CN113998983A - Composite thermal insulation material integrally formed with battery shell and preparation process thereof - Google Patents
Composite thermal insulation material integrally formed with battery shell and preparation process thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 239000012774 insulation material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000004964 aerogel Substances 0.000 claims abstract description 112
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000835 fiber Substances 0.000 claims description 49
- 239000011810 insulating material Substances 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
- 238000004146 energy storage Methods 0.000 claims description 26
- 239000011232 storage material Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 17
- 239000010445 mica Substances 0.000 claims description 15
- 229910052618 mica group Inorganic materials 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 230000002431 foraging effect Effects 0.000 claims description 10
- 239000002390 adhesive tape Substances 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- 239000003094 microcapsule Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004966 Carbon aerogel Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052845 zircon Inorganic materials 0.000 claims description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 4
- 229920002748 Basalt fiber Polymers 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000009413 insulation Methods 0.000 abstract description 16
- 239000000654 additive Substances 0.000 abstract description 10
- 230000000996 additive effect Effects 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000004321 preservation Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005338 heat storage Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010425 asbestos Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B30/00—Compositions for artificial stone, not containing binders
- C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/117—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/121—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/30—Deferred-action cells
- H01M6/36—Deferred-action cells containing electrolyte and made operational by physical means, e.g. thermal cells
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00853—Uses not provided for elsewhere in C04B2111/00 in electrochemical cells or batteries, e.g. fuel cells
Abstract
The invention provides a composite thermal insulation material integrally formed with a battery shell, which comprises: the aerogel material comprises 0.5-60% by mass of aerogel material and 40-99.5% by mass of inorganic fiber. The invention has the advantages that the aerogel has low thermal conductivity due to the unique network structure and high porosity, but the aerogel has uneven internal pore size distribution, large pressure difference between pores and easy deformation and rupture of the internal structure, and can fully utilize the auxiliary supporting function of the additive through integral molding, avoid the macroscopic deformation of the aerogel material in the thermal battery assembly process, maintain the unique pore structure in the aerogel and fully exert the thermal insulation and heat preservation performance of the aerogel.
Description
Technical Field
The invention belongs to the technical field of thermal batteries, and particularly relates to a composite heat-insulating material integrally formed with a battery shell and a preparation process thereof.
Background
The thermal battery is a primary battery using high-temperature molten salt as electrolyte, when the internal temperature is induced by the heat provided by the internal heating material to reach the melting point of the molten salt, the battery is activated to work, and then the heat dissipation in the battery is inhibited by the heat insulation and heat preservation material, so that the internal temperature of the thermal battery is kept above the melting point of the molten salt as much as possible, and the thermal battery can work for a long time and has high energy output.
The common thermal battery heat-insulating material is asbestos, inorganic fiber paper, composite ceramic paper and other materials. Asbestos and inorganic fiber materials have high thermal conductivity and are difficult to meet the working requirements of thermal batteries. The aerogel material is added into the composite ceramic paper material, so that the thermal conductivity is improved to a certain extent, but the difference between the thermal conductivity of the composite ceramic paper material and the thermal conductivity of the aerogel material is larger. The aerogel is used as a good heat insulation material with the heat conductivity coefficient lower than 0.015W/m.K, and the application of the aerogel as a heat insulation surrounding lining in a thermal battery is limited due to the poor mechanical property of the aerogel.
In the prior art, no matter be the thermal battery field or compound insulation material field, though can the certain degree improve aerogel material's intensity through modifying the aerogel, nevertheless be difficult to satisfy the good pliability that thermal battery keeps warm and encloses the lining requirement. Particularly in the field of thermal batteries, aerogel is generally used as an additive of thermal insulation materials, and the good thermal insulation performance of aerogel is not fully exerted and utilized.
Disclosure of Invention
The invention aims to provide a composite thermal insulation material integrally formed with a battery shell and a preparation process thereof, and effectively solves the problems that the prior art is difficult to meet the requirement of good flexibility of a thermal insulation surrounding lining of a thermal battery, and aerogel is usually used as an additive of a thermal insulation material, and the good thermal insulation performance of aerogel is not fully exerted and utilized.
In order to solve the technical problems, the invention adopts the technical scheme that: a composite thermal insulation material integrally formed with a battery case, comprising: the aerogel material comprises 0.5-60% by mass of aerogel material and 40-99.5% by mass of inorganic fiber.
Preferably, the aerogel material is SiO2Aerogel, TiO2Aerogel, Al2O3Aerogel, ZrO2Aerogel, carbon aerogel, Fe2O3Aerogel, V2O5Aerogel, WO3Aerogel, SiO2/Al2O3/ZrO2One or more of aerogels.
Preferably, the inorganic fiber is one or more of SiC fiber, carbon fiber, quartz fiber, glass fiber, basalt fiber, mullite fiber, alumina silicate fiber, silica fiber, and zirconia fiber.
A process for preparing a composite thermal insulation material integrally formed with a battery case, comprising:
fixing the inorganic fibers into a fiber body in a crossed manner, wrapping the fiber body along the outer surface of the pile model rod, and then inserting the fiber body into a battery case to obtain a prefabricated body;
adding an infrared shielding agent and a phase change energy storage material with certain mass into the aerogel precursor solution, and uniformly stirring to obtain a mixed solution;
adding the mixed solution into the prefabricated body, standing in a closed environment for aging, and obtaining gel with stable appearance by heating and pressurizing or inflating and pressurizing after aging;
and drying the gel to obtain the aerogel material, and separating the aerogel material from the pile model rod to obtain the composite heat-insulating material integrally formed with the battery shell.
Preferably, before wrapping the fiber body along the outer surface of the pile model rod, wrapping a layer of insulating mica on the outer surface of the pile model rod along the circumferential direction, and fixing the insulating mica by using a high-temperature insulating adhesive tape; and then wrapping the fiber body along the high-temperature insulating tape.
Preferably, in the step of adding a certain mass of infrared shielding agent and phase-change energy storage material into the aerogel precursor solution, the mass of the infrared shielding agent accounts for 1-20% of the mass of the composite heat-insulating material; the mass of the phase change energy storage material accounts for 1-20% of the mass of the composite heat insulation material.
Preferably, the infrared shielding agent is TiO2One or more of powder, SiC powder, potassium hexatitanate whisker, zircon powder, graphene and carbon nano tube; the phase change energy storage material is a sodium nitrate inorganic salt material coated by microcapsules.
Preferably, the mixed solution is added into the prefabricated body, the prefabricated body is placed in a closed environment and stands for aging, and in the step of obtaining the gel with stable appearance through heating and pressurizing or inflating and pressurizing after aging, the aging is carried out at normal temperature and normal pressure for 24-48 h; if the gel is obtained by adopting a heating and pressurizing mode after aging, the heating temperature is 200-400 ℃, and the pressure is 10-30 MPa; if the gel is obtained by adopting an inflation pressurization mode after aging, the inflation pressurization pressure is 10-30 MPa.
Preferably, the gel is dried under the condition of normal pressure in the process of drying the aerogel material to obtain the aerogel material, the drying temperature is 20-100 ℃, and the drying time is 12-48 h.
Preferably, in the process of separating the pile model rod, the high-temperature insulating tape is cut to separate the pile model rod from the insulating mica, so that the composite thermal insulation material integrally formed with the battery shell is obtained.
By adopting the technical scheme, the inorganic fiber in the composite thermal insulation material can share the stress borne by the aerogel network framework, so that the macroscopic brittleness of the aerogel is greatly reduced, and the overall strength and toughness are improved; the addition of the infrared shielding agent can obviously improve the high-temperature heat radiation inhibition capability of the material, so that the heat insulation capability of the novel composite heat insulation material in a high-temperature environment is obviously superior to that of the current heat insulation material; the heat transferred to the heat insulation structure can be absorbed by the addition of the phase-change energy storage material, so that the heat insulation capacity of the material is improved, meanwhile, the heat is uniformly distributed and reasonably utilized in multiple stages by virtue of the heat storage and release capacity of the phase-change energy storage material, and the heat utilization rate of a heat supply system in the thermal battery is improved; the unique network structure of aerogel and high porosity make it have low thermal conductivity, but the inside pore size distribution of aerogel is uneven, and the pressure difference between hole and hole is big, and the inner structure easily takes place the deformation and breaks, through integrated into one piece, can make full use of additive's auxiliary stay effect to avoid aerogel material macroscopic deformation in the thermal battery assembling process, maintain the inside unique pore structure of aerogel, full play its thermal insulation performance.
Drawings
FIG. 1 is a temperature variation curve of the surface of a case in the discharge process of a thermal battery with an integrally formed thermal insulation material according to an embodiment of the present invention
Detailed Description
The invention is further illustrated by the following examples and figures:
the following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions of the basic embodiments of the present invention are also included in the scope of the present invention as claimed in the claims.
A composite thermal insulation material integrally formed with a battery case, comprising: the aerogel material comprises 0.5-60% by mass of aerogel material and 40-99.5% by mass of inorganic fiber.
The aerogel material is SiO2Aerogel, TiO2Aerogel, Al2O3Aerogel, ZrO2Aerogel, carbon aerogel, Fe2O3Aerogel, V2O5Aerogel, WO3Aerogel, SiO2/Al2O3/ZrO2One or more of aerogels.
The inorganic fiber is one or more of SiC fiber, carbon fiber, quartz fiber, glass fiber, basalt fiber, mullite fiber, alumina silicate fiber, silica fiber and zirconia fiber.
The aerogel material is a modified aerogel material, and is modified by adding a certain mass of additives, wherein the additives are an infrared shielding agent and a phase change energy storage material, and the mass of the infrared shielding agent accounts for 1-20% of the mass of the composite heat insulation material; the mass of the phase-change energy storage material accounts for 1-20% of the mass of the composite heat-insulating material.
TiO is selected as the infrared shielding agent2One or more of powder, SiC powder, potassium hexatitanate whisker, zircon powder, graphene and carbon nano tube; the phase change energy storage material is a sodium nitrate inorganic salt material coated by microcapsules.
A process for preparing a composite thermal insulation material integrally formed with a battery case, comprising:
s1: film forming of the preform: fixing inorganic fibers into a fiber body in a crossed manner, wrapping the fiber body along the outer surface of the pile model rod, and then inserting the fiber body into a battery shell to obtain a prefabricated body; wherein the content of the first and second substances,
the pile model rod is a temperature-resistant pile model rod with the diameter consistent with that of an assembled pile, a layer of insulating mica is wrapped on the outer surface of the pile model rod in the circumferential direction, and the insulating mica is fixed on the outer surface of the pile model rod by a high-temperature insulating adhesive tape;
the selection of the inorganic fiber is the same as the selection of the inorganic fiber, and the description is omitted, and the fiber diameter of the inorganic fiber is 10-40 nm, and the length of the inorganic fiber is 3-20 mu m; the mass of the inorganic fiber accounts for 40-99.5% of the mass of the composite heat-insulating material;
and regularly stacking multiple layers of inorganic fibers, fixing the inorganic fibers in a cross mode by adopting a needle punching method to form a fiber body, wrapping the fiber body along the outer surface of the high-temperature insulating tape, and then inserting the fiber body into a battery case to obtain a prefabricated body.
S2: sol pouring: adding an infrared shielding agent and a phase change energy storage material with certain mass into the aerogel precursor solution, and uniformly stirring to obtain a mixed solution; wherein the content of the first and second substances,
the aerogel precursor solution is different in aerogel selection and corresponding mass ratio, so that the aerogel precursor solution is different in aerogel selection and the corresponding mass ratioCan clearly write out a range value, and the aerogel precursor solution can be SiO2Aerogel precursor solution, TiO2Aerogel precursor solution, Al2O3Aerogel precursor solution, ZrO2Aerogel precursor solution, carbon aerogel precursor solution and Fe2O3Aerogel precursor solution, V2O5Aerogel precursor solution, WO3Aerogel precursor solution, SiO2/Al2O3/ZrO2One or more of aerogel precursor solutions;
the infrared shielding agent accounts for 1-20% of the composite heat-insulating material, and TiO is selected as the infrared shielding agent2One or more of powder, SiC powder, potassium hexatitanate whisker, zircon powder, graphene and carbon nano tube;
the mass of the phase-change energy storage material accounts for 1-20% of the mass of the composite heat-insulating material, and the phase-change energy storage material is a sodium nitrate inorganic salt material coated by microcapsules;
and adding the infrared shielding agent and the phase-change energy storage material into the aerogel precursor solution, and stirring to uniformly disperse the additive to obtain a mixed solution.
S3: curing and forming: adding the mixed solution into the prefabricated body, standing in a closed environment for aging, and obtaining gel with stable appearance by heating and pressurizing or inflating and pressurizing; wherein the content of the first and second substances,
the closed environment is a closed environment at normal temperature and normal pressure, and the mixed solution is added into the prefabricated character closed environment for aging for 24-48 h;
after aging, a stable gel can be obtained by adopting a heating and pressurizing or inflating and pressurizing mode, and if the gel is obtained by adopting the heating and pressurizing mode after aging, the heating temperature is 200-400 ℃, and the pressure is 10-30 MPa; if the gel is obtained by adopting an inflation pressurization mode after aging, the inflation pressurization pressure is 10-30 MPa.
S4: drying and mold taking: drying the gel to obtain an aerogel material, separating the aerogel material from the pile model rod to obtain the composite heat-insulating material integrally formed with the battery shell, wherein,
drying the gel at the normal pressure at the temperature of 20-100 ℃ for 12-48h in the process of drying the gel to obtain the aerogel material;
and in the process of separating the pile model rod, the high-temperature insulating adhesive tape is cut to separate the pile model rod from the insulating mica, so that the composite heat-insulating material integrally formed with the battery shell is obtained.
The composite thermal insulation material prepared by the method has good thermal insulation performance, strength and toughness, and heat storage/release capacity, realizes the application of the aerogel material in the thermal insulation surrounding lining of the thermal battery, and has the advantages that:
(1) the addition of the inorganic fiber can share the stress borne by the aerogel network framework, so that the macroscopic brittleness of the aerogel is greatly reduced, and the overall strength and toughness are improved.
(2) The addition of the infrared shielding agent can obviously improve the high-temperature heat radiation inhibition capability of the material, so that the heat insulation capability of the novel composite heat insulation material in a high-temperature environment is obviously superior to that of the current heat insulation material.
(3) The heat transferred to the heat insulation structure can be absorbed by the addition of the phase-change energy storage material, the heat insulation capacity of the material is improved, meanwhile, the heat is uniformly distributed and reasonably utilized in multiple stages by means of the heat storage and release capacity of the phase-change energy storage material, and the heat utilization rate of a heat supply system in the thermal battery is improved.
(4) The unique network structure of aerogel and high porosity make it have low thermal conductivity, but the inside pore size distribution of aerogel is uneven, and the pressure difference between hole and hole is big, and the inner structure easily takes place the deformation and breaks, through integrated into one piece, can make full use of additive's auxiliary stay effect to avoid aerogel material macroscopic deformation in the thermal battery assembling process, maintain the inside unique pore structure of aerogel, full play its thermal insulation performance.
Several examples and comparative examples are listed below:
example 1
S1: film forming of the preform: fixing inorganic fibers into a fiber body in a crossed manner, wrapping the fiber body along the outer surface of the pile model rod, and then inserting the fiber body into a battery shell to obtain a prefabricated body; wherein the content of the first and second substances,
the pile model rod is a temperature-resistant pile model rod with the diameter consistent with that of an assembled pile, a layer of insulating mica is wrapped on the outer surface of the pile model rod in the circumferential direction, and the insulating mica is fixed on the outer surface of the pile model rod by a high-temperature insulating adhesive tape;
the selection of the inorganic fiber is the same as that of the inorganic fiber, and the description is omitted, and the fiber diameter of the inorganic fiber is 30nm, and the length of the inorganic fiber is 10 mu m; the mass of the inorganic fiber accounts for 50% of the mass of the composite heat-insulating material;
regularly stacking multiple layers of inorganic fibers, fixing the inorganic fibers in a cross mode by adopting a needle punching method to form a fiber body, wrapping the fiber body along the outer surface of a high-temperature insulating tape, and then inserting the fiber body into a battery case to obtain a prefabricated body, wherein the size of the battery case is phi 66.8mm multiplied by 74mm multiplied by delta 1.0 mm.
S2: sol pouring: adding an infrared shielding agent and a phase change energy storage material with certain mass into the aerogel precursor solution, and uniformly stirring to obtain a mixed solution; wherein the content of the first and second substances,
the aerogel precursor solution is different in aerogel selection, corresponding mass ratios are different, so that a range value cannot be clearly written, and the aerogel precursor solution is made of SiO2An aerogel precursor solution;
the infrared shielding agent accounts for 5% of the composite heat-insulating material, and TiO is selected as the infrared shielding agent2Powder;
the mass of the phase-change energy storage material accounts for 10% of that of the composite heat-insulating material, and the phase-change energy storage material is a sodium nitrate inorganic salt material coated by microcapsules;
and adding the infrared shielding agent and the phase-change energy storage material into the aerogel precursor solution, and stirring to uniformly disperse the additive to obtain a mixed solution.
S3: curing and forming: adding the mixed solution into the prefabricated body, standing in a closed environment for aging, and heating and pressurizing to obtain gel with stable appearance; wherein the content of the first and second substances,
the closed environment is a closed environment at normal temperature and normal pressure, and the mixed solution is added into the prefabricated character closed environment for aging for 35 hours;
after aging, stable gel can be obtained by heating and pressurizing, and after aging, gel is obtained by heating and pressurizing at 300 ℃ and under 20 MPa.
S4: drying and mold taking: drying the gel to obtain an aerogel material, separating the aerogel material from the pile model rod to obtain the composite heat-insulating material integrally formed with the battery shell, wherein,
drying the gel at the normal pressure for 36h at 70 ℃ in the process of drying the gel to obtain the aerogel material;
and in the process of separating the pile model rod, the high-temperature insulating adhesive tape is cut to separate the pile model rod from the insulating mica, so that the composite heat-insulating material integrally formed with the battery shell is obtained.
Example 2
S1: film forming of the preform: fixing inorganic fibers into a fiber body in a crossed manner, wrapping the fiber body along the outer surface of the pile model rod, and then inserting the fiber body into a battery shell to obtain a prefabricated body; wherein the content of the first and second substances,
the pile model rod is a temperature-resistant pile model rod with the diameter consistent with that of an assembled pile, a layer of insulating mica is wrapped on the outer surface of the pile model rod in the circumferential direction, and the insulating mica is fixed on the outer surface of the pile model rod by a high-temperature insulating adhesive tape;
the selection of the inorganic fiber is the same as that of the inorganic fiber, and the description is omitted, and the fiber diameter of the inorganic fiber is 30nm, and the length of the inorganic fiber is 10 mu m; the mass of the inorganic fiber accounts for 50% of the mass of the composite heat-insulating material;
regularly stacking multiple layers of inorganic fibers, fixing the inorganic fibers in a cross mode by adopting a needle punching method to form a fiber body, wrapping the fiber body along the outer surface of a high-temperature insulating tape, and then inserting the fiber body into a battery case to obtain a prefabricated body, wherein the size of the battery case is phi 66.8mm multiplied by 74mm multiplied by delta 1.0 mm.
S2: sol pouring: adding an infrared shielding agent and a phase change energy storage material with certain mass into the aerogel precursor solution, and uniformly stirring to obtain a mixed solution; wherein the content of the first and second substances,
the aerogel precursor solution is TiO precursor solution, because different aerogels are selected, the corresponding mass ratios are inconsistent, the range value cannot be clearly written out2An aerogel precursor solution;
the infrared shielding agent accounts for 5% of the composite heat-insulating material, and TiO is selected as the infrared shielding agent2Powder;
the mass of the phase-change energy storage material accounts for 10% of that of the composite heat-insulating material, and the phase-change energy storage material is a sodium nitrate inorganic salt material coated by microcapsules;
and adding the infrared shielding agent and the phase-change energy storage material into the aerogel precursor solution, and stirring to uniformly disperse the additive to obtain a mixed solution.
S3: curing and forming: adding the mixed solution into the prefabricated body, standing in a closed environment for aging, and heating and pressurizing to obtain gel with stable appearance; wherein the content of the first and second substances,
the closed environment is a closed environment at normal temperature and normal pressure, and the mixed solution is added into the prefabricated character closed environment for aging for 35 hours;
after aging, stable gel can be obtained by heating and pressurizing, and after aging, gel is obtained by heating and pressurizing at 300 ℃ and under 20 MPa.
S4: drying and mold taking: drying the gel to obtain an aerogel material, separating the aerogel material from the pile model rod to obtain the composite heat-insulating material integrally formed with the battery shell, wherein,
drying the gel at the normal pressure for 36h at 70 ℃ in the process of drying the gel to obtain the aerogel material;
and in the process of separating the pile model rod, the high-temperature insulating adhesive tape is cut to separate the pile model rod from the insulating mica, so that the composite heat-insulating material integrally formed with the battery shell is obtained.
Comparative example 1
The composite ceramic paper adopted in the current thermal battery product is taken as the heat insulation material of a comparative example, the multilayer composite ceramic paper with the same thickness and size as those of the embodiment 1 and the embodiment 2 is wrapped inside a battery case by adopting the existing wrapping technology, and the size of the adopted battery case is phi 66.8mm multiplied by 74mm multiplied by delta 1.0 mm.
The heat insulating effect of the examples 1 and 2 and the comparative example 1 is shown in fig. 1, which is a temperature change curve of the surface of the case during the discharge of the thermal battery of the integrally formed heat insulating material.
The embodiments of the present invention have been described in detail, but the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (10)
1. A composite thermal insulation material integrally formed with a battery case, comprising: the aerogel material comprises 0.5-60% by mass of aerogel material and 40-99.5% by mass of inorganic fiber.
2. The composite thermal insulation material for a thermal battery according to claim 1, characterized in that: the aerogel material is SiO2Aerogel, TiO2Aerogel, Al2O3Aerogel, ZrO2Aerogel, carbon aerogel, Fe2O3Aerogel, V2O5Aerogel, WO3Aerogel, SiO2/Al2O3/ZrO2One or more of aerogels.
3. The composite thermal insulation material for a thermal battery according to claim 1 or 2, characterized in that: the inorganic fiber is one or more of SiC fiber, carbon fiber, quartz fiber, glass fiber, basalt fiber, mullite fiber, alumina silicate fiber, silica fiber and zirconia fiber.
4. A process for preparing the composite thermal insulation material of claim 1 integrally formed with a battery case, comprising:
fixing the inorganic fibers into a fiber body in a crossed manner, wrapping the fiber body along the outer surface of the pile model rod, and then inserting the fiber body into a battery case to obtain a prefabricated body;
adding an infrared shielding agent and a phase change energy storage material with certain mass into the aerogel precursor solution, and uniformly stirring to obtain a mixed solution;
adding the mixed solution into the prefabricated body, standing in a closed environment for aging, and obtaining gel with stable appearance by heating and pressurizing or inflating and pressurizing after aging;
and drying the gel to obtain the aerogel material, and separating the aerogel material from the pile model rod to obtain the composite heat-insulating material integrally formed with the battery shell.
5. The preparation process of the composite heat-insulating material integrally formed with the battery shell as claimed in claim 4, wherein the preparation process comprises the following steps: before wrapping the fiber body along the outer surface of the galvanic pile model rod, wrapping a layer of insulating mica on the outer surface of the galvanic pile model rod along the circumferential direction, and fixing the insulating mica by adopting a high-temperature insulating adhesive tape; and then wrapping the fiber body along the high-temperature insulating tape.
6. The preparation process of the composite heat-insulating material integrally formed with the battery shell as claimed in claim 4, wherein the preparation process comprises the following steps: in the step of adding a certain mass of infrared shielding agent and phase-change energy storage material into the aerogel precursor solution, the mass of the infrared shielding agent accounts for 1-20% of the mass of the composite heat-insulating material; the mass of the phase change energy storage material accounts for 1-20% of the mass of the composite heat insulation material.
7. The process for preparing the composite thermal insulation material integrally formed with the battery shell according to claim 4, 5 or 6, wherein: the infrared shielding agent is TiO2One or more of powder, SiC powder, potassium hexatitanate whisker, zircon powder, graphene and carbon nano tube; the phase change energy storageThe material is a sodium nitrate inorganic salt material coated by microcapsules.
8. The preparation process of the composite heat-insulating material integrally formed with the battery shell as claimed in claim 4, wherein the preparation process comprises the following steps: adding the mixed solution into the prefabricated body, standing in a closed environment for aging, and aging at normal temperature and normal pressure for 24-48h in the step of obtaining a gel with stable appearance by heating and pressurizing or inflating and pressurizing after aging; if the gel is obtained by adopting a heating and pressurizing mode after aging, the heating temperature is 200-400 ℃, and the pressure is 10-30 MPa; if the gel is obtained by adopting an inflation pressurization mode after aging, the inflation pressurization pressure is 10-30 MPa.
9. The preparation process of the composite heat-insulating material integrally formed with the battery shell as claimed in claim 4, wherein the preparation process comprises the following steps: and in the process of drying the gel to obtain the aerogel material, drying the gel at the normal pressure for 12-48h at the drying temperature of 20-100 ℃.
10. The preparation process of the composite heat-insulating material integrally formed with the battery shell as claimed in claim 4, wherein the preparation process comprises the following steps: and in the process of separating the pile model rod, the high-temperature insulating adhesive tape is cut to separate the pile model rod from the insulating mica, so that the composite heat-insulating material integrally formed with the battery shell is obtained.
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