CN104183805A - Preparation method for ceramic coating separator - Google Patents
Preparation method for ceramic coating separator Download PDFInfo
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- CN104183805A CN104183805A CN201310198195.0A CN201310198195A CN104183805A CN 104183805 A CN104183805 A CN 104183805A CN 201310198195 A CN201310198195 A CN 201310198195A CN 104183805 A CN104183805 A CN 104183805A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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Abstract
The invention relates to a preparation method for a ceramic coating separator material used to lithium ion batteries. The preparation method comprises steps of preparation of a ceramic slurry, separator pretreatment, precise coating, drying and the like. The prepared product has the characteristics that the ceramic coating is compact, uniformly and firm in adhesion and the separator is small in thermal shrinkage, and the prepared product has obvious effect on improving safety performance of the lithium ion battery and prolonging battery service life.
Description
Technical field
The present invention relates to the ceramic-coated separator that a kind of lithium ion battery is used, belong to new energy materials field.
Background technology
Since the nineties in lithium ion battery to 20 century, the portable electric appts such as notebook computer, digital camera, mobile phone have been widely used in.Simultaneously also by large-scale application in electric automobile, large-scale energy-storage system.
Lithium ion battery is that the secondary battery performance of current industrialization is best, has the good characteristics such as energy density is high, the life-span is long, power density is large, is the energy-storage battery of current electric automobile first-selection.But lithium-ion-power cell (general capacity is large, the higher lithium ion battery for fields such as electric automobiles of power be called lithium-ion-power cell) safety issue hidden danger such as () existence is caught fire, blasts still allows people satisfied not to the utmost.
The barrier film of lithium ion battery is one of key factor affecting its fail safe.The barrier film using is at present mainly PP(polypropylene), PE(polyethylene) microporous membrane of material, its general thickness is tens～tens microns; Under normal circumstances, lithium ion in electrolyte can be freely by embedding the work requirements of de-embedding to meet electrode material, when the abnormal conditions such as battery is short-circuited, overcharges, battery can generate heat, after temperature surpasses 90 ℃, the micropore of barrier film can shrink until seal, to block the further expansion of accident.But due to thermal inertia, even the sealing of barrier film micropore, battery could not rest on 90 ℃ yet, but can be raised to higher temperature, and particularly, when there is serious short circuit or electric current overcharges greatly, temperature can rise to 170 ℃, even more than 200 ℃! Now barrier film significantly shrinks generation integral body, thereby causes the direct large area short circuit of both positive and negative polarity of battery, by the temperature of battery further being raise, finally cause to catch fire, the serious accident such as blast.
Research shows, shows that coated with ceramic coating can effectively improve the shrinkage of barrier film, thereby increase substantially the security performance of battery at barrier film.Due to pottery (aluminium oxide, silica, zirconia, magnesium oxide etc.) stable in properties, do not decompose, do not burn, do not shrink, be coated on barrier film, can play the effect of " skeleton ", thereby stop the contraction of barrier film, so ceramic-coated separator can obviously improve the fail safe of lithium-ion-power cell.
At present the ceramic powders in the slurry of ceramic-coated separator mainly adopts alundum (Al2O3), and it has the advantages such as stable performance, price be low, can play the effect that " skeleton " is provided to barrier film.
Because the diaphragm material of lithium ion battery is polypropylene or vinyl polymer material, it is poor that these materials and water-base cement embody wetability, therefore there is the report that adopts organic gel system, as the adhering method that 1-METHYLPYRROLIDONE is bonding agent as solvent, polyacrylate or Kynoar of take adopting in patent 201210166837.4 < < high safe ceramics compound lithium ion barrier films and lithium battery > > thereof.But organic colloid is tied to form that this is higher, has organic substance volatilization when drying, and has certain pollution, need take environmental practice, and the organic gel micropore of filling part barrier film matrix, cause micropore to diminish, tail off, thereby affect the ion conduction property of barrier film.
Adopt water-base cement system to carry out bonding, can, because the wetability of glue and barrier film is poor, cause ceramic particle to be difficult to be uniformly distributed on barrier film, and a little less than bonding force, coating easily come off again.
It is raw material that nanometer/ultrafine ceramic powder and deionized water are take in the present invention, itself and bonding agent, wetting agent, dispersant etc. are combined together, the high-strength dispersion means that adopt high-speed stirred and ultrasonic wave to combine are made water-base cement slurries, guaranteed dispersion effect and the adhesive effect of water-base cement system, overcome and adopted common stirring to be difficult to the drawback that nanometer/ultrafine ceramic powder is effectively disperseed; In preferred scheme, adopt alundum (Al2O3) and magnesium oxide composite ceramics system simultaneously, not only alundum (Al2O3) can play the effect of " skeleton " to barrier film, and the magnesium oxide acid neutralization that can also form with the micro-moisture that exists in battery system and improve battery life.Before coating, barrier film base material is taked to ozone treatment, the wetability of barrier film and water-base cement is obviously improved, overcome due to barrier film base material and the poor ceramic coating causing of water-base cement system wetability is inhomogeneous, adhesive strength is low defect.Adopt again accurate coating technique that slurries are coated on barrier film, after drying, coiling, obtain ceramic-coated separator product.Above-mentioned measure can cover on barrier film matrix ceramic coating evenly, securely, make barrier film thermal contraction performance be improved significantly, the security performance of lithium ion battery is significantly improved.
Summary of the invention
The object of the present invention is to provide the preparation method of the diaphragm material with ceramic coating that a kind of lithium ion battery uses.
The preparation method that the present invention has the diaphragm material of ceramic coating is: barrier film base material is polypropylene, poly individual layer or the above composite membrane of their one deck; Thickness 9～40 μ m; Preparation technology comprises ceramic size preparation, barrier film preliminary treatment, accurate coating oven dry three large steps:
(1) ceramic size preparation
1. have at the same time the vacuum of supersonic oscillations function, at a high speed, in planet stirring equipment (rotating speed 0～3000r/min is adjustable, ultrasonic frequency 20kHz vibration) to add deionized water and granularity be one or more ceramic powders in the alundum (Al2O3), zirconia, silica, magnesium oxide, zinc oxide, titanium dioxide of 0.05～1.0 μ m, the weight ratio of ceramic powder and deionized water is (5～30): (95～70), high-speed stirred (rotating speed is greater than 1000r/min) while supersonic oscillations 0.5～2 hour;
2. add one or more the mixture in Sodium Polyacrylate, many sodium metaphosphates, sodium orthophosphate, sodium metasilicate, lauryl sodium sulfate, ammoniacal liquor, addition is slip 0.5～5%; High-speed stirred (rotating speed is greater than 1000r/min) while supersonic oscillations 0.5～2 hour;
3. add one or more the mixture in 1-METHYLPYRROLIDONE, alcohol, propylene carbonate, glycerine, dimethyl sulfoxide (DMSO), polyoxyethylated alkyl phenol, polyoxyethylene aliphatic alcohol ether, polyvinyl alcohol, addition is slip 0.5～10%; High-speed stirred (rotating speed is greater than 1000r/min) while supersonic oscillations 0.5～2 hour;
4. the carboxy styrene-butadiene rubber (SBR) (being mixed with in advance 50% emulsion) that adds slip amount 0.5～10%, adds the sodium carboxymethylcellulose (CMC) (being mixed with in advance 2% solution) of slip amount 0.3～5%; High-speed stirred (rotating speed is greater than 1000r/min) while supersonic oscillations 0.5～2 hour;
5. turn down below rotating speed to 500 r/min, close supersonic oscillations, open vacuum, stir 0.5～1 hour, then close and emit slip after Vacuum Balance atmospheric pressure to cross 200 mesh sieves standby.
(2) barrier film preliminary treatment
In order to improve the wettability of barrier film and slip, adopt the ozone of flow 0.5～5 L/min to process barrier film, 5～120 seconds processing times.
(3) accurate coating is dried
Pretreated barrier film is placed on nick version coating machine, and the slip preparing is placed in the hopper of nick version coating machine, is coated with, and coating speed is controlled at 2～20m/min; Adopt laser or gamma thickness gage to carry out on-line monitoring and control to coating layer thickness, guarantee the even of coating layer thickness, controlling coating layer thickness is 1～5 μ m; Coating post-drying, rolling are finished product.
Described ceramic size preparing process, is characterized in that preferred one or more mixtures that adopt in alundum (Al2O3), magnesium oxide and zinc oxide in described alundum (Al2O3), zirconia, silica, magnesium oxide, zinc oxide, titanium dioxide; More preferably adopt alundum (Al2O3) and magnesian mixture, alundum (Al2O3) and magnesium oxide ratio are (7～9.5): (3～0.5).
Described ceramic size preparing process, is characterized in that described CMC also can use hydroxypropyl methylcellulose (HPMC) replacement, and addition is slip 0.5～10%.
Described ceramic size preparing process, be further characterized in that SBR used and CMC also can polyvinyl alcohol (PVA) or LA132, L133, L134 lithium ion battery with a kind of the substituting in bonding agent, addition is slip 0.5～10%.
Described accurate coating process, is characterized in that adopting silk screen printing, transfer type coating or squash type coating process to replace nick version coating process.
It is raw material that nanometer/ultrafine ceramic powder and deionized water are take in the present invention, itself and bonding agent, wetting agent, dispersant etc. are combined together, the high-strength dispersion means that adopt high-speed stirred and ultrasonic wave to combine are made water-base cement slurries, dispersion effect and the adhesive effect of water-base cement system have been guaranteed, do not pollute, overcome and adopted common stirring to be difficult to the drawback that nanometer/ultrafine ceramic powder is effectively disperseed; In preferred scheme, adopt alundum (Al2O3) and magnesium oxide composite ceramics system simultaneously, not only alundum (Al2O3) can play the effect of " skeleton " to barrier film, and the magnesium oxide acid neutralization that can also form with the micro-moisture that exists in battery system and improve battery life.Before coating, barrier film base material is taked to ozone treatment, the wetability of barrier film and water-base cement is obviously improved, overcome due to barrier film base material and the poor ceramic coating causing of water-base cement system wetability is inhomogeneous, adhesive strength is low defect.Adopt again accurate coating technique that slurries are coated on barrier film, after drying, coiling, obtain ceramic-coated separator product.Above-mentioned measure can cover on barrier film matrix ceramic coating evenly, securely, make barrier film thermal contraction performance be improved significantly, the security performance of lithium ion battery and life-span are all significantly improved.
Accompanying drawing explanation
Fig. 1 is ceramic-coated separator stereoscan photograph prepared by the present invention, can find out that coating is even.
Fig. 2 is ceramic-coated separator stereoscan photograph prepared by comparative example, can find out that its coating is obviously inhomogeneous.
Embodiment
embodiment 1
(1) ceramic size preparation
1. have at the same time the vacuum of supersonic oscillations function, at a high speed, in planet stirring equipment (rotating speed 0～3000r/min is adjustable, ultrasonic frequency 20kHz vibration) to add deionized water and granularity be the silicon dioxide of 0.2 μ m, the weight ratio of ceramic powder and deionized water is 30:70,3000r/min high-speed stirred while supersonic oscillations 0.5 hour;
2. the Sodium Polyacrylate that adds slip amount 5%, 3000r/min high-speed stirred while supersonic oscillations 0.5 hour;
3. the glycerine that adds slip amount 0.5%, 3000r/min high-speed stirred while supersonic oscillations 2 hours;
4. the carboxy styrene-butadiene rubber (SBR) (being mixed with in advance 50% emulsion) that adds slip amount 10%, adds the sodium carboxymethylcellulose (CMC) (being mixed with in advance 2% solution) of slip amount 5%; 3000r/min high-speed stirred while supersonic oscillations 2 hours;
5. turn down rotating speed to 500 r/min, close supersonic oscillations, open vacuum, stir 0.5 hour, then close and emit slip after Vacuum Balance atmospheric pressure to cross 200 mesh sieves standby.
(2) barrier film preliminary treatment
In order to improve the wettability of barrier film and slip, the polypropylene single-layer septum that the ozone that adopts flow 0.5 L/min is 12 μ m to thickness is processed, 120 seconds processing times.
(3) accurate coating is dried
Pretreated barrier film is placed on nick version coating machine, and the slip preparing is placed in the hopper of nick version coating machine, is coated with, and coating speed is controlled at 10m/min; Adopt laser or gamma thickness gage to carry out on-line monitoring and control to coating layer thickness, guarantee the even of coating layer thickness, controlling coating layer thickness is 2 μ m; Coating post-drying, rolling are finished product.
Prepared ceramic-coated separator is made to 40Ah ferric phosphate lithium cell traditionally, and test its performance.The battery performance of the present embodiment product is in Table 1.
embodiment 2
(1) ceramic size preparation
1. have at the same time the vacuum of supersonic oscillations function, at a high speed, in planet stirring equipment (rotating speed 0～3000r/min is adjustable, ultrasonic frequency 20kHz vibration) to add deionized water and granularity be the silica of 0.8 μ m, the zirconia that granularity is 1.0, the zinc oxide (weight ratio is 7:2.5:0.5) that granularity is 0.4, ceramic powder (silica, zirconia, zinc oxide mixture) is 10:90 with the weight ratio of deionized water, 2000r/min high-speed stirred while supersonic oscillations 1 hour;
2. the sodium orthophosphate, sodium metasilicate, the lauryl sodium sulfate (weight ratio 1:1:1) that add slip amount 0.5%, 2000r/min high-speed stirred while supersonic oscillations 1 hour;
3. the 1-METHYLPYRROLIDONE, alcohol, the propylene carbonate (weight ratio 1:1:1) that add slip amount 10%, 2000r/min high-speed stirred while supersonic oscillations 1 hour;
4. the LA133 glue that adds slip amount 6%; 2000r/min high-speed stirred while supersonic oscillations 2 hours;
5. turn down rotating speed to 400 r/min, close supersonic oscillations, open vacuum, stir 1 hour, then close and emit slip after Vacuum Balance atmospheric pressure to cross 200 mesh sieves standby.
(2) barrier film preliminary treatment
In order to improve the wettability of barrier film and slip, the polypropylene single-layer septum that the ozone that adopts flow 2 L/min is 25 μ m to thickness is processed, 80 seconds processing times.
(3) accurate coating is dried
Pretreated barrier film is placed in transfer coater, and the slip preparing is placed in the hopper of transfer coater, is coated with, and coating speed is controlled at 2m/min; Adopt laser or gamma thickness gage to carry out on-line monitoring and control to coating layer thickness, guarantee the even of coating layer thickness, controlling coating layer thickness is 5 μ m; Coating post-drying, rolling are finished product.
Prepared ceramic-coated separator is made to 40Ah ferric phosphate lithium cell traditionally, and test its performance.The battery performance of the present embodiment product is in Table 1.
embodiment 3
(1) ceramic size preparation
1. have at the same time the vacuum of supersonic oscillations function, at a high speed, in planet stirring equipment (rotating speed 0～3000r/min is adjustable, ultrasonic frequency 20kHz vibration) to add deionized water and granularity be the alundum (Al2O3) of 0.4 μ m and the magnesium oxide (weight ratio 9:1) that granularity is 0.05, ceramic powder (alundum (Al2O3) and magnesian mixture) is 5:95 with the weight ratio of deionized water, 1500r/min high-speed stirred while supersonic oscillations 2 hours;
2. the many sodium metaphosphates and the ammoniacal liquor (weight ratio 3:1) that add slip amount 3%, 1500r/min high-speed stirred while supersonic oscillations 2 hours;
3. the dimethyl sulfoxide (DMSO), polyoxyethylated alkyl phenol, polyoxyethylene aliphatic alcohol ether, the polyvinyl alcohol (weight ratio 1:1:1:0.5) that add slip amount 5%, 1500r/min high-speed stirred while supersonic oscillations 2 hours;
4. the LA134 glue that adds slip amount 1%; 1500r/min high-speed stirred while supersonic oscillations 1 hour;
5. turn down rotating speed to 400 r/min, close supersonic oscillations, open vacuum, stir 0.5 hour, then close and emit slip after Vacuum Balance atmospheric pressure to cross 200 mesh sieves standby.
(2) barrier film preliminary treatment
In order to improve the wettability of barrier film and slip, three layers of composite diaphragm of polypropylene, polyethylene/polypropylene that the ozone that adopts flow 5 L/min is 40 μ m to thickness are processed, 10 seconds processing times.
(3) accurate coating is dried
Pretreated barrier film is placed on screen process press, and the slip preparing is placed in the hopper of screen process press, is coated with, and coating speed is controlled at 18m/min; Adopt laser or gamma thickness gage to carry out on-line monitoring and control to coating layer thickness, guarantee the even of coating layer thickness, controlling coating layer thickness is 1.5 μ m; Coating post-drying, rolling are finished product.
Prepared ceramic-coated separator is made to 40Ah ferric phosphate lithium cell traditionally, and test its performance.The stereoscan photograph of the present embodiment product as shown in Figure 1, with the battery performance of its manufacture in Table 1.
comparative example 1
(1) ceramic size preparation
1. in common mixer, adding deionized water and granularity is the alundum (Al2O3) of 0.4 μ m and the magnesium oxide (weight ratio 9:1) that granularity is 0.05, ceramic powder (alundum (Al2O3) and magnesian mixture) is 5:95 with the weight ratio of deionized water, and 1000r/min stirs 2 hours;
2. the many sodium metaphosphates and the ammoniacal liquor (weight ratio 3:1) that add slip amount 3%, 1000r/min stirs 2 hours;
3. the dimethyl sulfoxide (DMSO), polyoxyethylated alkyl phenol, polyoxyethylene aliphatic alcohol ether, the polyvinyl alcohol (weight ratio 1:1:1:0.5) that add slip amount 5%, 1000r/min stirs 2 hours;
4. the LA134 glue that adds slip amount 1%; 1000r/min stirs 1 hour;
5. turn down rotating speed to 400 r/min, stir 0.5 hour, then emitting slip, to cross 200 mesh sieves standby.
(2) accurate coating is dried
The three layers of composite diaphragm of polypropylene, polyethylene/polypropylene that are 40 μ m by the thickness without ozone treatment are placed on screen process press, and the slip preparing is placed in the hopper of screen process press, is coated with, and coating speed is controlled at 18m/min; Adopt laser or gamma thickness gage to carry out on-line monitoring and control to coating layer thickness, guarantee the even of coating layer thickness, controlling coating layer thickness is 1.5 μ m; Coating post-drying, rolling are finished product.
Prepared ceramic-coated separator is made to 40Ah ferric phosphate lithium cell traditionally, and test its performance.The stereoscan photograph of this comparative example product as shown in Figure 1, with the battery performance of its manufacture in Table 1.
comparative example 2
The three layers of composite diaphragm of polypropylene, polyethylene/polypropylene that are 40 μ m by the thickness without any processing are made 40Ah ferric phosphate lithium cell traditionally, and battery performance is in Table 1.
Battery performance and stereoscan photograph by above-described embodiment and comparative example can find out, the battery safety prepared without the common diaphragm of any processing is the poorest, the life-span is the shortest (comparative example 2); The ceramic-coated separator of not manufacturing by the slurry preparation method described in the claims in the present invention item, barrier film preprocess method, its coating is obviously inhomogeneous, and the battery safety of made and life-span are lower than the performance of the battery of preparing according to the technique of the claims in the present invention; The ceramic-coated separator that particularly adopts the technique of optimum of the present invention to prepare, has the uniform effect of coating, take that it is prepared battery as barrier film and has best security performance and cycle life.
Table 1
Note: 70 ℃ of cycle life test conditions: voltage range 2.5～3.6V, electric current 1C fills 1C to be put; During capacity attenuation to 80%, stop test.
Claims (7)
1. the present invention relates to the preparation method of the diaphragm material with ceramic coating that a kind of lithium ion battery uses; Barrier film base material is polypropylene, poly individual layer or the above composite membrane of their one deck; Thickness 9～40 μ m; Preparation technology comprises ceramic size preparation, barrier film preliminary treatment, accurate coating oven dry three large steps:
(1) ceramic size preparation
1. have at the same time the vacuum of supersonic oscillations function, at a high speed, in planet stirring equipment (rotating speed 0～3000r/min is adjustable, ultrasonic frequency 20kHz vibration) to add deionized water and granularity be one or more ceramic powders in the alundum (Al2O3), zirconia, silica, magnesium oxide, zinc oxide, titanium dioxide of 0.05～1.0 μ m, the weight ratio of ceramic powder and deionized water is (5～30): (95～70), high-speed stirred (rotating speed is greater than 1000r/min) while supersonic oscillations 0.5～2 hour;
2. add one or more the mixture in Sodium Polyacrylate, many sodium metaphosphates, sodium orthophosphate, sodium metasilicate, lauryl sodium sulfate, ammoniacal liquor, addition is slip 0.5～5%; High-speed stirred (rotating speed is greater than 1000r/min) while supersonic oscillations 0.5～2 hour;
3. add one or more the mixture in 1-METHYLPYRROLIDONE, alcohol, propylene carbonate, glycerine, dimethyl sulfoxide (DMSO), polyoxyethylated alkyl phenol, polyoxyethylene aliphatic alcohol ether, polyvinyl alcohol, addition is slip 0.5～10%; High-speed stirred (rotating speed is greater than 1000r/min) while supersonic oscillations 0.5～2 hour;
4. the carboxy styrene-butadiene rubber (SBR) (being mixed with in advance 50% emulsion) that adds slip amount 0.5～10%, adds the sodium carboxymethylcellulose (CMC) (being mixed with in advance 2% solution) of slip amount 0.3～5%; High-speed stirred (rotating speed is greater than 1000r/min) while supersonic oscillations 0.5～2 hour;
5. turn down below rotating speed to 500 r/min, close supersonic oscillations, open vacuum, stir 0.5～1 hour, then close and emit slip after Vacuum Balance atmospheric pressure to cross 200 mesh sieves standby.
2.(2) barrier film preliminary treatment
In order to improve the wettability of barrier film and slip, adopt the ozone of flow 0.5～5 L/min to process barrier film, 5～120 seconds processing times.
3.(3) accurate coating is dried
Pretreated barrier film is placed on nick version coating machine, and the slip preparing is placed in the hopper of nick version coating machine, is coated with, and coating speed is controlled at 2～20m/min; Adopt laser or gamma thickness gage to carry out on-line monitoring and control to coating layer thickness, guarantee the even of coating layer thickness, controlling coating layer thickness is 1～5 μ m; Coating post-drying, rolling are finished product.
4. ceramic size preparing process as claimed in claim 1, is characterized in that preferred one or more mixtures that adopt in alundum (Al2O3), magnesium oxide and zinc oxide in described alundum (Al2O3), zirconia, silica, magnesium oxide, zinc oxide, titanium dioxide; More preferably adopt alundum (Al2O3) and magnesian mixture, alundum (Al2O3) and magnesium oxide ratio are (7～9.5): (3～0.5).
5. ceramic size preparing process as claimed in claim 1, is characterized in that described CMC also can use hydroxypropyl methylcellulose (HPMC) replacement, and addition is slip 0.5～10%.
6. ceramic size preparing process as claimed in claim 1, be further characterized in that SBR used and CMC also can polyvinyl alcohol (PVA) or LA132, L133, L134 lithium ion battery with a kind of the substituting in bonding agent, addition is slip 0.5～10%.
7. accurate coating process as claimed in claim 3, is characterized in that adopting silk screen printing, transfer type coating or squash type coating process to replace nick version coating process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310198195.0A CN104183805B (en) | 2013-05-25 | 2013-05-25 | A kind of preparation method of ceramic-coated separator |
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| CN106299208A (en) * | 2016-10-12 | 2017-01-04 | 河北金力新能源科技股份有限公司 | A kind of preparation method of high temperature resistant low-resistivity lithium ion battery separator |
| CN106684438A (en) * | 2017-02-07 | 2017-05-17 | 上海璞泰来新能源科技股份有限公司 | Lithium battery capable of rapidly detecting safety |
| CN106784542A (en) * | 2017-02-13 | 2017-05-31 | 河北金力新能源科技股份有限公司 | A kind of lithium ion battery separator of the various coatings of high temperature resistant and preparation method thereof |
| CN107302075A (en) * | 2017-07-03 | 2017-10-27 | 河北金力新能源科技股份有限公司 | A kind of preparation method of lithium ion battery separator from reducing temperature for preventing closed pore |
| CN107611326A (en) * | 2017-09-22 | 2018-01-19 | 广东工业大学 | Cyclodextrin ceramic diaphragm coating slurry and lithium ion battery separator and lithium ion battery |
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| CN109411673A (en) * | 2018-09-28 | 2019-03-01 | 上海恩捷新材料科技有限公司 | Lithium ion battery separator slurry and preparation method and lithium ion battery separator |
| WO2020000164A1 (en) * | 2018-06-26 | 2020-01-02 | 深圳市星源材质科技股份有限公司 | Composite lithium battery separator and preparation method therefor |
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| CN106299208A (en) * | 2016-10-12 | 2017-01-04 | 河北金力新能源科技股份有限公司 | A kind of preparation method of high temperature resistant low-resistivity lithium ion battery separator |
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| CN106684438A (en) * | 2017-02-07 | 2017-05-17 | 上海璞泰来新能源科技股份有限公司 | Lithium battery capable of rapidly detecting safety |
| CN106684438B (en) * | 2017-02-07 | 2020-01-24 | 上海璞泰来新能源科技股份有限公司 | Lithium battery capable of rapidly detecting safety |
| CN106784542B (en) * | 2017-02-13 | 2019-08-06 | 河北金力新能源科技股份有限公司 | A kind of lithium ion battery separator and preparation method thereof of a variety of coatings of high temperature resistant |
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| CN107611326A (en) * | 2017-09-22 | 2018-01-19 | 广东工业大学 | Cyclodextrin ceramic diaphragm coating slurry and lithium ion battery separator and lithium ion battery |
| CN108807813A (en) * | 2018-05-25 | 2018-11-13 | 欣旺达电子股份有限公司 | Lithium ion battery, diaphragm and preparation method thereof |
| CN108807813B (en) * | 2018-05-25 | 2021-10-08 | 欣旺达电动汽车电池有限公司 | Lithium ion battery, diaphragm and preparation method thereof |
| US12021183B2 (en) | 2018-06-06 | 2024-06-25 | Ningde Amperex Technology Limited | Electrochemical device |
| US11264677B2 (en) | 2018-06-06 | 2022-03-01 | Ningde Amperex Technology Limited | Separator and electrochemical device |
| KR20210021585A (en) * | 2018-06-26 | 2021-02-26 | 셴젠 시니어 테크놀로지 매테리얼 씨오., 엘티디. | Composite lithium battery separator and manufacturing method thereof |
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| KR102543254B1 (en) * | 2018-06-26 | 2023-06-13 | 셴젠 시니어 테크놀로지 매테리얼 씨오., 엘티디. | Composite lithium battery separator and its manufacturing method |
| US12040507B2 (en) | 2018-06-26 | 2024-07-16 | Shenzhen Senior Technology Material Co., Ltd. | Composite lithium battery separator and preparation method therefor |
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| CN109300861A (en) * | 2018-09-28 | 2019-02-01 | 苏州清陶新能源科技有限公司 | A kind of oxidation silicon substrate communication substrate and its preparation process and application |
| CN114231105A (en) * | 2021-12-10 | 2022-03-25 | 河北金力新能源科技股份有限公司 | Low-moisture high-insulation lithium ion battery diaphragm and preparation method thereof |
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Effective date of registration: 20210204 Address after: 215636 new East Road, Daxin Town, Zhangjiagang City, Suzhou, Jiangsu Patentee after: ZHANGJIAGANG NENGCI MATERIAL SCIENCE & TECHNOLOGY Co.,Ltd. Address before: 410083 School of materials, Changsha Central South University, Changsha, Hunan Province (room 113, Mittal building) Patentee before: HUNAN ZHENGYUAN ENERGY STORAGE MATERIALS AND DEVICE INSTITUTE |