CN105111743A - Heat-conducting medium as well as application of heat-conducting medium in lithium battery pack and method for manufacturing heat-conducting medium - Google Patents
Heat-conducting medium as well as application of heat-conducting medium in lithium battery pack and method for manufacturing heat-conducting medium Download PDFInfo
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Abstract
The invention provides a heat-conducting medium which is low in cost, convenient to use, good in heat conductivity and high in flame retardancy as well as an application of the heat-conducting medium in a lithium battery pack and a method for manufacturing the heat-conducting medium. The heat-conducting medium is a colloidal paste made of silicone grease and a heat-conducting flame-retardant filer, wherein the mass ratio of the silicone grease to the heat-conducting flame-retardant filer is 100:(30-80); the viscosity of the colloidal paste is 10,000 CPS-1000,000 CPS, the mass content of silicon is 10%-30%, the heat conductivity is not lower than 1w/mk, and the density is 1.6g/cm<3>-3.5g/cm<3>. The lithium battery pack is filled with the colloidal paste, the cooling effect of the lithium battery pack can be improved greatly, and the lithium battery pack can be prevented from being burnt due to overheating effectively. The heat conductivity, the electric insulativity and the stability of the heat-conducting medium are good, the heat-conducting medium is free of maintenance cost and mobility, and the battery pack is not required to be sealed. The production process of the manufactured battery pack is simple, the maintenance cost is low, and the safety is good.
Description
Technical field
The present invention relates to a kind of heat-conducting medium, particularly a kind of for the heat-conducting medium with flame retardant resistance in lithium electricity series of cells and manufacture method thereof.
Background technology
Along with the development of new forms of energy, lithium electricity is widely used in the fields such as communication, mobile vehicle, energy storage, but lithium electricity battery core and series of cells in use exist certain equivalent internal resistance, add electric liquid decomposition in cell operations, positive polar decomghtion, negative pole and electric liquid react, SEI film reaction etc. all can produce heat.During low temperature, lithium electricity is mainly based on the joule heating that resistance produces, along with heat accumulation, temperature rising can increase fast with other chemical heat, if this partial heat distributes not in time, these thermal responses not only make battery life decline, can aggravate electrolyte decomposition simultaneously, cause combustion explosion to cause security incident time serious, therefore the reduction of temperature control and combustion explosion hidden danger is lithium electrical travelling industry important research field and the problem that need solve.Due to the position difference that each battery core or battery modules are residing in lithium cell group, thus the heat dispersal situations of each battery core or battery modules is just different, causes the temperature in this lithium cell group uneven thus.The inequality of temperature causes again the performance of battery core or battery modules inconsistent conversely.
Using electromobile: series of cells is as the key part of electromobile (xEV), and directly affect the performances such as the mileage of power truck, life-span and safety, temperature variation plays an important role to above-mentioned performance.If series of cells heat can not be derived in time and disperse, be in hot operation for a long time and will have a strong impact on battery life, high temperature easily causes electric liquid to decompose simultaneously, brings serious potential safety hazard to battery.Therefore produce heat to batteries of electric automobile group effectively derive or disperse the work-ing life to improving electromobile (xEV), improving security has Important Economic benefit and social effect.To this, temperature controls to study as an important technological problems of lithium electricity series of cells by industry.
At present, the problem that lithium electricity battery pack temperature raises is solved in industry in the following manner:
1) air is adopted to make heat-eliminating medium
Major advantage: structure is simple, and can get rid of obnoxious flavour in time, cost is low;
Shortcoming: the convection of air coefficient of heat transfer is lower, therefore battery and shell radiating efficiency lower, in addition, the equipment such as additional blower fan/cooling tube can increase overall weight, drop into and running cost also corresponding increase.
2) liquid (water) makes heat-eliminating medium
Major advantage: the radiating efficiency of battery and shell is high.
Shortcoming: stopping property requires high, battery quality increases, structure and maintenance complicated and cost of investment is high.
3) heat-eliminating medium made by phase change material (paraffin)
Major advantage: by force, temperature variation is little, can make battery temperature self-equilibrating, high with the radiating efficiency of shell for heat transfer, heat-sinking capability.
Shortcoming: cost is high, battery sealing-performance requires that high complex structure, the material cost of causing is high; In addition, the phase change materials such as paraffin belong to inflammable material, and potential safety hazard increases, and practicality is deteriorated.
In a word, adopt that air dielectric cost is low but thermal conductivity is low; Comparatively air is high but to battery case by tight requirements, application cost is high to adopt liquid medium thermal conductivity; Adopting phase change material, to do medium heat conduction thermal diffusivity good, but phase transition process also proposes stopping property requirement to shell, and the phase change material such as paraffin belongs to inflammable substance to series of cells and brings new potential safety hazard simultaneously, and cost is also higher.
The method controlling to adopt to the combustion completion of lithium electricity battery core in prior art is prevention and control.As by protecting sheet protection to overcharging, cross put, high temperature carries out job control; Such as modification is carried out to electric liquid, add in electric liquid the type fire retardants such as tricresyl phosphate fat to the decomposition voltage improving electric liquid realize to burning prevention and control etc.Though aforesaid method to a certain degree can reduce the incendivity of battery core, for spent battery core or series of cells then unprotect flame-retarding fire-extinguishing effect.Although have at battery core and battery-pack exterior casing coating flame retardant coating or install expanding material raising flame retardant properties additional, because flame retardant effect and increase process cost make its practical application limited.
Heat-conducting medium of the present invention then to battery core to produce while heat carries out heat conduction and heat radiation and when battery core is burnt by absorbing and cooling temperature and release non-flammable gas, thus deflagration and flame retardant effect can also be played.
Although industry has the technology report adopting different media to carry out series of cells heat conduction and heat radiation, but having no lithium electricity series of cells adopts silica-based heat-conducting medium to carry out written report and the patent of heat conduction and heat radiation, the present invention is except having heat conduction and heat radiation function in addition, also there is the effect of fire-retardant deflagration, therefore there is novelty and practicality.
The present invention is then different from above-mentioned technological line, and adopt heat-conducting medium, the technical problem solved is: to be derived fast by the heat that series of cells working process produces by thermally conductive material or dispersed, in addition; Carry out decomposing thermo-negative reaction reduce envrionment temperature when combustion position appears in series of cells and discharge non-flammable gas prevention or reduce spreading of burning.Different from the heat-conducting mode that medium made by existing employing liquid, air and phase change material, the heat conductive flame-retarding filler that the present invention adopts does not have a mobility, to series of cells without tight requirements, without the need to increasing application cost, thermal conductivity is high, is about 5 ~ 10 times of water, 100 times of air, in addition; Medium of the present invention also possesses fire retardation except heat conduction and heat radiation.Although industry has the technology report of multiple lithium conductance heat and heat radiation, the heat conduction and the heat radiation that silica-based heat-conducting medium are used for lithium electricity then have no report, and adopt and can more have no invention and report by fire-retardant heat-conducting medium.Therefore the present invention has novelty, novelty and practicality.
Prepare heat-conducting medium of the present invention main raw material used and equipment as following table:
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of cost is low, easy to use, thermal conductivity is good and the heat-conducting medium that flame retardant resistance is high and the application in lithium electricity series of cells thereof and manufacture its method.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
Heat-conducting medium of the present invention, is characterized in that: its gluey dope be made up of silicone grease and heat conductive flame-retarding filler, and wherein, the mass ratio of silicone grease and heat conductive flame-retarding filler is 100:(30-80); The viscosity of this gluey dope is 10000CPS-1000000CPS, and silicon mass content is 10%-30%, and its thermal conductivity is not less than 1w/mk, and density is 1.5g/cm
3-3.5g/cm
3.
One or more mixtures in the methyl-silicone oil of described silicone grease to be viscosity be 1000CPs-100000CPs, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, methylchlorophenyl silicone oil, MethylethoxylsiliconFluid Fluid, methyl trifluoro propyl silicone oil, methyl vinyl silicon oil, methylhydroxy silicone oil, ethyl containing hydrogen silicone oil, hydroxyl hydrogen silicone oil or functional group modified silicon oil, wherein silicone content should at 20%-40%.
Described heat conductive flame-retarding filler is particle diameter D50 is 0.2 μm-40 μm, thermal conductivity is not less than 5w/m.k and density is 1.5g/cm
3-3.5g/cm
3by heat conductive filler and fire-retardant filler with 100:(20-100) the mixture that forms of mass ratio, described heat conductive filler is the conductive powder of thermal conductivity > 10w/mk, can discharge the fireproof powder of non-flammable gas nitrogen or carbonic acid gas or water when described fire-retardant filler is burning.
Described conductive powder is one or more in aluminum oxide, zinc oxide, aluminium nitride, boron nitride, silicon carbide, CNT (carbon nano-tube), Graphene or Graphite Powder 99, and the diameter of particle of this conductive powder is D50=0.1 μm-40 μm; Described fireproof powder is two or more mixture in aluminium hydroxide, magnesium hydroxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, zinc borate, monoammonium phosphate, diammonium phosphate, Triphenyl phosphate, phosphoric acid ester melamine salt, boric acid, and the diameter of particle scope of this fireproof powder is D50=0.1 μm-20 μm.
The preparation method of heat-conducting medium of the present invention, comprises the following steps:
1) heat conductive filler and fire-retardant filler are pressed 100:(20-100) mass ratio by wet method homogeneous 15-60 minute, then solvent is carried out de-negative, in 40 DEG C of-150 DEG C of vacuum-dryings, make heat conductive flame-retarding filler, described heat conductive filler is the conductive powder of thermal conductivity > 10w/mk, can discharge the fireproof powder of non-flammable gas nitrogen or carbonic acid gas or water when described fire-retardant filler is burning;
2) be 100:(30-80 by mass ratio) silicone grease and described heat conductive flame-retarding filler be contained in reactor;
3) stir under 50 DEG C of-200 DEG C of conditions being heated to said mixture, 10 minutes-60 minutes reaction times;
4) after being reduced to normal temperature, with three-roll grinder carry out grinding form viscosity be 10000CPS-1000000CPS, thermal conductivity is not less than 1w/mk, silicon mass content is 10%-30%, density is 1.5g/cm
3-3.5g/cm
3the heat-conducting medium of jelly dope.
One or more mixtures in the methyl-silicone oil of described silicone grease to be viscosity be 1000CPs-100000CPs, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, methylchlorophenyl silicone oil, MethylethoxylsiliconFluid Fluid, methyl trifluoro propyl silicone oil, methyl vinyl silicon oil, methylhydroxy silicone oil, ethyl containing hydrogen silicone oil, hydroxyl hydrogen silicone oil or functional group modified silicon oil.
Described heat conductive filler is one or more in aluminum oxide, zinc oxide, aluminium nitride, boron nitride, silicon carbide, CNT (carbon nano-tube), Graphene or Graphite Powder 99; Described fire-retardant filler is two or more mixture in aluminium hydroxide, magnesium hydroxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, zinc borate, monoammonium phosphate, diammonium phosphate, tricresyl phosphate phenol, phosphoric acid ester melamine salt, boric acid.
Lithium electricity series of cells of the present invention, several lithium electricity battery cores that the employing series connection comprising battery-pack exterior casing and be placed in shell and/or parallel way fit together, described in adjacent two panels between battery core and between battery core and outer casing inner wall, be filled with a kind of heat-conducting medium, this heat-conducting medium is the gluey dope be made up of silicone grease and heat conductive flame-retarding filler, wherein, the mass ratio of silicone grease and heat conductive flame-retarding filler is 100:(30-80), the viscosity of this heat-conducting medium is 10000-1000000CPs, its thermal conductivity is not less than 1w/mk, silicone content 10%-30%, density is 1.5g/cm
3-3.5g/cm
3.
The heat-conducting medium be filled in described shell is the 0.5%-10% of wherein battery core gross weight, and this enclosure material is made by aluminum hull, box hat or plastics.
The lithium electricity battery core of described battery core to be its shell be aluminum hull, box hat or plastic-aluminum combined type enclosure, described lithium electricity battery core charging deboost is 3.5 ~ 5V.
Compared with prior art, the present invention adopts and silicone grease and heat conductive flame-retarding filler are mixed and made into viscosity is 10000CPS-1000000CPS, and silicon mass content is 10%-30%, and thermal conductivity is not less than 1w/mk and density is 1.5/cm
3-3.5g/cm
3gluey dope, be filled in lithium electricity series of cells, greatly can improve the radiating effect of lithium electricity series of cells and can effectively prevent this lithium electricity series of cells because crossing thermogenetic burning.The present invention has the following advantages: thermal conductivity, electrical insulating property, good stability, without maintenance cost, without mobility, series of cells without the need to airtight, heat-conducting medium of the present invention has fire retardation in addition, can effectively improve series of cells safety coefficient and the production technique of made series of cells is simple, maintenance cost is low, security is good.
Accompanying drawing explanation
Fig. 1 is that heat conductive flame-retarding filler SEM of the present invention schemes.
Fig. 2 is comparative example heat conductive filler (do not have flame retardant effect) SEM figure.
Fig. 3 is that heat-conducting medium smear SEM schemes (wherein, left figure and right figure belong to same of different magnification ratio scheme).
Fig. 4 is series of cells (Soft Roll-plastic-aluminum combined series of cells) schematic diagram loading conducting medium.
Fig. 5 is series of cells (cylinder-box hat series of cells) schematic diagram loading conducting medium.
Fig. 6 is battery embodiment 1 acupuncture assessment process figure.
Fig. 7 is series of cells comparative example 2 acupuncture assessment process figure.
Fig. 8 is series of cells comparative example 3 acupuncture assessment process figure.
Embodiment
Emphasis of the present invention is silica-based heat conductive flame-retarding medium (hereinafter referred to as heat-conducting medium), manufacture its processing method and its application in lithium electricity series of cells.Described heat-conducting medium is suitable for being filled in secondary lithium electricity series of cells, and it greatly can improve the radiating efficiency of this lithium electricity series of cells and have good flame retardant effect when it meets accident burning.
As shown in Figure 1,3, heat-conducting medium of the present invention, its gluey dope be made up of silicone grease and heat conductive flame-retarding filler, wherein, the mass ratio of silicone grease and heat conductive flame-retarding filler is 100:(30-80); The viscosity of this gluey dope is 10000CPS-1000000CPS, and silicon mass content is 10%-30%, and its thermal conductivity is not less than 1w/mk (the preferred thermal conductivity of the present invention is at 1w/m.k-8w/m.k), and density is 1.5g/cm
3-3.5g/cm
3.
One or more mixtures in the methyl-silicone oil of described silicone grease to be viscosity be 1000CPs-100000CPs, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, methylchlorophenyl silicone oil, MethylethoxylsiliconFluid Fluid, methyl trifluoro propyl silicone oil, methyl vinyl silicon oil, methylhydroxy silicone oil, ethyl containing hydrogen silicone oil, hydroxyl hydrogen silicone oil or functional group modified silicon oil, wherein silicon mass content should at 20%-40%.
The mixture that described heat conductive flame-retarding filler is made up of heat conductive filler and fire-retardant filler, the heat conductive flame-retarding packing material size D50 made 0.2 μm-40 μm, thermal conductivity is not less than 5w/m.k, density is 1.5g/cm
3-3.5g/cm
3.Wherein, heat conductive filler and fire-retardant filler mass ratio are 100:(20-100), heat conductive filler is that (the preferred conductive powder of the present invention is aluminum oxide for the conductive powder of thermal conductivity > 10w/mk, zinc oxide, aluminium nitride, boron nitride, silicon carbide, CNT (carbon nano-tube), one or more in Graphene or Graphite Powder 99, the diameter of particle of this conductive powder is D50=0.1 μm-40 μm, it can be spherical also can be unformed), fire-retardant filler can discharge the fireproof powder of the nitrogen of non-flammable gas or water or carbonic acid gas when being burning (the preferred fireproof powder of the present invention is aluminium hydroxide, magnesium hydroxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, zinc borate, monoammonium phosphate, diammonium phosphate, Triphenyl phosphate, phosphoric acid ester melamine salt, two or more mixture in boric acid, the diameter of particle scope of this fireproof powder is D50=0.1 μm-20 μm).
The preparation method of heat-conducting medium of the present invention, comprises the following steps:
1, heat conductive flame-retarding filler is prepared
Described heat conductive filler and fire-retardant filler are pressed 100:(20-100) mass ratio by wet method homogeneous 15-60 minute, realize dispersed, then solvent is carried out de-negative, in 40 DEG C of-150 DEG C of vacuum-dryings, make heat conductive flame-retarding filler, described heat conductive filler is the conductive powder of thermal conductivity > 10w/mk, can discharge the fireproof powder of non-flammable gas nitrogen or carbonic acid gas or water when described fire-retardant filler is burning;
2, heat-conducting medium is prepared
1) be 100:(30-80 by described silicone grease and the described heat conductive flame-retarding filler for preparing with mass ratio) ratio be contained in reactor and mix;
2) stir under 50 DEG C of-200 DEG C of conditions being heated to said mixture, 10 minutes-60 minutes reaction times;
3), after being reduced to normal temperature, carrying out grinding with three-roll grinder and form heat-conducting medium of the present invention.
As shown in Figure 4,5, lithium electricity battery capacity of the present invention is 10 ~ 1000Ah, it comprises several lithiums electricity battery cores that battery-pack exterior casing fits together with the employing series connection be placed in shell and/or parallel way, described in adjacent two panels between battery core and between battery core and outer casing inner wall, heat-conducting medium described in filling, the heat-conducting medium be filled in described shell is the 0.5%-10% of wherein battery core gross weight, and this enclosure material is made by aluminum hull, box hat or plastics.The housing of described battery core is the lithium electricity battery core of aluminum hull, box hat or Soft Roll type, and this lithium electricity battery core charging deboost is 3.5 ~ 5V.
Adopt heat-conducting medium of the present invention as the lithium electricity series of cells of heat conduction and heat sink material, use-pattern can be battery core surface-coated, also can be series of cells overall perfusion (filling).Its Main Function by heat-conducting medium, the heat that the discharge and recharge of lithium electricity produces is derived in time or disperseed, and effectively controls battery system temperature, improves and improve series of cells work-ing life.In addition; Medium of the present invention and series of cells, when combustion position appears in series of cells battery core, stop burnings spread or reduce rate of propagation by decomposing cooling and discharging non-flammable gas two kinds of forms, improve series of cells safe class.Series of cells of the present invention battery core used is obtain the types such as the box hat of energy, aluminum hull and Soft Roll by lithium ion mobility, and wherein battery core charging deboost is 3.5 ~ 5V.
Lithium electricity series of cells prepared by heat-conducting medium: by the gap of heat-conducting medium potting (filling) between battery core and battery core, between battery core and shell, series of cells is made to obtain compared with air dielectric, heat-conducting effect that water medium is higher, when combustion position appears in series of cells, associated materials can divide heat of desorption to discharge the combustion-supporting effect of non-flammable gas obstruct oxygen simultaneously simultaneously, reduces burning risk.
3, embodiment
1) heat conductive flame-retarding filler preparation
Filler embodiment 1:
300g water and 50g acetone add 1000ml dispersion tank respectively, open clarifixator, add 1.5g nano-dispersing agent, circulation 5min.Then add the ball-aluminium oxide micro mist 150g, CNT (carbon nano-tube) 50g, the aluminium hydroxide 40g that have weighed respectively, homogenisation cycle 60min, rear taking-up vacuum filtration, filter cake grinds after 150 DEG C of vacuum-drying, completes the preparation of heat conductive flame-retarding filler.
Filler embodiment 2:
350g water and 50g acetone add 1000ml dispersion tank respectively, open clarifixator, add 15g nano-dispersing agent, deflocculant 10g, circulation 5min.Then add the ball-aluminium oxide micro mist 150g, Graphene 5g, the antimonous oxide 80g that have weighed respectively, homogenisation cycle 60min, rear taking-up vacuum filtration, filter cake grinds after 100 DEG C of vacuum-drying, completes the preparation of heat conductive flame-retarding filler.
Filler embodiment 3:
150g water and 150g acetone add 1000ml dispersion tank respectively, open clarifixator, add 15g nano-dispersing agent, deflocculant 10g, circulation 5min.Then add the ball-aluminium oxide micro mist 150g, the Triphenyl phosphate 150g that have weighed respectively, homogenisation cycle 60min, rear taking-up vacuum filtration, filter cake grinds after 40 DEG C of vacuum-drying, completes the preparation of heat conductive flame-retarding filler.
Filler comparative example (comparative example is the filler not adding flame-retardant composition, and embodiment is for adding flame-retardant composition filler, lower same): get the ball-aluminium oxide 1500g, the CNT (carbon nano-tube) 500g that have weighed and carry out dry powder blend, obtained heat conductive filler.Form filler as shown in Figure 2 to be only made up of conductive powder without fireproof powder.
2) heat-conducting medium preparation
Heat-conducting medium embodiment 1:
By heat conductive flame-retarding powder prepared with filler embodiment 1 for methyl-silicone oil (viscosity 20000cps), homogeneous reactor is added by the mass ratio of 70:30, stir and be warming up to 50 DEG C in lower 30 minutes-60 minutes, stir 15 minutes, then discharging, is cooled to room temperature, rolls 5 times with three-roll grinder, then carry out detecting (see with following table one), the obtained heat-conducting medium of packaging.
Heat-conducting medium embodiment 2:
By heat conductive flame-retarding powder prepared with filler embodiment 1 for methyl-silicone oil (viscosity 4000cps), homogeneous reactor is added by the mass ratio of 20:80, stir and be warming up to 100 DEG C in lower 30 minutes-60 minutes, stir 10 minutes, then discharging, is cooled to room temperature, 10 times are rolled with three-roll grinder, then carry out viscosity, then carry out detecting (see with following table one), the obtained heat-conducting medium of packaging.
Heat-conducting medium embodiment 3:
By heat conductive flame-retarding powder prepared with filler embodiment 1 for methyl trifluoro propyl silicone oil (viscosity 15000cps), homogeneous reactor is added by the mass ratio of 50:50, stir and be warming up to 200 DEG C in lower 30 minutes-60 minutes, stir 60 minutes, then discharging, is cooled to room temperature, 10 times are rolled with three-roll grinder, then carry out viscosity, then carry out detecting (see with following table one), the obtained heat-conducting medium of packaging.
Heat-conducting medium embodiment 4:
By heat conductive flame-retarding powder prepared with filler embodiment 2 for methyl-silicone oil (viscosity 4000cps) methyl trifluoro propyl silicone oil (viscosity 15000cps), homogeneous reactor is added by the mass ratio of 20:30:50, stir and be warming up to 100 DEG C in lower 30 minutes-60 minutes, stir 60 minutes, then discharging, is cooled to room temperature, rolls 10 times with three-roll grinder, then carry out detecting (see with following table one), the obtained heat-conducting medium of packaging.
Heat-conducting medium embodiment 5:
By heat conductive flame-retarding powder prepared for methyl-silicone oil (viscosity 10000cps) filler embodiment 3, homogeneous reactor is added by the mass ratio of 40:60, stir and be warming up to 150 DEG C in lower 30 minutes-60 minutes, stir 60 minutes, then discharging, is cooled to room temperature, rolls 10 times with three-roll grinder, then carry out detecting (see with following table one), the obtained heat-conducting medium of packaging.
Heat-conducting medium embodiment 6:
By methyl-silicone oil (10000cps), methyl trifluoro propyl silicone oil (viscosity 10000cps) and the heat conductive flame-retarding powder prepared by filler embodiment 3, homogeneous reactor is added by the mass ratio of 15:15:70, stir and be warming up to 80 DEG C in lower 30 minutes-60 minutes, stir 40 minutes, then discharging, is cooled to room temperature, rolls 10 times with three-roll grinder, then carry out detecting (see with following table one), the obtained heat-conducting medium of packaging.
Heat-conducting medium comparative example:
By heat conductive flame-retarding powder prepared with filler comparative example for methyl-silicone oil (10000cps), homogeneous reactor is added by the mass ratio of 30:70, stir and be warming up to 80 DEG C in lower 30 minutes-60 minutes, stir 40 minutes, then discharging, is cooled to room temperature, rolls 10 times with three-roll grinder, then carry out detecting (see with following table one), the obtained heat-conducting medium of packaging.
Be not difficult to draw to draw a conclusion from table one correlation data: add the heat-conducting medium of flame-retardant composition and there is flame retardant effect, the good but viscosity increase of silicone content low heat conductivity.
3) heat conduction series of cells is prepared
Battery embodiment 1:
Get 12 joint box hat 1800mA1650NCM111 battery cores, carry out six and two strings connect, be assembled into 10A series of cells and install square aluminum shell additional, the heat-conducting medium 50g that filling heat-conductive media embodiment 3 is prepared between battery core and battery core, between battery core and shell, then encapsulates.Carry out battery core table temperature measurement with the charge and discharge of 5C multiplying power, and carry out lancing test (the results are shown in following table two and Fig. 6 acupuncture course picture) at full power state.
Series of cells comparative example 2:
Get 12 joint box hat 1800mA1650NCM111 battery cores, carry out six and two strings connect, be assembled into 10A series of cells and install square aluminum shell additional, the heat-conducting medium 50g that between battery core and battery core, between battery core and shell prepared by filling heat-conductive medium comparative example, then encapsulates.Carry out battery core table temperature measurement with the charge and discharge of 5C multiplying power, and carry out lancing test (the results are shown in following table two and Fig. 7 acupuncture course picture) at full power state.
Series of cells comparative example 3:
Get 12 joint box hat 1800mA1650NCM111 battery cores, carry out six and two strings connect, be assembled into 10A series of cells and install square aluminum shell additional, being medium not filling heat-conductive medium with air between battery core and battery core, between battery core and shell, then encapsulating.Carry out battery core table temperature measurement with the charge and discharge of 5C multiplying power, and carry out lancing test (the results are shown in following table two and Fig. 8 acupuncture course picture) at full power state.
As follows from table two Test and analysis:
1) series of cells comparative example 2 adopts the heat-conducting medium without fireproof powder, can effectively derive and disperse, but lancing test has naked light to produce to the heat produced in series of cells working process.
2) make medium with air between the battery core in series of cells comparative example 3, battery core internal temperature is higher, and combustion explosion appears in lancing test.
3) heat that battery embodiment 1 adopts heat-conducting medium of the present invention that battery core can be made to produce is derived fast, this heat-conducting medium has certain flame retardant effect (see Fig. 6 acupuncture course picture) simultaneously, the medium that heat-conducting medium embodiment 3 of the present invention is manufactured is filled between battery core, charge and discharge process each point for measuring temperature temperature is basically identical, lancing test does not produce naked light blast, only has smog to produce.
To sum up analyze, adopt the series of cells of manufacture of the present invention can improve battery life and improve security simultaneously.
Table one, heat-conducting medium Testing index:
Table two, series of cells test and appraisal (the continuous charge and discharge of discharge and recharge condition: 5C4.2V-3V 10 times, envrionment temperature 27 ± 0.5 DEG C)
Claims (10)
1. a heat-conducting medium, is characterized in that: its gluey dope be made up of silicone grease and heat conductive flame-retarding filler, and wherein, the mass ratio of silicone grease and heat conductive flame-retarding filler is 100:(30-80); The viscosity of this gluey dope is 10000CPS-1000000CPS, and silicon mass content is 10%-30%, and its thermal conductivity is not less than 1w/mk, and density is 1.5g/cm
3-3.5g/cm
3.
2. heat-conducting medium according to claim 1, it is characterized in that: one or more mixtures in the methyl-silicone oil of described silicone grease to be viscosity be 1000CPs-100000CPs, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, methylchlorophenyl silicone oil, MethylethoxylsiliconFluid Fluid, methyl trifluoro propyl silicone oil, methyl vinyl silicon oil, methylhydroxy silicone oil, ethyl containing hydrogen silicone oil, hydroxyl hydrogen silicone oil or functional group modified silicon oil, wherein silicone content should at 20%-40%.
3. heat-conducting medium according to claim 1, is characterized in that: described heat conductive flame-retarding filler is particle diameter D50 is 0.2 μm-40 μm, thermal conductivity is not less than 5w/m.k and density is 1.5g/cm
3-3.5g/cm
3by heat conductive filler and fire-retardant filler with 100:(20-100) the mixture that forms of mass ratio, described heat conductive filler is the conductive powder of thermal conductivity > 10w/mk, can discharge the fireproof powder of non-flammable gas nitrogen or carbonic acid gas or water when described fire-retardant filler is burning.
4. heat-conducting medium according to claim 3, it is characterized in that: described conductive powder is one or more in aluminum oxide, zinc oxide, aluminium nitride, boron nitride, silicon carbide, CNT (carbon nano-tube), Graphene or Graphite Powder 99, and the diameter of particle of this conductive powder is D50=0.1 μm-40 μm; Described fireproof powder is two or more mixture in aluminium hydroxide, magnesium hydroxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, zinc borate, monoammonium phosphate, diammonium phosphate, Triphenyl phosphate, phosphoric acid ester melamine salt, boric acid, and the diameter of particle scope of this fireproof powder is D50=0.1 μm-20 μm.
5. a preparation method for heat-conducting medium, is characterized in that: comprise the following steps:
1) heat conductive filler and fire-retardant filler are pressed 100:(20-100) mass ratio by wet method homogeneous 15-60 minute, then solvent is carried out de-negative, in 40 DEG C of-150 DEG C of vacuum-dryings, make heat conductive flame-retarding filler, described heat conductive filler is the conductive powder of thermal conductivity > 10w/mk, can discharge the fireproof powder of non-flammable gas nitrogen or carbonic acid gas or water when described fire-retardant filler is burning;
2) be 100:(30-80 by mass ratio) silicone grease and described heat conductive flame-retarding filler be contained in reactor;
3) stir under 50 DEG C of-200 DEG C of conditions being heated to said mixture, 10 minutes-60 minutes reaction times;
4) after being reduced to normal temperature, with three-roll grinder carry out grinding form viscosity be 10000CPS-1000000CPS, thermal conductivity is not less than 1w/mk, silicon mass content is 10%-30%, density is 1.5g/cm
3-3.5g/cm
3the heat-conducting medium of jelly dope.
6. method according to claim 5, is characterized in that: one or more mixtures in the methyl-silicone oil of described silicone grease to be viscosity be 1000CPs-100000CPs, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, methylchlorophenyl silicone oil, MethylethoxylsiliconFluid Fluid, methyl trifluoro propyl silicone oil, methyl vinyl silicon oil, methylhydroxy silicone oil, ethyl containing hydrogen silicone oil, hydroxyl hydrogen silicone oil or functional group modified silicon oil.
7. method according to claim 5, is characterized in that: described heat conductive filler is one or more in aluminum oxide, zinc oxide, aluminium nitride, boron nitride, silicon carbide, CNT (carbon nano-tube), Graphene or Graphite Powder 99; Described fire-retardant filler is two or more mixture in aluminium hydroxide, magnesium hydroxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, zinc borate, monoammonium phosphate, diammonium phosphate, tricresyl phosphate phenol, phosphoric acid ester melamine salt, boric acid.
8. a lithium electricity series of cells, several lithium electricity battery cores that the employing series connection comprising battery-pack exterior casing and be placed in shell and/or parallel way fit together, it is characterized in that: described in adjacent two panels between battery core and between battery core and outer casing inner wall, be filled with a kind of heat-conducting medium, this heat-conducting medium is the gluey dope be made up of silicone grease and heat conductive flame-retarding filler, wherein, the mass ratio of silicone grease and heat conductive flame-retarding filler is 100:(30-80), the viscosity of this heat-conducting medium is 10000-1000000CPs, its thermal conductivity is not less than 1w/mk, silicone content 10%-30%, density is 1.5g/cm
3-3.5g/cm
3.
9. lithium electricity series of cells according to claim 8, is characterized in that: the heat-conducting medium be filled in described shell is the 0.5%-10% of wherein battery core gross weight, and this enclosure material is made by aluminum hull, box hat or plastics.
10. lithium according to claim 9 electricity series of cells, is characterized in that: the lithium electricity battery core of described battery core to be its shell be aluminum hull, box hat or plastic-aluminum combined type enclosure, described lithium electricity battery core charging deboost is 3.5 ~ 5V.
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