ionochromic effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
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- 238000001139 pH measurement Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- PRZSXZWFJHEZBJ-UHFFFAOYSA-N thymol blue Chemical compound C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C(=CC(O)=C(C(C)C)C=2)C)=C1C PRZSXZWFJHEZBJ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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Abstract
The invention discloses a pH value sensitive color-changing inorganic material and a preparation method thereof. The preparation method comprises the following steps: with Li2CO3Ammonium polyphosphate, Al2O3、TiO2、MnCO3Synthesis of LATP and LiMnPO4Ceramic powder, LATP ceramic powder and 10-40% LiMnPO4Mixing the ceramic powder, adding alcohol, and performing ball milling, drying and sieving to obtain mixed powder; adding a binder into the mixed powder for granulation, tabletting, preparing a green body, and sintering in an atmosphere to prepare the pH value sensitive color-changing ceramic; and directly sintering the mixed powder in the atmosphere, mashing, ball-milling and sieving to obtain pH value sensitive color-changing powder, and mixing the color-changing powder with other resin solution or emulsion to obtain the pH value sensitive color-changing coating or film material. The pH value sensitive color-changing inorganic material prepared by the invention is safe and reliable, has simple preparation process, is economic and environment-friendly, and can realize industrial production.
Description
Technical Field
The invention relates to the technical field of color-changing materials, in particular to a preparation method of a pH value sensitive color-changing inorganic material.
Background
Color plays a very important role in people's daily life, and color changes can be used as an important visual signal. In recent decades, color-changing materials that reversibly change color upon exposure to external stimuli have attracted considerable attention. For example, photochromic materials are induced by light to change color, thermochromic materials are induced by heat to change color, and ionochromic materials are induced by ions to change color. The color-changing materials have long been used in our daily life, such as goggles made of photochromic lenses, thermochromic temperature indicators on baby spoons, and the like.
The pH-sensitive color-changing material is a material that changes color in a solution due to a change in pH of the solution. The pH is one of the most important physicochemical parameters of aqueous solutions. All natural phenomena, chemical changes and processes involving aqueous solutions are related to pH, and therefore, pH measurements are needed in the industrial, agricultural, medical, environmental and scientific fields. Two of the three commonly used pH value measuring methods (chemical titration method, test paper method and electrode potential method) are used as pH value sensitive color-changing materials. The electrode potential method is superior to the former two in universality and cost because of the need of special instruments and the need of maintenance of the instruments.
The pH value sensitive color-changing material mainly comprises organic materials such as methyl red, bromocresol green, thymol blue, phthalide, azo dyes, complex formed by metal ions and chelate, and the like, and the reports of inorganic materials are less. Organic materials have many advantages, but the preparation process is cumbersome and the yield is not high, and various waste liquids are generated during the preparation process, which must be treated without harms before being discharged, increasing the manufacturing cost. Also, some organic materials may themselves be carcinogenic or cause other diseases.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the preparation method of the pH value sensitive color-changing inorganic material, which has the advantages of simple preparation process, economy, energy conservation, safety, environmental protection and no pollution in each link.
The purpose of the invention is realized by the following technical scheme:
a pH value sensitive color-changing inorganic material and a preparation method thereof, which take ammonium polyphosphate as a phosphorus source, lithium carbonate as a lithium source, titanium dioxide as a titanium source, alumina as an aluminum source and manganese carbonate as a manganese source, concretely comprises the following steps:
(1) mixing Li with purity of more than 99%2CO3Ammonium polyphosphate, Al2O3、TiO2According to Li1+xAlxTi2-xP3O12(LATP) formula, wherein x = 0.3-0.4. Ball-milling for 90 minutes (solvent is alcohol, rotating speed is 300R/min), drying, pre-sintering in air to obtain ceramic powder, wherein the pre-sintered powder has a Nasicon structure as main crystal phase and R3C as space group. The planetary ball milling is carried out in a ball milling tank, the ball milling tank is made of polytetrafluoroethylene, a ball milling medium is 1mm zirconium dioxide balls, and a solvent is alcohol, wherein the volume ratio of the balls to the powder to the alcohol is 1:1: 1.1.
(2) With purity of over 99% Li2CO3、MnCO3Ammonium polyphosphate as raw material according to LiMnPO4And (3) ball-milling and mixing the formula ingredients for 90 minutes, drying and then pre-burning in an air atmosphere to obtain pre-burned LMP powder. The powder material has a single-phase orthogonal olivine crystal structure, and the space group is Pmnb.
(3) Mixing the pre-burned LATP powder with LMP, adding alcohol, carrying out planetary ball milling for 90 minutes, drying and sieving to obtain powder.
(4) And (4) adding the powder obtained in the step (3) into a binder for granulation, pressing out a wafer green compact with the diameter of 15 mm and the thickness of 2 mm under the pressure of 10MPa by uniaxial pressing, and finally sintering in an atmospheric atmosphere to prepare the pH value sensitive color-changing ceramic.
(5) And (4) sintering the powder in the step (3) in an atmospheric atmosphere, and then mashing, ball-milling and sieving the sintered blocks to prepare the pH value sensitive color-changing inorganic powder. Mixing the sensitive color-changing inorganic powder with the resin solution according to the mass ratio of 1:1, coating the mixture on a ceramic substrate, and drying the ceramic substrate at 80 ℃ for 1 hour to obtain a pH value sensitive color-changing coating, or mixing the sensitive color-changing inorganic powder with the emulsion according to the mass ratio of 3:10, and drying the mixture at 80 ℃ for 1 hour to obtain the pH value sensitive color-changing film.
Preferably, the pre-sintering temperature in the step (1) is 750-800 ℃, and the time is 2-3 hours.
Preferably, the pre-sintering temperature in the step (2) is 550-650 ℃, and the time is 2-3 hours.
Preferably, the LMP proportion in the step (3) is 10-40%.
Preferably, the ball milling time in the steps (1), (2) and (3) is 60-120 minutes.
Preferably, the binder in the step (4) is a polyvinyl alcohol solution with the mass concentration of 10%, and the proportion is 5-15%.
Preferably, the sintering temperature in the steps (4) and (5) is 800-900 ℃ and the time is 2-4 hours.
Preferably, in the step (5), the resin solution is acrylic resin, and the emulsion is polytetrafluoroethylene emulsion.
Preferably, in the step (5), the powder, the resin solution and the emulsion are mixed according to a mass ratio of 1: 1-1: 5, and are dried for 1-3 hours at a temperature of 80-120 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the pH value sensitive color-changing ceramic prepared by the invention has the advantages of high temperature resistance, ageing resistance, suitability for various environments and long-term storage. Compared with equipment such as a pH meter, an online pH meter and the like, the pH meter is low in price, simple to use and free of maintenance; compared with an organic color-changing material, the preparation process is environment-friendly and pollution-free, does not need to carry out harmless treatment on the discharged product, reduces the cost, and is green and healthy.
(2) The invention uses the solid-phase sintering method to prepare the pH value sensitive color-changing inorganic material, the preparation method is easy to operate, the required equipment is simple, the cost is low, and industrialization can be rapidly formed.
(3) The invention can be applied in several fields: a pH value sensor, a color-changing dye, a color-changing warning coating and the like. Due to the reversible color change characteristic, the product can be repeatedly used.
(4) The invention has a new idea on the color change principle design, the composite material comprises a lithium ion electrolyte material and a lithium ion anode battery material, the transmission of lithium ions between the two materials is fully utilized, the valence change of the two transition metal ions under the induction of acid and alkali is realized, and the obvious color change effect is achieved.
Drawings
FIG. 1a is a Ti element X-ray photoelectron spectroscopy (XPS) graph of a LATP/LMP color-changing material before an alkali treatment color-changing treatment.
FIG. 1b is a Ti element X-ray photoelectron spectroscopy (XPS) graph of the LATP/LMP color-changing material after the alkali treatment color-changing treatment.
FIG. 1c is a Ti element X-ray photoelectron spectroscopy (XPS) graph of the LATP/LMP color-changing material after the sample is subjected to acid treatment and inverse color-changing treatment in b.
FIG. 2a and FIG. 2b are Mn element X-ray photoelectron spectroscopy (XPS) charts of the LATP/LMP color-changing material before and after the alkali treatment color-changing treatment, respectively.
FIG. 3 is a schematic diagram showing the change of color of the LATP/LMP color-changing ceramic prepared in example 1 of this experiment under alkaline conditions and reversible change of color under acidic conditions.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
preparation of pH value sensitive allochroic ceramic
(1) Mixing Li with purity of more than 99%2CO3Ammonium polyphosphate, Al2O3、TiO2According to Li1+xAlxTi2-xP3O12(LATP) formula blend, wherein x = 0.3. Ball-milling for 60 minutes by a planet (the solvent is alcohol, the rotating speed is 300R/min), drying, pre-burning in air at 800 ℃ for 2 hours to prepare ceramic powder, wherein the main crystal phase of the pre-burned powder is Nasicon structure, and the space group is R3C. The planetary ball milling is carried out in a ball milling tank, the ball milling tank is made of polytetrafluoroethylene, a ball milling medium is 1mm zirconium dioxide balls, and a solvent is alcohol, wherein the volume ratio of the balls to the powder to the alcohol is 1:1: 1.1.
(2) With purity of over 99% Li2CO3、MnCO3Ammonium polyphosphate as raw material according to LiMnPO4Molecular formula ingredients are ball milledMixing for 60 minutes, drying, and presintering for 2 hours in an air atmosphere at 650 ℃ to obtain the presintered LMP powder. The powder material has a single-phase orthogonal olivine crystal structure, and the space group is Pmnb.
(3) Mixing the pre-burned LATP powder with LMP with the mass ratio of 10%, adding alcohol, carrying out planetary ball milling for 60 minutes, adding a binder with the mass ratio of 10% into the dried and sieved powder, and granulating to obtain powder. Pressing out a wafer green compact with the diameter of 15 mm and the thickness of 2 mm by uniaxial pressing at the pressure of 10MPa, and finally sintering at 900 ℃ for 3 hours in atmospheric atmosphere to prepare the pH value sensitive color-changing ceramic. The effect is shown in figure 3: the pH value sensitive color-changing ceramic is purple, can present gray, dark brown or even black after being treated by an alkaline solution with the pH value of 12-14 for 0.5-6 h, and can be restored to the original purple after being treated by an acidic solution with the pH =1 for 3-15 min, and the process can be repeated for many times.
According to the X-ray photoelectron spectrum of FIG. 1, Ti element is in positive quadrivalence (a, c) when the sample is in the original color, and a peak in positive tervalence (b) appears after the alkali treatment discoloration, which indicates that Ti element is reduced during the discoloration process. According to the X-ray photoelectron spectrum of FIG. 2, the Mn element is (a) in the positive divalent state when the sample is in the original color, and (b) shows a peak in the positive trivalent state after the alkali treatment for color change, which indicates that the Mn element is oxidized during the color change. LATP is a lithium-ion electrolyte material with a three-dimensional framework that facilitates the transport of lithium ions between them. LMP is an anode material of lithium ion battery with high Li/Li content+The redox potential (4.1V) is such that the Mn element is converted into valence by intercalation/deintercalation of lithium ions during charge and discharge. After co-firing, the LMP cells are covered by LATP cells, which are oxidized during alkali treatment, when lithium ions have to conduct through LATP, during which Ti is reduced. The oxidation of the Mn element and the reduction of the Ti element together cause discoloration of the sample. In the acid treatment reverse discoloration process, H+Trivalent Ti is oxidized together with air to replace lithium ions, so that the lithium ions are inserted into LMP, and Mn element is reduced.
Example 2
preparation of pH value sensitive allochroic paint
(1) Mixing Li with purity of more than 99%2CO3Ammonium polyphosphate, Al2O3、TiO2According to Li1+xAlxTi2-xP3O12(LATP) formula (i) blend, wherein x = 0.4. Ball-milling for 120 minutes in a planetary way (the solvent is alcohol, the rotating speed is 300R/min), drying, presintering in air at 750 ℃ for 3 hours to prepare ceramic powder, wherein the presintering powder has a Nasicon structure as a main crystal phase, and the space group is R3C. The planetary ball milling is carried out in a ball milling tank, the ball milling tank is made of polytetrafluoroethylene, a ball milling medium is 1mm zirconium dioxide balls, and a solvent is alcohol, wherein the volume ratio of the balls to the powder to the alcohol is 1:1: 1.1.
(2) With purity of over 99% Li2CO3、MnCO3Ammonium polyphosphate as raw material according to LiMnPO4The formula ingredients are ball-milled and mixed for 120 minutes, and then are pre-sintered for 3 hours in air atmosphere at 550 ℃ after being dried, so as to obtain pre-sintered LMP powder. The powder material has a single-phase orthogonal olivine crystal structure, and the space group is Pmnb.
(3) Mixing the pre-sintered LATP powder with LMP with the mass ratio of 40%, adding alcohol, carrying out planetary ball milling for 90 minutes, sintering the dried and sieved powder for 2 hours at 800 ℃ in an atmosphere, crushing the sintered block, carrying out ball milling and sieving, and preparing the pH value sensitive color-changing inorganic powder.
(4) And mixing the sensitive color-changing inorganic powder with the acrylic resin emulsion in a mass ratio of 1:1, and ultrasonically stirring for 1h to obtain the pH value sensitive color-changing coating. Coating the coating on a ceramic substrate in a coating manner, and drying at 80 ℃ for 1h to obtain the pH value sensitive color-changing coating.
Example 3
preparation of pH value sensitive color-changing film layer
(1) Mixing Li with purity of more than 99%2CO3Ammonium polyphosphate, Al2O3、TiO2According to Li1+xAlxTi2-xP3O12(LATP) formula (i) blend, wherein x = 0.35. Ball-milling with a planet ball for 90 min (solvent is alcohol, rotation speed is 300 r/min), oven-drying, and heating at 775 deg.CAnd pre-burning in air for 2.5 hours to obtain ceramic powder, wherein the main crystal phase of the pre-burned powder is of a Nasicon structure, and the space group is R3C. The planetary ball milling is carried out in a ball milling tank, the ball milling tank is made of polytetrafluoroethylene, a ball milling medium is 1mm zirconium dioxide balls, and a solvent is alcohol, wherein the volume ratio of the balls to the powder to the alcohol is 1:1: 1.1.
(2) With purity of over 99% Li2CO3、MnCO3Ammonium polyphosphate as raw material according to LiMnPO4The formula ingredients are ball-milled and mixed for 90 minutes, and then are pre-sintered for 2.5 hours in the air atmosphere at 600 ℃ after being dried, so as to obtain the pre-sintered LMP powder. The powder material has a single-phase orthogonal olivine crystal structure, and the space group is Pmnb.
(3) Mixing the pre-sintered LATP powder with LMP with the mass ratio of 20%, adding alcohol, carrying out planetary ball milling for 120 minutes, sintering the dried and sieved powder for 4 hours at 850 ℃ in atmospheric atmosphere, crushing the sintered block, carrying out ball milling and sieving, and preparing the pH value sensitive color-changing inorganic powder.
(4) And mixing the sensitive color-changing inorganic powder with the polytetrafluoroethylene emulsion according to the mass ratio of 1:5, and drying at 120 ℃ for 3h to obtain the pH value sensitive color-changing film.
Claims (10)
1. A preparation method of a pH value sensitive color-changing inorganic material is characterized by comprising the following steps:
(1) mixing Li2CO3Ammonium polyphosphate, Al2O3、TiO2According to Li1+xAlxTi2-xP3O12Carrying out ball milling and mixing on molecular formula ingredients, drying, and presintering at 750-800 ℃ for 2-3 hours to obtain LATP ceramic powder; wherein x is more than or equal to 0.3 and less than or equal to 0.4;
(2) with Li2CO3、MnCO3Ammonium polyphosphate as raw material according to LiMnPO4Mixing the materials according to the molecular formula, ball-milling, drying, and presintering in air atmosphere at 550-650 ℃ for 2-3 hours to obtain LiMnPO4Ceramic powders, i.e., LMP;
(3) mixing the LATP ceramic powder with LMP, adding alcohol, ball-milling, drying and sieving to obtain mixed powder;
(4) adding a binder with the mass ratio of 5-15% into the prepared mixed powder for granulation to obtain new mixed powder; and pressing out a wafer green compact with the diameter of 15 mm and the thickness of 2 mm by uniaxial pressing at the pressure of 10MPa, and sintering in an atmospheric atmosphere to obtain the pH value sensitive color-changing ceramic.
2. The method for preparing the pH-sensitive color-changing inorganic material according to claim 1, wherein the ball milling in the steps (1), (2) and (3) is planetary ball milling, the rotating speed is 300 r/min, and the time is 60-120 min.
3. The method as claimed in claim 1, wherein the LATP ceramic powder obtained in step (1) has a Nasicon structure as a main crystal phase and R3C as a space group.
4. The method of claim 1, wherein the LiMnPO of the step (2) is formed by a method of forming a pH-sensitive color-changing inorganic material4The powder is in the orthorhombic olivine phase and the space group is Pmnb.
5. The method as claimed in claim 1, wherein said LATP ceramic powder of step (3) is mixed with LiMnPO4Mixing ceramic powder, wherein the LMP ratio is 10-40%.
6. The method for preparing the inorganic material with the pH value sensitive color change according to claim 1, wherein the binder in the step (4) is a polyvinyl alcohol solution with a mass concentration of 10%, the addition amount is 5-15% of the ceramic powder by mass, the sintering temperature is 800-900 ℃, and the time is 2-4 hours.
7. A preparation method of a pH value sensitive color-changing inorganic material is characterized by comprising the following steps:
(1) mixing Li2CO3Ammonium polyphosphate, Al2O3、TiO2According to Li1+xAlxTi2-xP3O12Carrying out ball milling and mixing on molecular formula ingredients, drying, and presintering at 750-800 ℃ for 2-3 hours to obtain LATP ceramic powder; wherein x is more than or equal to 0.3 and less than or equal to 0.4;
(2) with Li2CO3、MnCO3Ammonium polyphosphate as raw material according to LiMnPO4Mixing the materials according to the molecular formula, ball-milling, drying, and presintering in air atmosphere at 550-650 ℃ for 2-3 hours to obtain LiMnPO4Ceramic powders, i.e., LMP;
(3) mixing the LATP ceramic powder with LMP, adding alcohol, ball-milling, drying and sieving to obtain mixed powder;
(4) sintering the prepared mixed powder for 2-4 hours at 800-900 ℃ in an atmosphere, and mashing, ball-milling and sieving the sintered blocks to prepare the pH value sensitive color-changing inorganic powder.
8. A method for preparing a pH-sensitive color-changing inorganic material, characterized in that the pH prepared according to claim 7 is used
The sensitive color-changing inorganic powder and the acrylic resin solution are mixed according to the mass ratio of 1: 1-1: 5, coated on a ceramic substrate, and dried at 80-120 ℃ for 1-3 hours to obtain the pH value sensitive color-changing coating.
9. A preparation method of a pH value sensitive color-changing inorganic material is characterized in that the pH value sensitive color-changing inorganic powder prepared according to claim 7 and tetrafluoroethylene emulsion are dried for 1-3 hours at 80-120 ℃ in a mass ratio of 1: 1-1: 5 to obtain a pH value sensitive color-changing film.
10. The pH-sensitive color-changing inorganic material prepared by the preparation method of any one of claims 1 to 9.
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