CN1834194A - Compsn. of releasing heat after contacting air - Google Patents
Compsn. of releasing heat after contacting air Download PDFInfo
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- CN1834194A CN1834194A CN 200610072518 CN200610072518A CN1834194A CN 1834194 A CN1834194 A CN 1834194A CN 200610072518 CN200610072518 CN 200610072518 CN 200610072518 A CN200610072518 A CN 200610072518A CN 1834194 A CN1834194 A CN 1834194A
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Abstract
This invention relates to a composite that can release heat when contacting the air. The composite is composed of: metal powders that can release heat when reacting with the air, electronic conductive materials and ionic conductive materials at a volume ratio of 2~8:2~8:1~8. The composite can exist in the form of powder, particle or cream. The metal can be reduced Fe, Zn, or Mg alloy or Al alloy that can form metal-air battery in experimental conditions. This invention has such characteristics as easy usage, simple process, and controllable heat release. The composite can be widely used as mounting materials for heat-release rubber hard plaster or balck plaster, heat-release medical products for hot fomrntation, and other industrial products.
Description
Technical field
The material technology field that heats of electrochemical reaction takes place when the present invention relates to use, and specifically is a kind of metal and air (O of utilizing
2) between have potential difference, contact back produces short-circuit current and the heat release mixture that generates heat.
Background technology
The domestic chemical heat release method that is used to keep healthy is a lot, principle has following several: 1, the NaAc supersaturated solution excites the post crystallization heat release by exciting sheet, (Qiang Shi heat bag) on sale on this produce market, its shortcoming is that heat release is concentrated, the heat release time is short, temperature fluctuation is big, can not controls.2, iron powder heating: the domestic publication that the heating of use iron powder is arranged, as CN03129979.2 " a kind of heating bag "; CN200410006553.4 " a kind of heating bag "; CN03149782.9 " spontaneous heating material composition and flame-less heating formula well heater " etc., materials such as iron powder, water, gac, inorganic salt have been used, these patent possible in theory, but moisture content meeting rapid evaporation in the actual heating process, thereby reduce or lose calorific value, be difficult for making product.
Summary of the invention
The purpose of this invention is to provide a kind of mixture that contacts the back heat release with air, be characterized in: with discharge heat after air contacts, easy to use, disposable use, technology is simple, and is with low cost, of many uses.The heating that can be widely used in preparation rubber emplastrum or black plaster mount Heat treatment kneepad that material, body surface hot compress use, protect navel etc. and need the medical product of heating or other mechanicals.
Main technical schemes of the present invention is: a kind of mixture that contacts the back heat release with air, it is characterized in that containing following different materials: a, with the metallic substance of air reaction heat release, b, electronic conductive material, c, ion conductive material.Above-mentioned metallic substance can be reduced iron, zinc (containing iron-zinc alloy etc.), or experiment condition can form down the magnesium alloy or the aluminium alloy of metal-air battery, wherein one or more; Above-mentioned electronic conductive material is that the room temperature electronic conductivity is greater than 10
-3The electronic conductive material of s/cm; Three kinds of Material Physics blend front volume portion rates are 2～8: 2～8: 2～8.Its use, when storing, can be provided with and make it the ventilating structure and/or the sealed structure that contacts with air, the ventilation property of ventilating structure can be selected according to needs, can itself and air be completely cut off with sealed structure etc. when not needing heat release.
The above-mentioned mixture form that contacts the back heat release with air can be powder, particle or paste, by making after described three kinds of Material Physics blend; Described metallic substance form is a powder.
Above-mentioned electronic conductive material can be Powdered raw material of wood-charcoal material, C-S-T, N-S-T, conductive titanium dioxide, conductive mica powder, conductive silicon oxide, conduction kaolin, conductive zinc oxide, conduction ATO or electronic conductive polymer.
Above-mentioned Powdered raw material of wood-charcoal material is gac, acetylene black.
Above-mentioned ion conductive material can be an ionic liquid at room temperature, and its content is so that mixture can form paste or particulate state is advisable; Conductivity at room temperature is greater than 10
-6The copolymer solid electrolyte of the Solid solution of the salt of s/cm or support metal ion transport is good; Described ion conductive material can form behind physical blending.
Above-mentioned ionic liquid at room temperature can be room temperature congruent melting salt or list-compound etc.
Above-mentioned room temperature congruent melting salt can be made up of urea, acid amides, Sodium Bromide, or is made up of aluminum chloride and organic compound.
The Solid solution of above-mentioned salt or copolymer solid electrolyte conductivity at room temperature are greater than 10
-4S/cm is good.
Above-mentioned copolymer solid electrolyte can be Polymer in Salt type copolymer solid electrolyte, polymer gel solid electrolyte or polymkeric substance-salt type (salt in polymer type) solid electrolyte etc.
The Solid solution of above-mentioned salt can be the inorganic salt Solid solution of inorganic salt and urea and/or thiocarbamide formation.
Above-mentioned polymer gel solid electrolyte can be the polymer gel solid electrolyte of ion liquid polymer ionogen or solvent-salt and macromolecular compound composition etc.
Above-mentioned Polymer in Salt type copolymer solid electrolyte can be: with Y type fragrant organism is that main body and macromolecular compound are formed, this Y type aromaticity organism can be urea, thiocarbamide, this macromolecular compound can be PEO, PPO, PEG, PVA or PAN, for example each composition weight umber proportioning can be 20～80 parts of ureas, 20～80 parts of thiocarbamides, 0～20 part of ammonium thiocyanate, 1～10 part of macromolecular compound; Or form by thiocyanate-, nitrate, iodine or bromine salt and macromolecular compound, this salt is potassium, sodium, ammonium salt, this macromolecular compound is PEO, PPO, PEG, PVA, wherein 4 kinds of substance weight portion rates of thiocyanate-, nitrate, iodine or bromine salt and macromolecular compound are 30～70: 30～70: 5～30: 0.5～10, and can congruent melting.
Main base reason of the present invention is: the present invention has utilized metal-air (O
2) battery principle, selected Solid solution, solid electrolyte, ion liquid ion conductive material from salt; Metallic substance from iron, aluminium, zinc, magnesium; A kind of heating mixture that forms from the electronic conductive material physical blending of gac, acetylene black.The present invention is with after air contacts, owing to have potential difference between metal and the oxygen, the local formation with the metal powder granulates of microcosmic is the metal-air battery of negative pole, because physical blending makes between ion, the electronic conductive material and is cross-linked with each other, just forms a large amount of short-circuit currents in the mixture and generates heat again.From another angle, the present invention creates conditions to quicken the oxidation of metal.
Form of the present invention can be powder, particulate state, and making has certain contact area between mixture and the air, and the paste mixture is meant the mixture that ionic liquid at room temperature forms as ion conductive material.The granularity of the ionic conductivity of ion conductive material, material powder (especially metal-powder) is the important factor that influences the heat release effect, is proportionate with the heat release effect in the certain proportion scope.
Heat release of the present invention is except that quick heat release, and slowly heat release also is one of purpose, as be used for hot compress knee-pad, protect navel and can require goods gradual slow heat release in 15 days or longer time.Some ion conductive material be used for heat release of the present invention after for some time the heat release rate slow down, applying external force accelerates as rubbing the back heat release rate, reason is contact interface redistribution between the material, and these characteristics also adapt to heating purpose of the present invention (knee-pad, protect navel move with human body).
Advantage of the present invention is:
1, form can be all solid state: select inorganic salt Solid solution or suitable SPE can prepare all solid state heat release mixture as ion conductive material, the material of mounting, body surface hot compress that is used to prepare the rubber emplastrum that can generate heat or black plaster with Heat treatment kneepad, protect medical product or other mechanicalss that need such as navel generate heat.
2, high-energy-density: burning discharges a large amount of heat energy, is example with aluminium, and aluminium powder ignites and can blast, aluminium and Fe
3O
4The thermite of forming can produce 3500 ℃ high temperature and be used to weld rail, and the heat that complete oxidation of the present invention discharged that contains 500g aluminium is equivalent to 1 kilowatt of power. hour Electric stove burning 4 hours 03 minute.The electrochemical properties of gas battery that several metal is formed is relatively as table 1.
Table 1
| Metal anode | The atom variation of valence | Electrochemical equivalent (Ah/g) | Theoretical specific energy (Kw.h/kg) |
| Magnesium | 2 | 2.20 | 6.8 |
| Aluminium | 3 | 2.98 | 8.1 |
| Zinc | 2 | 0.82 | 1.35 |
| Iron | 2 | 30.96 | 1.2 |
3, good heat release effect: ionic liquid at room temperature conducts electricity very well, does not have vapour pressure, there is not evaporation, selects ionic liquid at room temperature, the inorganic salt Solid solution of high conductance, ionic liquid gel ionogen to have heat release rate faster as ion conductive material.
4, the may command of heat discharges: the present invention has selected the Solid solution, SPE, ionic liquid of salt as ion conductive material, and its ionic conductivity is 10
-1--10
-6S/cm does not wait, and selects the ion conductive material of different specific conductivity that different heat release rates is arranged, and the air-permeable envelope control mixture that uses different porositys and the amount of contact of air can realize the sustained release of heat.
5, easy to use, technology is simple, and is with low cost: metallic substance that the present invention relates to and electro-conductive material economy are easy to get, and good processing properties is arranged, and preparation technology only comprises simple process such as fusion, blend.
Embodiment
Be described further below in conjunction with embodiment, but not as a limitation of the invention.
Embodiment 1:
Reagent: zinc powder 50g, gac 15g, ionic liquid [BMIM] [BF
4] (chemistry by name 1-methyl-3-butyl imidazole a tetrafluoro borate) an amount of.
Zinc powder and gac are mixed, add ionic liquid and stir and make the paste that the becomes wet mixture that must generate heat, mixture is wrapped up with nylon mircofabric, thermometer is put at the center, the observation temperature variation.The result: temperature rises to 180 ℃ and lasting more than 30 minutes rapidly.
Embodiment 2:
Reagent: urea 30g, ethanamide 40g, Sodium Bromide 20g, zinc powder 50g, gac 15g.
Take by weighing urea, ethanamide Sodium Bromide according to quantity, mix the post-heating fusion, get low-temperature eutectic salt.Gac is mixed with the zinc powder equal-volume, add above-mentioned low-temperature eutectic salt, stir and to make the paste that the becomes wet mixture that must generate heat, mixture is wrapped up with nylon mircofabric, thermometer is put at the center, the observation temperature variation.The result: temperature rises to 150 ℃ and lasting more than 30 minutes rapidly.
Embodiment 3:
Reagent: urea 30g, propionic acid amide 40g, Sodium Bromide 20g, zinc powder 50g, gac 15g.
Take by weighing urea, propionic acid amide Sodium Bromide according to quantity, mix the back and in container, stir, get ionic liquid at room temperature (room temperature congruent melting salt).Gac is mixed with zinc powder, add above-mentioned ionic liquid at room temperature, stir and to make the paste that the becomes wet mixture that must generate heat, mixture is wrapped up with nylon mircofabric, thermometer is put at the center, the observation temperature variation.The result: temperature rises to 150 ℃ and lasting more than 30 minutes rapidly.
Embodiment 4:
Reagent: urea 85g, thiocarbamide 80g, PEG6000 5g, zinc powder 100g, gac 20g.
Take by weighing urea, thiocarbamide, PEG mixing according to quantity, 150 ℃ of 30min of constant temperature stir, and get Polymerin Salt type solid electrolyte after the cooling.Get above-mentioned solid electrolyte and zinc powder, gac in mortar, mix the heating mixture, mixture is wrapped up with nylon mircofabric, thermometer is put at the center, observes temperature variation.The result: the heating mixture is higher than envrionment temperature 20-3 ℃ and continues more than 72 hours.
Embodiment 5:
Reagent: urea 85g, thiocarbamide 80g, PEG6000 5g, iron powder 100g, gac 20g.
Take by weighing urea, thiocarbamide, PEG6000 according to quantity, mix 150 ℃ of 30min of back constant temperature, stir, cool off, get Polymer in Salt type solid electrolyte.Get above-mentioned copolymer solid electrolyte and iron powder, gac in mortar, mix the heating mixture, mixture is wrapped up with nylon mircofabric, thermometer is put at the center, observes temperature variation.The result: the heating mixture is higher than envrionment temperature 20-3 ℃ and continues more than 72 hours.Metapyretic mixture is uniform brown, shows that iron ion is uniformly distributed in the mixture.
Embodiment 6:
Reagent: ammonium thiocyanate 17g, ammonium nitrate 14g, potassiumiodide 8.5g, PEG6000 1.5g, zinc powder 50g,
Gac 15g.
Take by weighing Sodium Thiocyanate 99 according to quantity, SODIUMNITRATE, sodium iodide, cools off to such an extent that Polymer in Salt type solid electrolyte is standby at the fusion of PEG600 blend post-heating.By measure zinc powder, gac and above-mentioned Solid solution in mortar, mix the heating mixture, mixture is wrapped up with nylon mircofabric, thermometer is put at the center, observes temperature variation.The result: the heating mixture is higher than more than envrionment temperature 15-5 ℃ lasting more than 70 hours.
Embodiment 7:
Reagent: urea 15g, propionic acid amide 20g, Sodium Bromide 10g, PEG6000 80g, zinc powder 50g, gac 30g.
Take by weighing urea, propionic acid amide Sodium Bromide, the fusion of PEG6000 mixing post-heating according to quantity, add above-mentioned ionic liquid at room temperature, make the cooling back become gel state, get the ion liquid polymer ionogen.Gac is mixed with zinc powder, and the above-mentioned polymer gel solid electrolyte after the adding fusion is granulated, and the mixture that must generate heat wraps up mixture with fine and close nylon mircofabric, and thermometer is put at the center, observes temperature variation.The result: temperature is higher than 15 ℃ of envrionment temperatures and continues more than 30 hours.
Embodiment 8:
Reagent: ammonium thiocyanate 50g, urea 50g, gac 20g, iron powder 100g.
Take by weighing ammonium thiocyanate, urea according to quantity, the fusion of blend post-heating, cool off to such an extent that the Solid solution of ammonium thiocyanate is standby.By measure iron powder, gac and above-mentioned Solid solution in mortar, mix the heating mixture, mixture is wrapped up with nylon mircofabric, thermometer is put at the center, observes temperature variation.The result: the heating mixture is higher than envrionment temperature 150-100 ℃ and continues more than 1.5 hours.
Embodiment 9:
Reagent: zinc acetate is an amount of, urea 50g, zinc powder 50g, gac 15g.
Take by weighing zinc acetate, urea according to quantity, the fusion of blend post-heating, cool off to such an extent that the Solid solution of zinc acetate is standby.By measure zinc powder, gac and above-mentioned Solid solution in mortar, mix the heating mixture, mixture is wrapped up with nylon mircofabric, thermometer is put at the center, observes temperature variation.The result: the heating mixture is higher than more than envrionment temperature 15-5 ℃ lasting more than 3.0 hours.
Embodiment 10:
Reagent: EDTA2Na is an amount of, thiocarbamide 50g, iron powder 50g, gac 15g.
Take by weighing EDTA2Na, the fusion of thiocarbamide blend post-heating according to quantity, cool off to such an extent that the Solid solution of EDTA2Na is standby.By measure zinc powder, gac and above-mentioned Solid solution in mortar, mix the heating mixture, mixture is wrapped up with nylon mircofabric, thermometer is put at the center, observes temperature variation.The result: the heating mixture was higher than envrionment temperature 3-5 ℃ more than lasting 1O hour.
Embodiment 11:
Reagent: zinc powder 50g, crystalline hydrate calcium chloride (CaCl
2.2H
2O) 30g, gac 15g.
Take by weighing mentioned reagent according to quantity, in mortar, mix the heating mixture, mixture is wrapped up with nylon mircofabric, thermometer is put in the centre, observes temperature variation.The result: the heating mixture is higher than envrionment temperature 30-4 ℃ and continues more than 15 hours.
Embodiment 12:
Reagent: crystalline hydrate calcium chloride (CaCl
2.2H
2O) 30g, conductive mica powder 50g, zinc powder 100g.
Take by weighing mentioned reagent according to quantity, in mortar, mix the heating mixture, mixture is wrapped up with nylon mircofabric, thermometer is put at the center, observes temperature variation.The result: the heating mixture is higher than envrionment temperature 8-4 ℃ and continues more than 15 hours.
Embodiment 13～22 sees Table 2.
Table 2
Annotate: on show embodiment by metal (iron, zinc, magnesium or aluminium) powder: electronic conductive material (aerated Powdered Activated Carbon or acetylene black): on show intermediate ion electro-conductive material=2～8: 2～8: 2～8 (volume ratios) batching, and, all can reach heating and requiring (data slightly) with reference to above-mentioned technology making mixing.
During use, ventilating structure can be fine and close nylon mircofabric, the air-permeable envelope that blocks water, apertured plastic films parcel or cover, or be plastics casing, the metal casing of with holes or valve, and sealed structure not can be sealed plastic film or sealed plastics casing, metal casing etc. outside the time spent.
Above-mentioned notion of using among the present invention and explanation thereof, explanation:
1, mixture: according to the definition of International Standards Organization (IS03252): the powder that each particle all is made up of two or more materials, and yardstick is enough to show macroscopic property separately to (usually＞0.5 μ m) greatly.The present invention has selected three kinds of necessary materials, but adds other materials in the mixture for increasing itself and air contact area or other purposes, being not precluded within when making goods.
2, physical blending: purpose is that each component of co-mixing system is disperseed mutually, to obtain the uniform material of component, comprises methods such as dry powder blend, melt blended, solution blending, emulsion blending.As the prerequisite that forms localized metallic-gas battery, among the present invention between employed three kinds of materials, all should have contact interface between three kinds of materials and the air.The contriver thinks that the mixture for preparing behind the physical blending exists with powder, particulate state can reach this purpose.
3, ion conductive material (ionic conductor, ionconductive material): be to be the electro-conductive material of current carrier with the zwitterion, ion conductive material of the present invention is meant the material with ionic conduction ability, does not get rid of its electronic conduction ability.The SPE specific conductivity that is used for all-solid-state battery is 10
-3The s/cm order of magnitude can obtain continual and steady electric current, and the present invention can be used for long-time slowly heat release purpose, does not require that material has high ionic conductivity.As the prerequisite of making product, can not take place between ion conductive material of the present invention, electronic conductive material, the metallic substance redox reaction or each other catalysis issue the reaction of separating estranged.For example: some acidic electrolyte solutions can produce chemical reaction with metal; Decomposition etc. can take place in the NSC 11801 (EC) that is usually used in preparing the polymer gel solid electrolyte under gac, metal oxide, iron catalysis, these materials all are not suitable for the present invention, because the ion conductive material that the present invention relates to is of a great variety, the contriver can not enumerate one by one.
Electrolytical crystal water and thing also can be used for the present invention, and reason may be that lattice was destroyed after electrolytical crystal water and thing were used for the present invention, the local ionic liquid that forms of microcosmic.The embodiment of the invention 11,12 has been introduced the heat release effect of using crystal water and calcium chloride to reach, and this embodiment explanation: the ion conductive material in the mixture can form behind physical blending.
4, electronic conductive material (electronic conductor): be meant that with electronics or hole be the electro-conductive material of current carrier, electronic conductive material room temperature electronic conductivity of the present invention is σ＞10
-3S/cm.Carbon material and some non-carbon materials such as C-S-T, N-S-T, conductive titanium dioxide, conductive mica powder, conductive silicon oxide, conduction kaolin, conductive zinc oxide, conduction ATO, electronic conductive polymer etc. all belong to this type of material, and C-S-T, N-S-T are the body electro-conductive material.Carbon material good permeability, electric conductivity height, cheap are the optimal selections of electronic conductive material.The room-temperature conductivity of some electronic conductive polymers has entered the metal category, is called metallized polymeric (metallic polymer), introduces visible reference in detail.The embodiment of the invention 12 has been introduced the heating effect of conductive mica powder as electronic conductive material.[reference: Zhao Wenyuan, Wang Yijun etc. research of electron conductive type macromolecular material and prospect. the journal .1995 of Shandong Textile Engineering College, 10 (2): 69-81]
5, ionic liquid (ionic liquids): the main liquid that constitutes by ion, as the high concentration solution of fused salt, salt etc.In the high concentration solution of salt, because hydration can be ignored as the existence of aqueous solvent molecule, its character and fused salt are similar.Ionic liquid is to be made of the ion of positively charged and electronegative ion, and it all is liquid state between-100-200 ℃, and ionic liquid has 1,000,000,000,000 kinds theoretically.
6, ionic liquid at room temperature (room temperature ionic liquids): be meant the ionic liquid that under near temperature room temperature or the room temperature, is in a liquid state.Ionic liquid at room temperature has extremely low vapour pressure and ionic state completely basically, and good ionic conductivity is arranged, and non-volatile in wide temperature range, nonflammable, fusing point generally is lower than 100 ℃.It is liquid that ionic liquid at room temperature of the present invention should be under use temperature.Room temperature congruent melting salt belongs to ionic liquid at room temperature of the present invention, and the congruent melting salt fusing point that forms as urea-propionic acid amide-Sodium Bromide can reach 0 ℃, and aluminium salt and some organic compound also can form room temperature congruent melting salt.The embodiment of the invention 1 has been introduced use ionic liquid [BNIM] [BF4], and embodiment 2,3 has introduced the heat release effect that room temperature congruent melting salt that use urea, propionic acid amide (ethanamide), Sodium Bromide form reaches.
7, the Solid solution of salt: the inorganic salt Solid solution that forms after some inorganic salt (as lithium salts) and small organic molecule (as the urea) congruent melting has the ionic conduction ability, and its ionic conductivity can reach 10
-3The s/cm order of magnitude.Because the Solid solution that some small molecules organic salts form is not got rid of ionic conductivity is not arranged, used this notion of Solid solution of salt in the claim of the present invention.Solid solution, embodiment 10 that the embodiment of the invention 8 has been introduced ammonium thiocyanate and urea have introduced the Solid solution of small molecules organic salt EDTA2Na and thiocarbamide formation, the Solid solution that embodiment 13 has introduced Sodium Bromide and thiocarbamide, the Solid solution that embodiment 15 has introduced ammonium thiocyanate and thiocarbamide, embodiment 14 has introduced the heat release effect [reference: Zhao Dishun that Solid solution reached of iron trichloride, Sodium Bromide, urea, Zhang Xingchen etc. the inorganic salt Solid solution is to the influence of polymer solid electrolyte specific conductivity. Hebei University of Science and Technology's journal, 2001,22 (1): 1-6; Tong Yexiang, Liu Peng etc. Fe in urea-NaBr low-temperature molten salt
3+And Sm
3+Electrochemical behavior and induced codeposition thereof. Chinese rare-earth journal, 2002,20 (1): 11-15]
8, copolymer solid electrolyte (solid polymer electrolyte is called for short SPE): claiming ionic conductive polymer (ion-conducting polymer) again, is that a class is the material of the support ion migration of matrix with the polymkeric substance.SPE quantity is various, and good film forming and other processing characteristicies are arranged, and can be divided three classes by its form: (1) all solid state SPE: be with salt, polymer body and salt and add the system that mineral filler constitutes by the polymer body (comprising blend) of macromolecule; (2) gel state SPE (polymer gels); (3) porous SPE: refer to that polymer body has microvoid structure, softening agent and salt and is present in the cavernous structure.1973, after Wright had reported that the mixture of polyethylene oxide (PEO) and an alkali metal salt has ionic conductivity, people began the research of SPE, and the SPE of former studies is mainly used in all-solid-state battery, and employed ionogen is generally lithium salts.The contriver thinks: meet the SPE characteristic, have the material of corresponding ionic conduction ability, all belong to SPE of the present invention.The polymkeric substance that has the ion-electron conductive capability concurrently also belongs to SPE of the present invention.[reference: Wang Jingru. polymer solid electrolyte research new development. chemical propellant and macromolecular material, 2004,2 (3): 18-26]
9, polymer gel solid electrolyte: a class SPE of form similar gels behind the adding liquid plasticizer.Compare with full SPE admittedly, added the higher polar liquid solvent of some constant that is situated between in its system, with solvent-free SPE significant difference is arranged on structure and some performance, wherein the complete solvation of liquid solvent and polymer body forms homogeneous system.The gel state electrolyte that the compound back of ionic liquid at room temperature and some macromolecular compounds forms should belong to polymer gel solid electrolyte of the present invention, this ionogen combines ion liquid ionic conducting property and polymer properties, because it is not all solid state, the someone is referred to as the ionic liquid gel ionogen.The embodiment of the invention 7,21 has been introduced urea, propionic acid amide, the congruent melting salt of Sodium Bromide and the electrolytical heat release effect of ionic liquid gel that PEG6000, PVA congruent melting form.[reference: Jiang Jing, Su Guangyao. ion liquid polymer ionogen progress. battery, 2005,35 (6): 474-476; Acute gold is blue, Gu Qingchao. the new ideas of polymer solid electrolyte design. and polymer circular 2002 (2): 1-8]
10, polymer in salt type copolymer solid electrolyte:, add the SPE that a small amount of macromolecular compound (as PEO) is constituted based on low-temperature eutectic salt.Under this class SPE room temperature rubbery state or high visco-elasticity class solid matter, wherein the content of low-temperature eutectic salt accounts for 80-90%, the principal element that influences its specific conductivity is a low-temperature eutectic salt, the preparation method is made by low-temperature eutectic salt and polymkeric substance congruent melting postcooling, and this class SPE supports metal ion transport.The material of being made up of Solid solution and a small amount of macromolecular compound of a large amount of salt with ionic conduction ability also belongs to polymer in salt type SPE.Claim 10 of the present invention has related to the SPE based on Y aromaticity organism, SPE as urea, thiocarbamide, ammonium thiocyanate, macromolecular compound composition, this class SPE is formed by some Solid solutions and macromolecular compound congruent melting, belongs to polymer in salt type SPE.The embodiment of the invention 22 has been introduced the polymer insalt type SPE that uses urea, ethanamide, Sodium Bromide, PEO to form, embodiment 4,5,18,19 has introduced the heat release effect that polymer in salt type SPE that use urea, thiocarbamide, ammonium thiocyanate, PEG (PVA) form reaches, the preparation method of this two class polymer in salt type SPE document that sees reference.[reference: Zhao Yingxin, Liu Changyan. a kind of electroconductibility research of New Polymer Solid Electrolytes. polymer journal, 1999,3:373-376; Zhao Yingxin, Liu Changyan. a kind of electroconductibility research of New Polymer Solid Electrolytes. electrochemistry, 1999,5 (1): 94-98; Zhao ground is suitable, Sun Fengxia etc. polymeric solid investigation of materials new development. and functional polymer journal, 200013 (4): 469-473; Zhang Xingchen etc. macromolecale rapid ionic conductive research new development. Hebei College of Light Chemical Industry's journal, 199819 (4): 16-19; Hu Fuxin, Wang Hui. a kind of preparation of new kind of solid polymer electrolytes. Xinyang Normal College's journal (natural science edition), 200215 (4): 438-440]
11, alloy material: the described aluminium alloy of claim 1 is can form aluminium under the experiment condition--the alloy material of gas battery.Aluminium powder surface in oxidising process produces the continuation that the compact aluminum oxide film stops oxidising process, some alloy materials can destroy the compact aluminum oxide film is continued oxidising process, described aluminum alloy materials comprise aluminium and bismuth (Bi), indium (In), plumbous (Pb), mercury (Hg), gallium (Ga), tin (Sn), cadmium (Cd), molybdenum (Mo), tungsten (W), chromium (Cr), vanadium (V), germanium (Ge), arsenic (As), antimony (Sb), strontium (Sr), cerium (Ce), top (Tl), manganese (Mn), magnesium (Mg), zinc (Zn), alloy, aluminium content＞99% wherein.The same, described magnesium alloy also is the magnesium alloy materials that can form magnesium-gas battery under the experiment condition.Theoretically, the alloy material that contains iron, zinc also can be used for the present invention.[reference: Xu Wenjiang, Wang Xiangdong etc. the research of aluminum anode of aluminium/gas battery. rare metal, 199923 (5): 366-369; Ren Xueyou. the progress of aluminium/gas battery. battery, 1,995 25 (1): 38-40; Chen Changguo. aluminium/gas battery present Research of aluminium negative pole. battery, 2,004 34 (6): 453-454]
Above-mentioned several Chinese name of writing a Chinese character in simplified form: PVA----polyvinyl alcohol, PE0----polyoxyethylene ether, PEG----polyoxyethylene glycol, PPO----polyoxytrimethylene ether, PAN----polyacrylonitrile.
Claims (10)
1, a kind of mixture that contacts the back heat release with air is characterized in that containing following different materials:
A, with the metallic substance of air reaction heat release,
B, electronic conductive material,
C, ion conductive material;
Described metallic substance is reduced iron, zinc, or experiment condition can form down the magnesium alloy or the aluminium alloy of metal-air battery, wherein one or more; Described electronic conductive material is that the room temperature electronic conductivity is greater than 10
-3The electronic conductive material of s/cm; Three kinds of Material Physics blend front volume portion rates are 2～8: 2～8: 2～8.
2, the mixture that contacts the back heat release with air according to claim 1, it is characterized in that: the mixture form of described heat release is powder, particle or paste, by making after described three kinds of Material Physics blend, described metallic substance form is a powder.
3, the mixture that contacts the back heat release with air according to claim 1, it is characterized in that: described electronic conductive material is powder formed carbon material, C-S-T, N-S-T, conductive titanium dioxide, conductive mica powder, conductive silicon oxide, conduction kaolin, conductive zinc oxide, conduction ATO or electronic conductive polymer.
4, the mixture that contacts the back heat release with air according to claim 3, it is characterized in that: described powder formed carbon material is gac, acetylene black.
5, the mixture that contacts the back heat release with air according to claim 1 is characterized in that described ion conductive material is: ionic liquid at room temperature, and its consumption is so that mixture can form paste or particulate state is advisable; Conductivity at room temperature is greater than 10
-6The copolymer solid electrolyte of the Solid solution of the salt of s/cm or support metal ion transport.
6, the mixture that contacts the back heat release with air according to claim 5, the conductivity at room temperature that it is characterized in that the Solid solution of described salt or support the circuitous copolymer solid electrolyte that moves of metal ion is greater than 10
-4S/cm.
7, according to claim 5 or the 6 described mixtures that contact the back heat release with air, it is characterized in that described copolymer solid electrolyte is Polymer in Salt type copolymer solid electrolyte or polymer gel solid electrolyte.
8, the mixture that contacts the back heat release with air according to claim 7, it is characterized in that: described Polymer in Salt type copolymer solid electrolyte is that main body and macromolecular compound are formed by Y type fragrant organism, this Y type aromaticity organism is urea, thiocarbamide, and this macromolecular compound is PEO, PPO, PEG, PVA or PAN; Or form by thiocyanate-, nitrate, iodine or bromine salt and macromolecular compound, this salt is potassium, sodium, ammonium salt, this macromolecular compound is PEO, PPO, PEG, PVA, wherein thiocyanate-, nitrate, iodine or bromine salt, 4 kinds of substance weight portion rates of macromolecular compound are 30～70: 30～70: 5～30: 0.5～10, and can congruent melting.
9, according to claim 5 or the 6 described mixtures that contact the back heat release with air, it is characterized in that: the inorganic salt Solid solution that the Solid solution of described salt is made up of inorganic salt and urea and/or thiocarbamide.
10, the mixture that contacts the back heat release with air according to claim 7, it is characterized in that: described polymer gel solid electrolyte is the ion liquid polymer ionogen;
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