CN106379942A - Preparation method of low-density foam MnOOH - Google Patents
Preparation method of low-density foam MnOOH Download PDFInfo
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- CN106379942A CN106379942A CN201610783520.3A CN201610783520A CN106379942A CN 106379942 A CN106379942 A CN 106379942A CN 201610783520 A CN201610783520 A CN 201610783520A CN 106379942 A CN106379942 A CN 106379942A
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- preparation
- mnooh
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- foam
- potassium permanganate
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- 229910003174 MnOOH Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004620 low density foam Substances 0.000 title claims abstract description 10
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 11
- 150000002696 manganese Chemical class 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 239000006260 foam Substances 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 13
- 239000002070 nanowire Substances 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 239000007772 electrode material Substances 0.000 abstract 1
- 238000009775 high-speed stirring Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229940023462 paste product Drugs 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- -1 Ru Shui Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- KQFUCKFHODLIAZ-UHFFFAOYSA-N manganese Chemical compound [Mn].[Mn] KQFUCKFHODLIAZ-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910006290 γ-MnOOH Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of low-density foam MnOOH, wherein the preparation method includes the steps: (1) preparing a mixed solution A of an alkali and potassium permanganate; (2) dropwise adding a manganese salt solution B to the solution A under high speed stirring to obtain a solution C; (3) transferring the solution C into a high-pressure reaction kettle, and carrying out a reaction to obtain a reaction product D; and (4) freeze-drying the reaction product D to obtain the foam MnOOH material having the density of less than 1 g/cm<3>. The preparation method has mild conditions, the porous foam MnOOH material composed of nanowires is obtained, and the material has the advantages of plasticity, low density and high porosity, and can be used in the fields of material separation, catalysts, electrode materials and the like.
Description
Technical field
The present invention relates to a kind of preparation method of low density foam MnOOH material, specifically, it is related to a kind of new, multiplex
On the way, the preparation method of the foam MnOOH of low-density, high porosity.
Background technology
MnOOH material not only can be widely applied to the fields such as absorption, catalysis, electrode, and is also used as forerunner's system
Standby lithium manganese oxide spinel structure and other Mn oxides such as MnO2、Mn2O3、Mn3O4It is considered to be it is the simplest to prepare Mn oxide
Just practical predecessor.The crystal morphology of MnOOH, crystal structure have great impact to its performance.Compared with nano-particle,
Monodimension nanometer material and its has a wide range of applications on nano-device due to its unique performance as nanometer rods, nano wire.One
As using reverse micelle method or under the auxiliary of surfactant Hydrothermal Synthesiss can prepare γ-MnOOH monodimension nanometer material,
But these methods typically require template, organic solvent or surfactant, its synthesis condition is complicated, production cost is high, easy dirt
Dye environment, and wayward material shape, density is more than the density of water it is impossible to swim in water.
Foamed materialss mainly contain the three-dimensional porous material of a large amount of hilums, have porosity height, and specific surface area is big, weight
Gently, permeability is good, and energy absorption is strong, the low advantage of pyroconductivity, and foam metal material has been widely used in Aero-Space, work
The fields such as industry catalysis, electromagnetic shielding.Preparation method with regard to foam metal material is much reported, such as China Patent Publication No.
CN103301839A utilizes steam phase inversion, by template, the fischer-tropsch catalysts of technical grade is converted into nanowire foam and urges
Agent, have high dispersive, do not reunite, the advantage such as high temperature resistant and abrasion performance.China Patent Publication No. CN1781595A is using chemistry
The noble metal active component of effective dose is carried on foam metal plating method, is prepared for a kind of foam metal hydrogenating catalyst, tool
There is catalysis activity high, active component is firmly combined with carrier, good stability, carrier porosity are high, also provide enough gas-liquids to connect
Contacting surface is amassed, and is conducive to the mass transfer between gas-liquid two-phase.But how to prepare the material of the metal oxide-type with foaming structure still
Have no relevant report.
Content of the invention
The invention aims to improving the deficiencies in the prior art and providing a kind of system of low density foam MnOOH
Preparation Method, prepares low density foam MnOOH material and finds that it can float in the liquid such as Ru Shui, ethanol, it will help
Expand the application of MnOOH material further.
The technical scheme is that：A kind of preparation method of low density foam MnOOH, it comprises the following steps that：
(1) alkali is added to the water with potassium permanganate, prepares the mixed solution A of alkali and potassium permanganate；
(2) Deca manganese salt solution B obtains solution C to solution A under high velocity agitation；
(3) obtain product D by carrying out hydro-thermal reaction in solution C immigration autoclave；
(4) product D is carried out lyophilization and obtain low-density foam MnOOH.
Alkali described in preferred steps (1) is the mixture of one or more of NaOH, KOH or LiOH.Preferred steps
(1) alkali described in is 2-6 with the mol ratio of potassium permanganate：1.
Above-mentioned manganese salt solution B is the aqueous solution (addition of water is dissolving manganese salt) of manganese salt；Preferably above-mentioned manganese salt
Manganese salt in solution B is the mixture of one or more of manganese chloride, manganese nitrate or manganese sulfate；The dripping quantity of manganese salt solution is
Manganese salt is controlled to be 2-4 with the mol ratio of potassium permanganate：1.
The mixing speed of the high-speed stirred described in preferred steps (2) is 300-1500rpm.
The temperature of the hydro-thermal reaction described in preferred steps (3) is 140-300 DEG C；The time of hydro-thermal reaction is 3-20h.
Cryodesiccated temperature described in preferred steps (4) is -10～-50 DEG C；The cryodesiccated time is 24-72h.
Beneficial effect：
Compared with prior art, the present invention has the advantage that：
1st, the foam MnOOH prepared by the present invention is to be combined by nano wire, have density low (less than 1g/cm3), hole
The high advantage of gap rate, can have excellent performance in the fields such as absorption, catalysis, electrochemistry.
2nd, the preparation method of the present invention, it is not necessary to adding organic solvent, surfactant and not having the effect of template, is adopted
Be can be prepared by with simple hydro-thermal method, there is with low cost, simple to operate, environmental protection.
Brief description
Fig. 1 is the hydrothermal product outward appearance photo that the embodiment of the present invention 1 is obtained；
Fig. 2 is the foam MnOOH outward appearance photo that the embodiment of the present invention 1 is obtained；
Fig. 3 is the prepared foam MnOOH of the embodiment of the present invention 1 in water float photo；
Fig. 4 is the XRD figure of the foam MnOOH that the embodiment of the present invention 1 is obtained；
Fig. 5 is the SEM photograph of the foam MnOOH that the embodiment of the present invention 1 is obtained.
Specific embodiment
Method of testing：
1st, density：Quality of materials obtains divided by volume, and its volume measures Size calculation by slide gauge, and quality is using electricity
Sub- balance measurement.
2nd, porosity：Measure foam MnOOH volume V1, after pulverizing, survey its volume V2, porosity=(V1-V2)/V1.
Embodiment 1：
Weigh 7.5mmol sodium hydroxide and 3.75mmol potassium permanganate, add 30mL deionized water, to be mixed uniformly after,
The manganese chloride aqueous solution of Deca 7.5mmol under the mixing speed of 300rpm, reaction mixture is moved into 50mL autoclave
In, react 3h in 140 DEG C, after Temperature fall, generate the brownish black paste product with water heating kettle same volume, as shown in figure 1 ,-
Lyophilization 24h at 10 DEG C, obtains foam MnOOH, as shown in Fig. 2 its volume is identical with water heating kettle volume, density is 0.25g/
cm3, may float in water, as shown in Figure 3；The XRD figure of obtained foam MnOOH is as shown in figure 4, SEM photograph such as Fig. 5 institute
Show；Its porosity is 95% after tested, through sem analysis, its by diameter 10nm, the nano wire composition that 20 μm about of length.
Embodiment 2：
Weigh 11.25mmol potassium hydroxide and 3.75mmol potassium permanganate, add 30mL deionized water, to be mixed uniform
Afterwards, under the mixing speed of 600rpm Deca 9.375mmol manganese nitrate aqueous solution, will reaction mixture move into 50mL high pressure anti-
Answer in kettle, react 6h in 180 DEG C, after Temperature fall, generate the brownish black paste product with water heating kettle same volume, at -20 DEG C
Lyophilization 36h, obtains foam MnOOH, and its volume is identical with water heating kettle, and density is 0.20g/cm3, may float in water, hole
Gap rate is 96%, and through sem analysis, it is diameter 15nm, the nano wire that 20 μm about of length.
Embodiment 3：
Weigh 15mmol Lithium hydrate and 3.75mmol potassium permanganate, add 30mL deionized water, to be mixed uniformly after,
The manganese sulfate solution of Deca 11.25mmol under the mixing speed of 900rpm, reaction mixture is moved into 50mL autoclave
In, react 10h in 220 DEG C, after Temperature fall, generate the brownish black paste product with water heating kettle same volume, freeze at -30 DEG C
48h is dried, obtains foam MnOOH, its volume is identical with water heating kettle, density is 0.30g/cm3, may float in water, porosity
For 94%, through sem analysis, it is diameter 20nm, the nano wire that 20 μm about of length.
Embodiment 4：
Weigh 18.75mmol sodium hydroxide and 3.75mmol potassium permanganate, add 30mL deionized water, to be mixed uniform
Afterwards, under the mixing speed of 1200rpm Deca 13.125mmol manganese chloride aqueous solution, by reaction mixture move into 50mL high pressure
In reactor, react 15h in 260 DEG C, after Temperature fall, generate the brownish black paste product with water heating kettle same volume, at -40 DEG C
Lower lyophilization 60h, obtains foam MnOOH, and its volume is identical with water heating kettle, and density is 0.15g/cm3, may float in water,
Porosity is 96%, and through sem analysis, it is diameter 30nm, the nano wire that 10 μm about of length.
Embodiment 5：
Weigh 22.5mmol Lithium hydrate and 3.75mmol potassium permanganate, add 30mL deionized water, to be mixed uniformly after,
The manganese nitrate aqueous solution of Deca 15mmol under the mixing speed of 1500rpm, reaction mixture is moved into 50mL autoclave
In, react 20h in 300 DEG C, after Temperature fall, generate the brownish black paste product with water heating kettle same volume, freeze at -50 DEG C
72h is dried, obtains foam MnOOH, its volume is identical with water heating kettle, density is 0.15g/cm3, may float in water, porosity
For 97%, through sem analysis, it is diameter 50nm, the nano wire that 10 μm about of length.
Claims (7)
1. a kind of preparation method of low density foam MnOOH, it comprises the following steps that：
(1) alkali is added to the water with potassium permanganate, prepares the mixed solution A of alkali and potassium permanganate；
(2) Deca manganese salt solution B obtains solution C to solution A under high velocity agitation；
(3) obtain product D by carrying out hydro-thermal reaction in solution C immigration autoclave；
(4) product D is carried out lyophilization and obtain low-density foam MnOOH.
2. preparation method according to claim 1 is it is characterised in that the alkali described in step (1) is NaOH, KOH or LiOH
One or more of mixture.
3. preparation method according to claim 1 it is characterised in that the alkali described in step (1) and potassium permanganate mole
Than for 2-6：1.
4. preparation method according to claim 1 is it is characterised in that manganese salt in the manganese salt solution B described in step (2)
Mixture for one or more of manganese chloride, manganese nitrate or manganese sulfate；Manganese salt is 2-4 with the mol ratio of potassium permanganate：1.
5. preparation method according to claim 1 is it is characterised in that the mixing speed of the high-speed stirred described in step (2)
For 300-1500rpm.
6. preparation method according to claim 1 is it is characterised in that the temperature of the hydro-thermal reaction described in step (3) is
140-300℃；The time of hydro-thermal reaction is 3-20h.
7. preparation method according to claim 1 it is characterised in that the cryodesiccated temperature described in step (4) be-
10～-50 DEG C；The cryodesiccated time is 24-72h.
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| CN201610783520.3A CN106379942B (en) | 2016-08-31 | 2016-08-31 | A kind of low density foam MnOOH preparation method |
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| CN201610783520.3A CN106379942B (en) | 2016-08-31 | 2016-08-31 | A kind of low density foam MnOOH preparation method |
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| Publication Number | Publication Date |
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| CN106379942B CN106379942B (en) | 2018-02-23 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108059191A (en) * | 2018-01-24 | 2018-05-22 | 安徽大学 | A kind of alkali formula manganese oxide of nano wire pattern and preparation method thereof |
| CN111187599A (en) * | 2020-02-25 | 2020-05-22 | 桂林电子科技大学 | Three-dimensional basic manganese oxide nanorod foam composite phase change material and preparation method and application thereof |
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|---|---|---|---|---|
| CN103496745A (en) * | 2013-10-09 | 2014-01-08 | 南京信息工程大学 | Method for preparing multi-branched nanometer gamma-MnOOH |
| CN105271422A (en) * | 2015-10-08 | 2016-01-27 | 吉林大学 | Method for preparing ultralight manganese dioxide aerogel |
| CN105329948A (en) * | 2015-11-16 | 2016-02-17 | 国电科学技术研究院 | Novel preparation method for gamma-MnOOH of net structure |
| CN105329947A (en) * | 2015-10-28 | 2016-02-17 | 上海大学 | Preparation method of nano-manganese oxide of flocculent structure |
-
2016
- 2016-08-31 CN CN201610783520.3A patent/CN106379942B/en active Active
Patent Citations (4)
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| CN103496745A (en) * | 2013-10-09 | 2014-01-08 | 南京信息工程大学 | Method for preparing multi-branched nanometer gamma-MnOOH |
| CN105271422A (en) * | 2015-10-08 | 2016-01-27 | 吉林大学 | Method for preparing ultralight manganese dioxide aerogel |
| CN105329947A (en) * | 2015-10-28 | 2016-02-17 | 上海大学 | Preparation method of nano-manganese oxide of flocculent structure |
| CN105329948A (en) * | 2015-11-16 | 2016-02-17 | 国电科学技术研究院 | Novel preparation method for gamma-MnOOH of net structure |
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| A. BAYOUDH等: "Hydrothermal synthesis,characterizationandelectrochemicalproperties of γ-MnOOH nanobelts", 《CERAMICS INTERNATIONAL》 * |
| GUOHONG QIU等: "Oxidation behavior and kinetics of sulfide by synthesized manganese oxide minerals", 《J SOILS SEDIMENTS》 * |
| LI ZHONGCHUN等: "Facile Hydrothermal Synthesis of MnOOH Nanorods and Their Application", 《RARE METAL MATERIALS AND ENGINEERING》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108059191A (en) * | 2018-01-24 | 2018-05-22 | 安徽大学 | A kind of alkali formula manganese oxide of nano wire pattern and preparation method thereof |
| CN111187599A (en) * | 2020-02-25 | 2020-05-22 | 桂林电子科技大学 | Three-dimensional basic manganese oxide nanorod foam composite phase change material and preparation method and application thereof |
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| CN106379942B (en) | 2018-02-23 |
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