CN108795389A - A kind of compound cold-storage material of slow-release - Google Patents
A kind of compound cold-storage material of slow-release Download PDFInfo
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- CN108795389A CN108795389A CN201810853169.XA CN201810853169A CN108795389A CN 108795389 A CN108795389 A CN 108795389A CN 201810853169 A CN201810853169 A CN 201810853169A CN 108795389 A CN108795389 A CN 108795389A
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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Abstract
The present invention relates to agro-ecology science and technology fields, and in particular to a kind of compound cold-storage material of slow-release.The component of the compound cold-storage material includes:Temperature control sustained release agent, calcium chloride, ammonium chloride, mannitol, polyvinyl alcohol, thickener, Boratex, preservative and water.Wherein, temperature control sustained release agent is a kind of special compound, has good adsorptivity and water-retaining property, becomes gel-like product after water suction, and the effect of curing components and cold sustained release can be played in cold-storage material;Thickener selects guar gum or xanthans;Preservative is one kind or arbitrary a variety of mixture in potassium sorbate, sorbic acid, sodium benzoate and natamycin.The type cold-storage material has cold storage capacity big, and latent heat of phase change is higher, releases the longer feature of cool time, and cold-storage material can recycle, the short distance cold chain transportation suitable for products such as vegetable and fruit, aquatic products and drugs.
Description
Technical field
The present invention relates to agro-ecology science and technology fields, and in particular to a kind of compound cold-storage material of slow-release.
Background technology
Cold-storage material is a kind of ergastic substances being made of organic or inorganic compound, the sticky glue being generally translucent,
It can absorb at low temperature and store a large amount of colds, and a large amount of colds can be released when temperature is higher, the long period keeps itself
And the low temperature environment of surrounding a small range.Cold-storage material is used mainly as the cold-storage filler in ice bag, and ice bag is in cold chain transportation
In have very important effect, almost the various food for needing cold fresh preservations, the food and medicine of Cord blood are required to use
Ice bag keeps the low-temperature condition of storage ambient, ensures the quality and safety of transport product.
Energy storage material can be divided into three classes by energy storage mode:Sensible heat formula, latent heat formula and partly latent hot type, sensible heat type energy storage material exist
While energy storage, it is unable to control environment temperature, and energy storage density is relatively low, device volume is larger, therefore application value is not high.Half
Hidden heat energy storage is the absorption and release that heat is carried out using reversible reaction, and energy storage density is larger, but technical sophistication and is operated
Property is not strong, is only taken seriously at present in field of solar energy, still farther out from practical application.Hidden heat energy storage is to utilize material in phase transformation
It absorbs or heat release comes energy storage or release, not only energy density is higher for this material, and device is simple, small etc., Er Qiecai
Expect approximately constant temperature, the temperature of control system can be carried out with this.Therefore latent heat of phase change stored energy application is relatively broad.
Supercooling in cold-storage material refers to that liquid does not crystallize when being cooled to solidification point, and must be cooled to solidification point or less
Certain temperature when side the phenomenon that starting crystallization, the temperature difference between the practical crystallization temperature of such liquid and theoretical crystallization temperature is
For degree of supercooling.In inorganic salts phase-change material, crystalline hydrate salt easy tos produce this unfavorable factor of supercooling, seriously affects cold-storage material
Use.To expand the application range of cold-storage material, need to find the method for effectively reducing cold-storage material degree of supercooling.
In addition, conventional cold-storage material storage cold is relatively high, but the cold of cold-storage material release process is more rapid, releases cold
Time is shorter;Cold, which can not carry out sustained release, can influence the using effect of cold-storage material, holding time for low temperature be reduced, to Cord blood
The quality safety of product impacts.
Invention content
For problems of the prior art, the present invention provides a kind of compound cold-storage material of slow-release, the type cold-storage materials
Big with cold storage capacity, latent heat of phase change is higher, releases the longer feature of cool time, and cold-storage material can recycle, and be suitable for
The short distance cold chain transportation of the products such as vegetable and fruit, aquatic products and drug.
In order to achieve the above object, the present invention is achieved through the following technical solutions:
A kind of compound cold-storage material of slow-release, according to mass fraction, the component of compound cold-storage material includes:7-12 parts of temperature control sustained release agent,
3-5 parts of calcium chloride, 2-4 parts of ammonium chloride, 1-5 parts of mannitol, 5-8 parts of polyvinyl alcohol, 0.5-1.2 parts of thickener, Boratex 1-2
Part, 0.2-0.5 parts of preservative, 85-90 parts of water.
Preferably, according to mass fraction, the component of compound cold-storage material includes:8-11 parts of temperature control sustained release agent, calcium chloride 3.4-
4.2 parts, 2.6-3.4 parts of ammonium chloride, 2-4 parts of mannitol, 6-7 parts of polyvinyl alcohol, 0.7-0.9 parts of thickener, Boratex 1.5-1.8
Part, 0.3-0.4 parts of preservative, 87-89 parts of water.
It is further preferred that according to mass fraction, the component of compound cold-storage material includes:10 parts of temperature control sustained release agent, calcium chloride 4
Part, 3 parts of ammonium chloride, 3 parts of mannitol, 6.5 parts of polyvinyl alcohol, 0.8 part of thickener, 1.7 parts of Boratex, 0.3 part of preservative, water 88
Part.
In the present invention, the preparation method of temperature control sustained release agent includes the following steps:
(1)According to 4:1:Acrylic acid, Methacrylamide and methacrylic acid are mixed to get monomer solution by 2 molar ratio, to
The sodium hydroxide that 25wt% is added dropwise in monomer solution neutralizes monomer solution, according to mass fraction, after 250 parts are neutralized
Monomer solution is added in reaction kettle, and nitrogen atmosphere is passed through in reaction kettle and is protected, and reduces the dissolved oxygen amount in solution to not high
In 1ppm, 0.15g sodium peroxydisulfates, 0.1g L-AA salt, 4.2ml propylene glycol and 6.8ml alkane are then added into reaction kettle
Base phenol polyethenoxy ether, and carry out initiated polymerization in conjunction with ultraviolet light irradiation, keep 80-85 DEG C of temperature polymerizations to react 30-
35min obtains aquogel polymer A;
(2)The aquogel polymer A of upper step is sent to continuous cutting and crushing in multisection type roller pulverizer, is refined into grain size
For the particle of 1mm, particle is in drying machine with 170-180 DEG C of temperature, continuous heated-air drying 30-40min, by particulate matter after drying
It is sent in standard screen, screening obtains the required powdery resin B that grain size is 250-550 μm;
(3)According to mass fraction, by 1.5 parts of ethylene glycol diglycidylethers, 0.8 part of methyl propanediol and 0.6 part of sodium citrate
It is added in 15 parts of organic solvents, is sufficiently stirred dissolving and obtains cross-linked modifier, by 80 parts of powdery resin B and 25 parts of starch phosphorus
Acid esters, which is added in batch mixer, stirs to get mixture, then sprays application to modifying agent in mixture in the way of spraying, and
The mixed at high speed 8-15min on rotary mill completes required cross-linking modified processing, obtains required cross-linked composite C;
(4)By 2.3 parts of aerosils, 1.5 parts of aluminium oxide and 4 parts of polyethyleneimines, 0.7 part of Imidamide are added to 25 parts
It in deionized water, is stirred to obtain dispersion liquid, dispersion liquid is added in cross-linked composite C, continue in rotary mill
Mixture, is then sent on pneumatic drier by middle mixing 3-5min, is heated and is dried with 150-200 DEG C of temperature
80-100min obtains required temperature control sustained release agent.
Wherein, step(1)Monomer solution in solute three total mass fraction be 40-42.3%.
Step(3)In organic solvent select ethyl alcohol, propyl alcohol, isopropanol or acetone.
Step(4)In aluminium oxide select grain size be 20-50nm Alpha-alumina.
Preferably, thickener selects guar gum or xanthans.
Preferably, preservative is one kind or arbitrary a variety of in potassium sorbate, sorbic acid, sodium benzoate and natamycin
Mixture.
The preparation method of cold-storage material provided by the invention is:
According to mass fraction, temperature control sustained release agent, calcium chloride, ammonium chloride and Boratex are added in batch mixer and are pre-mixed uniformly
Solid-phase component is obtained, after heating water to 35-40 DEG C, mannitol, polyvinyl alcohol and preservative mixing is added thereto and disperses
To liquid phase ingredient, solid-phase component is added in liquid phase ingredient, and thickener is added simultaneously, 10-15min is mixed, obtains
Gel containing water complex be needed for compound cold-storage material;Pack exhaust finally is carried out to compound cold-storage material and sealing is produced
Product.
The present invention has following advantageous effect:
The compound cold-storage material of the type is in addition to using the phase-change materials such as polyvinyl alcohol, chlorination salting liquid in conventional cool storage material to constitute master
Except energy storage agent, a kind of special temperature control sustained release agent is specially added in component, this temperature control sustained release agent is by polypropylene tree
The Multiple components such as fat, starch phosphate and aerosil, by the composite material that special preparation and modified technique produce,
The material has good water lock and dispersibility, and material compatibility is preferable, improves the latent heat of phase change of cold-storage material in cold-storage material
Addition can improve the latent heat of phase change of cold-storage material, play cold slow releasing function, extend the cold release time of cold-storage material.
In addition, the thickener in component can be played with temperature control sustained release agent and be acted synergistically, thus by inorganic salt solution phase transformation
Material and mannitol etc. carry out solidification absorption, form stable gel state product, cold-storage material is avoided to cross cold crystallization or leakage.Component
In Boratex can improve the surfusion of material;Preservative can prevent phase-change material from going bad because of microbial infection,
The health of the product preserved to cold-storage material is avoided to impact.
Description of the drawings
Attached drawing is used to provide further understanding of the present invention, and a part for constitution instruction, the reality with the present invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention, in attached drawing:
Fig. 1 is the line chart of heat-insulating property test data in embodiment.
Specific implementation mode
The specific implementation mode of the present invention is further described with reference to embodiment, following embodiment is only used for more
Technical scheme of the present invention is clearly demonstrated, and not intended to limit the protection scope of the present invention.
In following embodiment, the preparation method of temperature control sustained release agent includes the following steps:
(1)According to 4:1:Acrylic acid, Methacrylamide and methacrylic acid are mixed to get monomer solution by 2 molar ratio, to
The sodium hydroxide that 25wt% is added dropwise in monomer solution neutralizes monomer solution, according to mass fraction, after 250 parts are neutralized
Monomer solution is added in reaction kettle, and nitrogen atmosphere is passed through in reaction kettle and is protected, and reduces the dissolved oxygen amount in solution to not high
In 1ppm, 0.15g sodium peroxydisulfates, 0.1g L-AA salt, 4.2ml propylene glycol and 6.8ml alkane are then added into reaction kettle
Base phenol polyethenoxy ether, and carry out initiated polymerization in conjunction with ultraviolet light irradiation, it keeps 80 DEG C of temperature polymerizations to react 35min, obtains
To aquogel polymer A;
(2)The aquogel polymer A of upper step is sent to continuous cutting and crushing in multisection type roller pulverizer, is refined into grain size
For the particle of 1mm, particulate matter is sent to 175 DEG C of temperature, continuous heated-air drying 35min after dry by particle in drying machine
In standard screen, screening obtains the required powdery resin B that grain size is 250-550 μm;
(3)According to mass fraction, by 1.5 parts of ethylene glycol diglycidylethers, 0.8 part of methyl propanediol and 0.6 part of sodium citrate
It is added in 15 parts of organic solvents, is sufficiently stirred dissolving and obtains cross-linked modifier, by 80 parts of powdery resin B and 25 parts of starch phosphorus
Acid esters, which is added in batch mixer, stirs to get mixture, then sprays application to modifying agent in mixture in the way of spraying, and
The mixed at high speed 10min on rotary mill completes required cross-linking modified processing, obtains required cross-linked composite C;
(4)By 2.3 parts of aerosils, 1.5 parts of aluminium oxide and 4 parts of polyethyleneimines, 0.7 part of Imidamide are added to 25 parts
It in deionized water, is stirred to obtain dispersion liquid, dispersion liquid is added in cross-linked composite C, continue in rotary mill
Mixture, is then sent on pneumatic drier by middle mixing 5min, and 90min is heated and be dried with 180 DEG C of temperature, is obtained
To required temperature control sustained release agent.
Wherein, step(1)Monomer solution in solute three total mass fraction be 41%.
Step(3)In organic solvent select ethyl alcohol.
Step(4)In aluminium oxide select grain size be 20-50nm Alpha-alumina.
Embodiment 1
A kind of compound cold-storage material of slow-release, according to mass fraction, the component of compound cold-storage material includes:7 parts of temperature control sustained release agent, chlorination
3 parts of calcium, 2 parts of ammonium chloride, 1 part of mannitol, 5 parts of polyvinyl alcohol, 0.5 part of thickener, 1 part of Boratex, 0.2 part of preservative, water 85
Part.
Wherein, thickener selects guar gum.
Preservative is potassium sorbate.
The preparation method of cold-storage material provided in this embodiment is:
According to mass fraction, temperature control sustained release agent, calcium chloride, ammonium chloride and Boratex are added in batch mixer and are pre-mixed uniformly
Solid-phase component is obtained, after heating water to 35 DEG C, mannitol, polyvinyl alcohol and preservative mixing is added thereto and disperses to obtain liquid
Solid-phase component is added in liquid phase ingredient by phase constituent, and thickener is added simultaneously, and 10min, obtained gel is mixed
It is required compound cold-storage material containing water complex;Pack exhaust finally is carried out to compound cold-storage material and sealing obtains product.
Embodiment 2
A kind of compound cold-storage material of slow-release, according to mass fraction, the component of compound cold-storage material includes:12 parts of temperature control sustained release agent, chlorine
Change 5 parts of calcium, 4 parts of ammonium chloride, 5 parts of mannitol, 8 parts of polyvinyl alcohol, 1.2 parts of thickener, 2 parts of Boratex, 0.5 part of preservative, water
90 parts.
Wherein, thickener selects xanthans.
Preservative be potassium sorbate and sodium benzoate etc. quality compare mixture.
The preparation method of cold-storage material provided in this embodiment is:
According to mass fraction, temperature control sustained release agent, calcium chloride, ammonium chloride and Boratex are added in batch mixer and are pre-mixed uniformly
Solid-phase component is obtained, after heating water to 40 DEG C, mannitol, polyvinyl alcohol and preservative mixing is added thereto and disperses to obtain liquid
Solid-phase component is added in liquid phase ingredient by phase constituent, and thickener is added simultaneously, and 15min, obtained gel is mixed
It is required compound cold-storage material containing water complex;Pack exhaust finally is carried out to compound cold-storage material and sealing obtains product.
Embodiment 3
A kind of compound cold-storage material of slow-release, according to mass fraction, the component of compound cold-storage material includes:10 parts of temperature control sustained release agent, chlorine
Change 4 parts of calcium, 3 parts of ammonium chloride, 3 parts of mannitol, 6.5 parts of polyvinyl alcohol, 0.8 part of thickener, 1.7 parts of Boratex, preservative 0.3
Part, 88 parts of water.
Wherein, thickener selects guar gum.
Preservative is sorbic acid, sodium benzoate and natamycin according to 1:5:The mixture of 2 mass ratio compounding.
The preparation method of cold-storage material provided in this embodiment is:
According to mass fraction, temperature control sustained release agent, calcium chloride, ammonium chloride and Boratex are added in batch mixer and are pre-mixed uniformly
Solid-phase component is obtained, after heating water to 37 DEG C, mannitol, polyvinyl alcohol and preservative mixing is added thereto and disperses to obtain liquid
Solid-phase component is added in liquid phase ingredient by phase constituent, and thickener is added simultaneously, and 13min, obtained gel is mixed
It is required compound cold-storage material containing water complex;Pack exhaust finally is carried out to compound cold-storage material and sealing obtains product.
Performance test
It selects the common Medical ice bag bought in the market as a control group, is carried out pair with the ice bag of filling the present embodiment cold-storage material
Than cold effect is released in the heat preservation for testing ice bag, and test method is:The ice bag of the present invention is glued respectively to the inner wall of foam insulation box
On, and thermometer is placed in incubator, the temperature in incubator then is read every 1h, obtains following statistical data:
Table 1:The heat-insulating property test result of different ice bags in the present embodiment
Group | Control group | Embodiment 1 | Embodiment 2 | Embodiment 3 |
0h | -5.0 | -5.0 | -5.0 | -5.0 |
1h | -4.8 | -4.6 | -4.6 | -4.6 |
2h | -4.5 | -4.1 | -4.1 | -4.1 |
3h | -4 | -3.7 | -3.6 | -3.7 |
4h | -3.5 | -2.4 | -2.5 | -2.4 |
5h | 1.0 | -1.2 | -1.3 | -1.1 |
6h | 2.4 | 0.5 | 0.8 | 0.7 |
7h | 3.2 | 1.2 | 1.3 | 1.2 |
8h | 4.1 | 1.8 | 1.9 | 1.7 |
9h | 5.0 | 2.3 | 2.4 | 2.3 |
10h | 5.9 | 2.8 | 2.9 | 2.9 |
11h | 6.1 | 3.4 | 3.5 | 3.4 |
12h | 7.0 | 4.1 | 4.2 | 4.1 |
13h | 7.9 | 4.7 | 4.7 | 4.8 |
14h | 8.9 | 5.2 | 5.2 | 5.1 |
15h | 9.8 | 5.8 | 5.8 | 5.8 |
16h | 10.7 | 6.4 | 6.4 | 6.5 |
17h | 11.9 | 6.9 | 6.9 | 6.8 |
18h | 13.0 | 7.2 | 7.3 | 7.2 |
19h | 13.5 | 7.7 | 7.7 | 7.8 |
20h | 13.8 | 8.2 | 8.1 | 8.2 |
21h | 13.9 | 8.6 | 8.7 | 8.6 |
22h | 14.2 | 9.1 | 9.2 | 9.0 |
Data conversion in table 1 is presented at the broken line diagram form of such as Fig. 1;Analytical table 1 and Fig. 1 numbers are it has been found that this implementation
Although the cold-storage material of example and the trend of control group temperature variation curve are almost the same, the cool storage material of the present invention is when identical
Between and state under total energy keep lower temperature, this feature to be become readily apparent from the extension of soaking time, therefore can
Chilling requirement to judge the cold-storage material of the present invention is more preferable, and is found by further analysis, right in the preceding 5h of insulating process
According to heat insulation effect it is obviously more preferable, but after 5h, the temperature of control group increases rapidly, and constant temperature is with higher rate
Increased, may determine that by data, the initial stage cold release of the ice bag of control group is more rapid, therefore, in the guarantor in later stage
Cold during temperature causes heat insulation effect to be remarkably decreased because release is excessive.And the cold controlled release of the cold-storage material of the present embodiment is made
With very good, it can keep relatively uniform and release cold-working use, to maintain good heat insulation effect.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although with reference to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution recorded in example is modified or equivalent replacement of some of the technical features.All essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (10)
1. a kind of compound cold-storage material of slow-release, it is characterised in that:According to mass fraction, the component of the compound cold-storage material includes:
7-12 parts of temperature control sustained release agent, 3-5 parts of calcium chloride, 2-4 parts of ammonium chloride, 1-5 parts of mannitol, 5-8 parts of polyvinyl alcohol, thickener 0.5-
1.2 parts, 1-2 parts of Boratex, 0.2-0.5 parts of preservative, 85-90 parts of water.
2. the compound cold-storage material of a kind of slow-release according to claim 1, it is characterised in that:It is described multiple according to mass fraction
Close cold-storage material component include:8-11 parts of temperature control sustained release agent, 3.4-4.2 parts of calcium chloride, 2.6-3.4 parts of ammonium chloride, mannitol 2-4
Part, 6-7 parts of polyvinyl alcohol, 0.7-0.9 parts of thickener, 1.5-1.8 parts of Boratex, 0.3-0.4 parts of preservative, 87-89 parts of water.
3. the compound cold-storage material of a kind of slow-release according to claim 2, it is characterised in that:It is described multiple according to mass fraction
Close cold-storage material component include:10 parts of temperature control sustained release agent, 4 parts of calcium chloride, 3 parts of ammonium chloride, 3 parts of mannitol, polyvinyl alcohol 6.5
Part, 0.8 part of thickener, 1.7 parts of Boratex, 0.3 part of preservative, 88 parts of water.
4. the compound cold-storage material of a kind of slow-release according to claim 1, it is characterised in that:The preparation of the temperature control sustained release agent
Method includes the following steps:
(1)According to 4:1:Acrylic acid, Methacrylamide and methacrylic acid are mixed to get monomer solution by 2 molar ratio, to
The sodium hydroxide that 25wt% is added dropwise in monomer solution neutralizes monomer solution, according to mass fraction, after 250 parts are neutralized
Monomer solution is added in reaction kettle, and nitrogen atmosphere is passed through in reaction kettle and is protected, and reduces the dissolved oxygen amount in solution to not high
In 1ppm, 0.15g sodium peroxydisulfates, 0.1g L-AA salt, 4.2ml propylene glycol and 6.8ml alkane are then added into reaction kettle
Base phenol polyethenoxy ether, and carry out initiated polymerization in conjunction with ultraviolet light irradiation, keep 80-85 DEG C of temperature polymerizations to react 30-
35min obtains aquogel polymer A;
(2)The aquogel polymer A of upper step is sent to continuous cutting and crushing in multisection type roller pulverizer, is refined into grain size
For the particle of 1mm, particle is in drying machine with 170-180 DEG C of temperature, continuous heated-air drying 30-40min, by particulate matter after drying
It is sent in standard screen, screening obtains the required powdery resin B that grain size is 250-550 μm;
(3)According to mass fraction, by 1.5 parts of ethylene glycol diglycidylethers, 0.8 part of methyl propanediol and 0.6 part of sodium citrate
It is added in 15 parts of organic solvents, is sufficiently stirred dissolving and obtains cross-linked modifier, by 80 parts of powdery resin B and 25 parts of starch phosphorus
Acid esters, which is added in batch mixer, stirs to get mixture, then sprays application to modifying agent in mixture in the way of spraying, and
The mixed at high speed 8-15min on rotary mill completes required cross-linking modified processing, obtains required cross-linked composite C;
(4)By 2.3 parts of aerosils, 1.5 parts of aluminium oxide and 4 parts of polyethyleneimines, 0.7 part of Imidamide are added to 25 parts
It in deionized water, is stirred to obtain dispersion liquid, dispersion liquid is added in cross-linked composite C, continue in rotary mill
Mixture, is then sent on pneumatic drier by middle mixing 3-5min, is heated and is dried with 150-200 DEG C of temperature
80-100min obtains required temperature control sustained release agent.
5. the compound cold-storage material of a kind of slow-release according to claim 4, it is characterised in that:The step(1)Monomer it is molten
The total mass fraction of solute three is 40-42.3% in liquid.
6. the compound cold-storage material of a kind of slow-release according to claim 4, it is characterised in that:The step(3)In it is organic
Solvent selects ethyl alcohol, propyl alcohol, isopropanol or acetone.
7. the compound cold-storage material of a kind of slow-release according to claim 4, it is characterised in that:The step(4)In oxidation
It is the Alpha-alumina of 20-50nm that aluminium, which selects grain size,.
8. the compound cold-storage material of a kind of slow-release according to claim 1, it is characterised in that:The thickener selects guar gum
Or xanthans.
9. the compound cold-storage material of a kind of slow-release according to claim 1, it is characterised in that:The preservative is sorbic acid
One kind in potassium, sorbic acid, sodium benzoate and natamycin or arbitrary a variety of mixture.
10. according to a kind of compound cold-storage material of slow-release described in any one of claim 1-9, which is characterized in that the cold-storage
The preparation method of agent is:
According to mass fraction, temperature control sustained release agent, calcium chloride, ammonium chloride and Boratex are added in batch mixer and are pre-mixed uniformly
Solid-phase component is obtained, after heating water to 35-40 DEG C, mannitol, polyvinyl alcohol and preservative mixing is added thereto and disperses
To liquid phase ingredient, solid-phase component is added in liquid phase ingredient, and thickener is added simultaneously, 10-15min is mixed, obtains
Gel containing water complex be needed for compound cold-storage material;Pack exhaust finally is carried out to compound cold-storage material and sealing is produced
Product.
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CN112850715A (en) * | 2021-01-06 | 2021-05-28 | 江苏福瑞士电池科技有限公司 | Nitrogen-boron co-doped nano silicon-carbon powder material, preparation method and application thereof |
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Application publication date: 20181113 |