CN110154181B - Preparation method of phase change energy storage wood with nano Ag coated Ti4O7 as filler - Google Patents
Preparation method of phase change energy storage wood with nano Ag coated Ti4O7 as filler Download PDFInfo
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- CN110154181B CN110154181B CN201910481785.1A CN201910481785A CN110154181B CN 110154181 B CN110154181 B CN 110154181B CN 201910481785 A CN201910481785 A CN 201910481785A CN 110154181 B CN110154181 B CN 110154181B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/005—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process employing compositions comprising microparticles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/007—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process employing compositions comprising nanoparticles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/32—Mixtures of different inorganic impregnating agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/0085—Thermal treatments, i.e. involving chemical modification of wood at temperatures well over 100°C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/04—Combined bleaching or impregnating and drying of wood
Abstract
The invention discloses a method for coating Ti with nano Ag4O7A method for preparing phase change energy storage wood as a filler. The filler is a core-shell structure composite material. Using nano Ag particles with an average particle size of 20-30 as a shell, and Ti with an average particle size of 50-100 nm4O7Is a core body, and the heat-conducting composite nano particles are prepared. And then the phase-change material is taken as a heat-conducting filler to be fully mixed with PEG-800, and the wood is impregnated by the phase-change material by adopting a vacuum pressurization method, so that the novel phase-change energy-storage wood capable of adjusting the room temperature is prepared. The invention adopts nano Ag to Ti4O7Coating is performed to Ti4O7The composite particles and PEG are blended to prepare the energy storage material, and the energy storage material can be impregnated into cell walls through wood micropores by a vacuum pressurization method, so that the shaping and packaging effects are achieved. The prepared phase change energy storage wood has ultraviolet-visible light section absorption capacity, can efficiently convert solar energy into internal energy, and realizes the functions of storing and releasing heat.
Description
(I) technical field
The invention relates to a method for coating Ti with nano Ag4O7A method for preparing phase change energy storage wood as a filler, in particular to nano Ag coated Ti4O7Core-shell structured photocatalytic composite particles.
(II) background of the invention
In recent years, the problems of energy conservation and environmental protection become one of the important factors influencing the development of socioeconomic performance. With the rapid development of the industrial society, the demand and the dependence degree of human beings on energy are increasingly strengthened, and the attention is increasingly paid to the development of novel green energy, the improvement of the energy utilization rate, the research and development of energy-saving technology and materials. The energy storage technology is developed at the same time, not only can reduce industrial production energy consumption and recover waste heat, but also can transfer redundant energy in a heat utilization valley period to a heat utilization peak period for use, and in addition, clean energy such as solar energy, geothermal energy and the like can be absorbed and utilized. The technology can effectively overcome the mismatching of heat energy supply and demand in time and space, reduce the consumption of non-renewable fossil energy, improve the utilization rate of energy and reduce environmental pollution. Currently, the commonly used energy storage technologies include sensible energy storage, chemical energy storage, and latent heat storage. Among the heat energy storage technologies, the latent heat energy storage density is high, the system temperature is basically constant in the energy storage process, the temperature of the surrounding environment can be regulated, and the method is the most promising energy storage mode at present. The phase-change material can absorb heat energy through phase change under the heating condition, release the heat energy in the cooling process, realize the storage and release of the heat energy according to different environmental temperatures, and effectively overcome the space-time limitation of heat energy supply. The organic solid-liquid phase change material is a relatively mature phase change material at present, has many types and wide temperature application range, but has the defects of low thermal conductivity, small density, easy loss and the like, so that the preparation of the composite phase change material to improve the performance of the single organic solid-liquid phase change material in practical application becomes the key point of the current research.
The compounding is an important trend of modern material development, and the innovative improvement and the cooperative optimization of the material performance can be realized through compounding different materials. The composite phase-change material is prepared by compounding two or more materials, so that the defects of low thermal conductivity, supercooling and phase separation phenomena, easy leakage in phase change and the like of a single phase-change material in the actual application process are overcome, the application value of the phase-change material is improved, generally, heat-conducting particles are added into the phase-change material to enhance the heat-conducting property of the phase-change material, and metal particles are common heat-conducting fillers, so that the heat-conducting efficiency of the phase-change material can be improved, and the mechanical property of a base material can also be improved. Composite formationThe metal particles can overcome the natural defects of the metal particles and exert the advantages of various materials. Found that Ti4O7Has high wear resistance and high heat stability, and can be used as a substitute material for petroleum extraction lubrication. Ti4O7The powder has traditional TiO2The powder material has high covering power, high dispersing power and excellent heat resistance, has better acid resistance, alkali resistance, surface activity and dispersibility, is completely nonmagnetic, is environment-friendly and nontoxic, meets food-grade safety standards, and is a high-end inorganic functional pigment with pure blackness. The nano Ag particles have high thermal conductivity, good reactivity, large specific surface area and good bacteriostasis, can absorb most sunlight, have high photo-thermal conversion efficiency and are an excellent heat-conducting metal material. However, due to the large surface activity of the nano Ag, particles are easy to generate soft aggregates to form soft aggregates with larger sizes, thereby influencing the development and application of the nano Ag powder and derivatives thereof. If can combine Ti with4O7Combined with the advantages of nano Ag, grafting nano Ag to Ti4O7On the surface, the core-shell nanometer heat conducting particle with good dispersibility and high conversion efficiency to sunlight can be prepared. And finally, the phase-change energy storage material is impregnated into wood by using a vacuum-pressurization method, so that the wood can obtain long-term and high-efficiency energy storage capacity. The product has the characteristics of energy conservation, environmental protection, room temperature balance and degradability, can be used for decoration of buildings, furniture and interior decoration, and creates a green, environment-friendly, energy-saving and comfortable working and living environment for people.
Disclosure of the invention
The invention aims to utilize nano Ag to conjugate graft Ti4O7Preparing core-shell structured photocatalytic composite particles, then taking the core-shell structured photocatalytic composite particles as a heat-conducting filler and blending the core-shell structured photocatalytic composite particles with polyethylene glycol to prepare a phase-change energy storage material, and finally impregnating the phase-change energy storage material into wood by using a vacuum-pressurization method to ensure that the wood obtains long-term and high-efficiency energy storage capacity
The technical scheme of the invention is as follows:
ti coated with nano Ag4O7A method for preparing phase change energy storage wood as a filler. The composite particle is a core-shell structure composite material. With Ti4O7The particles are used as a core body, and the surface of the particles is coated with nano Ag and used as a shell, so that the heat-conducting composite nano particles with strong absorption to ultraviolet-visible light are prepared. And then the phase-change material is taken as a heat-conducting filler to be fully mixed with PEG-800, and the wood is impregnated by the phase-change material by adopting a vacuum pressurization method, so that the novel phase-change energy storage wood capable of adjusting the room temperature is prepared. The method specifically comprises the following steps:
(1) firstly, placing the sliced wood in water, vacuumizing (-0.1MPa for 1h), discharging the air in the wood, and then preparing NaOH and Na with the mass ratio of 1% and 0.5%2SO3Heating the mixed solution to 95 ℃, putting the wood into the mixed solution, cooking for 24h (replacing the mixed solution for 3-4 times in the process), finally putting the cooked wood into an ethanol boiling solution at 78 ℃ for 1h, replacing the water in the wood, and storing the prepared wood in absolute ethanol.
(2) Weighing appropriate amount of nano Ag and Ti4O7The mass ratio is 4:1, for standby, firstly adding a proper amount of CTAB into deionized water, stirring uniformly, and then adding Ti4O7CTAB is Ti4O7And 0.02% of the total mass of deionized water; firstly stirring at 6000r/min for 10min, and then performing ultrasonic treatment at 600W for 10min to obtain cationic Ti4O7And (3) dispersing the mixture.
(3) Adding a proper amount of SDS into deionized water, uniformly stirring, and then adding nano-Ag, wherein the mass of the SDS is 0.05 percent of the total mass of the nano-Ag and the deionized water; firstly stirring at 6000r/min for 10min, and then performing ultrasonic treatment at 600W for 10min to obtain the anionic nano Ag dispersion.
(4) Mixing the nano Ag dispersion liquid with Ti4O7Mixing the dispersion, performing ultrasonic treatment for 10min, then performing vacuum filtration, and performing vacuum drying at 50 ℃ for 24h to obtain the nano Ag grafted Ti4O7。
(5) Weighing appropriate amount of PEG-800, placing in a 50 deg.C constant temperature water bath until melting, adding appropriate amount of anhydrous ethanol, stirring at high speed for 1h, wherein the mass ratio of PEG-800 to anhydrous ethanol is 7:3, and weighing 2 wt% of the mixtureNano Ag grafted Ti4O7Mixing with PEG-800, stirring at 6000r/min for 2 hr, and performing ultrasonic treatment at 600w for 20min to obtain phase change energy storage suspension.
(6) Impregnating the wood with the phase change energy storage material prepared in the step (5) by using a vacuum-pressurization method, firstly, vacuumizing a pretreated wood test piece at 90 ℃, enabling the vacuum degree to reach-0.1 MPa, injecting a phase change energy storage suspension under the negative pressure condition, maintaining the pressure for 30min, recovering the normal pressure, pressurizing an impregnation tank to 1.2MPa, and releasing the pressure after maintaining the pressure for 3 h; and (3) the vacuum degree of the post vacuum is-0.1 MPa, the vacuumizing time is 10min, the test piece is naturally dried for 48h, and then the test piece is placed into a drying oven to be slowly dried at a low temperature of 60 ℃ until the quality is constant, so that the phase change energy storage wood is obtained.
The method has the following advantages:
(1) the reaction condition is easy to control, and the operation is convenient and simple.
(2) Functionalized coated Ti4O7The heat conducting material has good dispersibility and full light section absorption capacity, and improves the heat conducting efficiency.
(3) Coating the Ti with the functionalization4O7The phase change energy storage material is dispersed into PEG-800, the heat storage and release capacity and the loss resistance of the PEG-800 are improved, and then the phase change energy storage material is shaped and packaged by taking wood as a support body, so that the wood has the capacity of regulating the room temperature, and the energy saving is facilitated.
(IV) description of the drawings
FIG. 1 is a technical scheme of the invention
(V) detailed description of the preferred embodiments
Example 1
Ti coated with nano Ag4O7The preparation method of the phase change energy storage wood as the filler comprises the following steps:
(1) the Pinus densiflora is selected, the specification is that the Pinus densiflora is 20mm long, 20mm wide and 20mm thick, and the defects of cracking, decay, discoloration and the like are avoided. After weighing, the wood test piece is placed in deionized water, vacuumized (-0.1MPa, 1h) and the air in the wood is discharged. 500ml of deionized water was poured into a beaker, and then 5g of NaOH and 2.5g of Na were added2SO3Heating to 95 deg.C, and placing the wood in the mixed solutionAnd (4) internally cooking for 24 hours (the mixed liquor is replaced for 3-4 times in the process), wherein the wood is ensured to be immersed in the solution. And finally, placing the cooked wood in an ethanol boiling solution at 78 ℃ for 1h, and replacing the water in the wood. The prepared wood is preserved in absolute ethyl alcohol.
(2) Weighing 20g of nano Ag and 5g of Ti4O7The mass ratio is 4:1, for standby, firstly adding a proper amount of CTAB into 100ml of deionized water, stirring uniformly, and then adding 5g of Ti4O7CTAB in an amount of 0.02g by mass; firstly stirring at 6000r/min for 10min, and then performing ultrasonic treatment at 600W for 10min to obtain cationic Ti4O7And (3) dispersing the mixture.
(3) Adding 0.06g of SDS into 100ml of deionized water, stirring uniformly, and adding 20g of nano Ag; firstly stirring at 6000r/min for 10min, and then performing ultrasonic treatment at 600W for 10min to obtain the anionic nano Ag dispersion.
(4) Mixing the nano Ag dispersion liquid with Ti4O7Mixing the dispersion, performing ultrasonic treatment for 10min, then performing vacuum filtration, and performing vacuum drying at 50 ℃ for 24h to obtain the nano Ag grafted Ti4O7。
(5) Weighing appropriate amount of 21g PEG-800, placing in a 50 deg.C constant temperature water bath until melting, adding 9g anhydrous ethanol, stirring at high speed for 1h, weighing 0.6g nanometer Ag grafted Ti4O7Mixing with PEG-800, stirring at 6000r/min for 2 hr, and performing ultrasonic treatment at 600w for 20min to obtain phase change energy storage suspension.
(6) Impregnating the wood with the phase change energy storage material prepared in the step (5) by using a vacuum-pressurization method, firstly, vacuumizing a pretreated wood test piece at 90 ℃, enabling the vacuum degree to reach-0.1 MPa, injecting a phase change energy storage suspension under the negative pressure condition, maintaining the pressure for 30min, recovering the normal pressure, pressurizing an impregnation tank to 1.2MPa, and releasing the pressure after maintaining the pressure for 3 h; and (3) the vacuum degree of the post vacuum is-0.1 MPa, the vacuumizing time is 10min, the test piece is naturally dried for 48h, and then the test piece is placed into a drying oven to be slowly dried at a low temperature of 60 ℃ until the quality is constant, so that the phase change energy storage wood is obtained.
Example 2
Ti coated with nano Ag4O7A method for preparing phase change energy storage wood as filler comprisesThe following steps:
(1) the white poplar is selected, the specification is 40mm long, 40mm wide and 20mm thick, and the defects of cracking, decay, discoloration and the like are overcome. After weighing, the wood test piece is placed in deionized water, vacuumized (-0.1MPa, 1h) and the air in the wood is discharged. 500ml of deionized water was poured into a beaker, and then 5g of NaOH and 2.5g of Na were added2SO3And after heating to 95 ℃, putting the wood into the mixed solution for cooking for 24 hours (the mixed solution is replaced for 3-4 times in the process), wherein the wood is ensured to be immersed in the solution. And finally, placing the cooked wood in an ethanol boiling solution at 78 ℃ for 1h, and replacing the water in the wood. The prepared wood is preserved in absolute ethyl alcohol.
(2) Weighing 40g of nano Ag and 10g of Ti4O7The mass ratio is 4:1, for standby, firstly adding a proper amount of CTAB into 200ml of deionized water, uniformly stirring, and then adding 10g of Ti4O7CTAB in an amount of 0.04g by mass; firstly stirring at 6000r/min for 10min, and then performing ultrasonic treatment at 600W for 10min to obtain cationic Ti4O7And (3) dispersing the mixture.
(3) Adding 0.12g of SDS into 200ml of deionized water, stirring uniformly, and adding 40g of nano Ag; firstly stirring at 6000r/min for 10min, and then performing ultrasonic treatment at 600W for 10min to obtain the anionic nano Ag dispersion.
(4) Mixing the nano Ag dispersion liquid with Ti4O7Mixing the dispersion, performing ultrasonic treatment for 10min, then performing vacuum filtration, and performing vacuum drying at 50 ℃ for 24h to obtain the nano Ag grafted Ti4O7。
(5) Weighing appropriate amount of 42g PEG-800, placing in a 50 deg.C constant temperature water bath until melting, adding 18g anhydrous ethanol, stirring at high speed for 1h, weighing 1.2g nanometer Ag grafted Ti4O7Mixing with PEG-800, stirring at 6000r/min for 2 hr, and performing ultrasonic treatment at 600w for 20min to obtain phase change energy storage suspension.
(6) Impregnating the wood with the phase change energy storage material prepared in the step (5) by using a vacuum-pressurization method, firstly, vacuumizing a pretreated wood test piece at 90 ℃, enabling the vacuum degree to reach-0.1 MPa, injecting a phase change energy storage suspension under the negative pressure condition, maintaining the pressure for 30min, recovering the normal pressure, pressurizing an impregnation tank to 1.2MPa, and releasing the pressure after maintaining the pressure for 3 h; and (3) the vacuum degree of the post vacuum is-0.1 MPa, the vacuumizing time is 10min, the test piece is naturally dried for 48h, and then the test piece is placed into a drying oven to be slowly dried at a low temperature of 60 ℃ until the quality is constant, so that the phase change energy storage wood is obtained.
Claims (1)
1. Ti coated with nano Ag4O7The preparation method of the phase change energy storage wood as the filler is characterized by comprising the following process steps:
(1) firstly, placing the sliced wood in water, vacuumizing for 1h under-0.1 MPa, discharging the air in the wood, and then preparing NaOH and Na with the mass ratio of 1% and 0.5%2SO3Heating the mixed solution to 95 ℃, putting the wood into the mixed solution, cooking for 24h, replacing the mixed solution for 3-4 times in the process, finally putting the cooked wood into an ethanol boiling solution at 78 ℃ for 1h, replacing the water in the wood, and storing the prepared wood in absolute ethanol;
(2) weighing appropriate amount of nano Ag and Ti4O7The mass ratio is 4:1, for standby, firstly adding a proper amount of CTAB into deionized water, stirring uniformly, and then adding Ti4O7CTAB is Ti4O7And 0.02% of the total mass of deionized water; firstly stirring at 6000r/min for 10min, and then performing ultrasonic treatment at 600W for 10min to obtain cationic Ti4O7A dispersion liquid;
(3) adding a proper amount of SDS into deionized water, uniformly stirring, and then adding nano-Ag, wherein the mass of the SDS is 0.05 percent of the total mass of the nano-Ag and the deionized water; firstly stirring at 6000r/min for 10min, and then performing ultrasonic treatment at 600W for 10min to obtain an anionic nano Ag dispersion liquid;
(4) mixing the nano Ag dispersion liquid with Ti4O7Mixing the dispersion, performing ultrasonic treatment for 10min, then performing vacuum filtration, and performing vacuum drying at 50 ℃ for 24h to obtain the nano Ag grafted Ti4O7；
(5) Weighing a proper amount of PEG-800, placing the PEG-800 in a constant-temperature water bath kettle at 50 ℃ until the PEG-800 is melted, then adding absolute ethyl alcohol, stirring the mixture at a high speed for 1 hour, wherein the mass ratio of the PEG-800 to the absolute ethyl alcohol is 7:3, and weighing 2 wt% of nano Ag grafted Ti4O7And PEG-800, stirring at 6000r/min for 2h, and then performing ultrasonic treatment at 600w for 20min to prepare phase change energy storage suspension;
(6) impregnating the wood with the phase change energy storage material prepared in the step (5) by using a vacuum-pressurization method, firstly, vacuumizing a pretreated wood test piece at 90 ℃, enabling the vacuum degree to reach-0.1 MPa, injecting a phase change energy storage suspension under the negative pressure condition, maintaining the pressure for 30min, recovering the normal pressure, pressurizing an impregnation tank to 1.2MPa, and releasing the pressure after maintaining the pressure for 3 h; and (3) the vacuum degree of the post vacuum is-0.1 MPa, the vacuumizing time is 10min, the test piece is naturally dried for 48h, and then the test piece is placed into a drying oven to be slowly dried at a low temperature of 60 ℃ until the quality is constant, so that the phase change energy storage wood is obtained.
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| CN108724384A (en) * | 2018-07-25 | 2018-11-02 | 东北林业大学 | A kind of preparation method of self-luminous timber that is while storing thermal energy and luminous energy |
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2019
- 2019-06-04 CN CN201910481785.1A patent/CN110154181B/en not_active Expired - Fee Related
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| US5202150A (en) * | 1991-03-13 | 1993-04-13 | The United States Of America As Represented By The United States Department Of Energy | Microwave impregnation of porous materials with thermal energy storage materials |
| CN101215401A (en) * | 2008-01-18 | 2008-07-09 | 厦门大学 | Method for preparing composite material of organic-inorganic nano spherical shell structure |
| CN106448795A (en) * | 2016-09-19 | 2017-02-22 | 成都锦钛精工科技有限公司 | Titanium-suboxide-metal composite conductive material and preparation method thereof |
| CN106625930A (en) * | 2016-12-28 | 2017-05-10 | 中南林业科技大学 | Phase-change energy storage heat-insulation solid wood and manufacturing method thereof |
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