CN102903879A - Method for preparing organic-inorganic composite diaphragm used for secondary cell - Google Patents
Method for preparing organic-inorganic composite diaphragm used for secondary cell Download PDFInfo
- Publication number
- CN102903879A CN102903879A CN2012102726108A CN201210272610A CN102903879A CN 102903879 A CN102903879 A CN 102903879A CN 2012102726108 A CN2012102726108 A CN 2012102726108A CN 201210272610 A CN201210272610 A CN 201210272610A CN 102903879 A CN102903879 A CN 102903879A
- Authority
- CN
- China
- Prior art keywords
- barrier film
- soluble
- organic
- salt
- bath
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for preparing an organic-inorganic composite diaphragm used for a secondary cell, which comprises the following steps: 1) the organic diaphragm with porousness is passed through a first soluble salt aqueous solution bath; 2) then the diaphragm is passed through a second soluble salt aqueous solution bath; 3) then diaphragm is passed through a deionized water bath; and 4) the organic-inorganic composite diaphragm used for the secondary cell can be obtained after drying. The first soluble salt and the second soluble salt can generate a chemical reaction, the inorganic sediment is generated and deposited on the surface of the organic diaphragm with porousness. The method increases the ion conductivity, the heat stability of a lithium ion battery diaphragm and ensure the security of the cell, the multiplying power performance of the lithium ion battery is increased, the cost of the raw material and technology is low, the operation method is simple, no harmlessness is generated on environment, and the method of the invention is convenient for industrialization.
Description
Technical field
The present invention relates to the secondary cell field, particularly relate to organic and inorganic composite diaphragm of a kind of lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery has had the history in more than 20 year from 1990 nearly since by the exploitation commercialization of Japanese Sony company.Because it has higher volumetric specific energy, gravimetric specific energy and the good feature of environmental protection, just progressively replace traditional lead-acid battery, NI-G and Ni-MH battery, and be widely used in the portable 3C electronic equipments such as mobile phone, notebook computer, captured rapidly very large market and fast development.Less, lighter along with in recent years electronic product being required, thinner demand is more and more stronger.In addition, lithium ion battery is used for electric tool and electric bicycle and mixed moving, the exploitation of electric automobile is an in recent years very large industry of various countries' dynamics of investment, this field succeed in developing the petroleum resources that can alleviate growing tension, therefore very high international economy strategy meaning is arranged.These chemical power source products are except comprising the lower price of pursuit, and pursuing higher energy density and fail safe becomes the strong actuating force of improving electronic product,
Lithium ion battery is mainly by positive/negative plate, barrier film, and electrolyte and battery case form.Wherein, barrier film is one of important component part, play a part to prevent interfacial structure and internal resistance that positive/negative plate is short-circuited and provides lithium ion transmission channel, its performance to determine lithium ion battery, and directly affected chemical property and the security performance of lithium ion battery.
So far commercial lithium ion battery separator material is occupied an leading position with polyolefin, and commercially produced product is with Celgard, Asahi, and Tonen, star sources etc. are representative.These barrier films have comparatively good wettability with traditional electrolyte usually, yet because its relatively low thermal deformation and/or melt temperature (125 ~ 150 ° about C) to have caused them be not very desirable to the fail safe of lithium ion battery, thereby limited the application of corresponding battery in the transportation power field.People are by various means development of new barrier films or existing barrier film is carried out the improvement of thermal stability and fail safe under this background.Existing technological means applies outside high energy source (such as plasma or electron beam irradiation except indivedual uses, infrared, ultra-violet radiation, cross-ventilation heat is transmitted (CN101626095A)) polyolefin substrate is carried out outside the thermal stability improvement, wherein normally used method is the organic-inorganic substances compound membrane of preparation.
The mode that document Journal of Power Sources 195 (2010) 8302 – 8305 adopt dip coated has prepared three layers of inorganic/organic/inorganic compound film will containing the Kynoar of alundum (Al2O3) particle-hexafluoropropylene copolymer solution thin-layer coating on the two sides of polymethyl methacrylate film.Increased at high rate performance by the cobalt acid lithium (LiCoO2) of this barrier film preparation/more commercial polyethylene barrier film of MCMB (MCMB) battery.Yet barrier film preparation process relative complex has wherein expended again a large amount of environmentally harmful organic solvents such as acetone, dimethylbenzene etc.
Document Journal of Power sources 196 (2011) 8125-8128 have adopted the method for organic solution casting film sequentially to coat polyacrylonitrile/silicon dioxide and porousness polyvinylidene difluoride film on the carbon negative pole.Nickel cobalt manganese 333 ternarys of preparation/more common polypropylene diaphragm of graphite battery has improved high rate performance and the thermal stability of battery thus.Clearly, this preparation process has process loaded down with trivial details too, and organic solvent (dimethyl formamide, acetone) is to the disadvantage of working the mischief property of environment.
The multilayer Kynoar of US Patent No. 6562511 preparation/silicon dioxide composite diaphragm also is the method that adopts the solution-cast film forming, and the essence of barrier film layers of material is the same, distinguish just inorganic, what difference of organic principle.
US Patent No. 2010/0009265A1 adopts the normally used Wet technique of Asahi to prepare polyethylene/silicon dioxide single-layer septum.The nano silicon of processing through surfactant is added in the mixture of high density polyethylene (HDPE) and atoleine.
Although above-mentioned these measures can make moderate progress to the performance of barrier film, the technical process more complicated of these methods, and mostly adopt organic solvent system processing, not only greatly increase the manufacturing cost of battery, and bring harm to environment.Use in addition the technology mode of coating easily to cause the part closed pore to cause porosity to reduce, therefore can't satisfy the extensive industrialized requirement of lithium ion battery.The present invention therefore.
Summary of the invention
The purpose of this invention is to provide a kind of for the preparation of the method for secondary cell with organic and inorganic Ceramic Composite barrier film.The method adopts cheap inorganic raw material to embed the nano inorganic ceramic particle in the mode of chemical reaction liquid phase deposition on the basis of the existing organic barrier film of porousness.Be immersed in through the barrier film of said method preparation and obviously improved ionic conductivity, thermal stability and fail safe in the electrolyte.In addition, another object of the present invention provides the nano ceramics barrier film of being produced by described method, and the barrier film of making thus can be used for making battery.
In order to solve these problems of the prior art, technical scheme provided by the invention is:
A kind of for the preparation of the method for secondary cell with organic and inorganic Ceramic Composite barrier film, it is characterized in that said method comprising the steps of:
(1) the organic barrier film of porousness is passed through the water-soluble bath of liquid of the first soluble-salt;
(2) and then with barrier film pass through the water-soluble bath of liquid of the second soluble-salt;
(3) then barrier film is passed through the deionization water-bath;
(4) dry barrier film.
Wherein said the first soluble-salt and the second soluble-salt can produce chemical reaction, and the generation inorganic precipitation is deposited on the organic membrane surface of porousness.
Preferably, the organic barrier film of porousness is selected from polyalkene diaphragm in the described method.
Preferably, the concentration of the first soluble aqueous solution of passing through of described method septation or the second soluble-salt aqueous solution is between 0.2 ~ 3.0M.
Preferably, described method step (1) or step (2) septation time of bathing by saline solution be controlled at 0.1 hour ~ 48 hours.
Preferably, cleaning the reagent that adopts in the described method step (3) is deionized water, and wash number is controlled at 1 ~ 5 time.
Preferably, in described method step (1) or the step (2) operation be normal temperature or intensification with the saline solution of agitating device in carry out; Under Elevated Temperature Conditions, solution is to operate under the mode that refluxes.
Preferably, described method step (4) drying is that temperature is controlled in the scope of 25 ° of C ~ 100 ° C and carries out in air.
Another object of the present invention is to provide a kind of secondary cell organic and inorganic Ceramic Composite barrier film for preparing, it is characterized in that said method comprising the steps of:
(1) the organic barrier film of porousness is passed through the water-soluble bath of liquid of the first soluble-salt;
(2) and then with barrier film pass through the water-soluble bath of liquid of the second soluble-salt;
(3) then barrier film is passed through the deionization water-bath;
(4) dry barrier film.
Wherein said the first soluble-salt and the second soluble-salt can produce chemical reaction, and the generation inorganic precipitation is deposited on the organic membrane surface of porousness.
Another purpose of the present invention is to provide a kind of secondary cell, comprising:
(1) anode;
(2) electrolyte;
(3) negative electrode;
(4) barrier film, its septation are a kind of ceramic diaphragms that is formed by technique claimed in claim 9.
The method of embodiments of the present invention aim to provide a kind of novel preparation organic-inorganic substances compound membrane.The method has avoided using a large amount of organic solvents.As mentioned below, the composite diaphragm for preparing with the method is used for secondary chemical cell, especially lithium ion battery, can improve its ionic conductivity in electrolyte, the thermal stability of battery and fail safe have method simple, cost is low, and is little to environmental hazard, is convenient to the advantage of industrialization.
Principle of the present invention is based on the reactant aqueous solution that a class can generate precipitation.The precipitation that generates can spontaneously deposit in the mode of liquid deposition and be adsorbed on the organic barrier film of porousness.
In various execution modes of the present invention, may further comprise the steps for the preparation of the technique of organic and inorganic composite diaphragm:
(1) the organic barrier film of porousness is passed through the water-soluble bath of liquid of the first soluble-salt;
(2) and then with barrier film pass through the water-soluble bath of liquid of the second soluble-salt;
(3) then barrier film is passed through the deionization water-bath;
(4) dry barrier film.
In various execution modes of the present invention, provide a kind of simple for the preparation of the organic and inorganic composite diaphragm, safety, cheaply technique.Wherein, above-mentioned used porousness barrier film can be any existing commercialization polyalkene diaphragm, also can be the organic barrier films of any homemade other porousness.
In various execution modes of the present invention, the first soluble-salt and the second soluble-salt comprise any two kinds of materials (or many kinds of substance) that can react the generation inorganic sediment, the selection that is to say the two has relevance, comprises that any two or more can carry out mutually the material that chemical reaction generates inorganic sediment.
In various execution modes of the present invention, the concentration range of the first soluble-salt or the second soluble-salt is between 0.2M ~ 3M.
In various execution modes of the present invention, the first of passing through or the second saline solution bathe operation can be normal temperature or intensification with the aqueous solution of agitating device in carry out, under Elevated Temperature Conditions, solution operates in the mode that refluxes, and can avoid like this loss of moisture.
In various execution modes of the present invention, be limited to 0.1 hour under the time of immersion, on be limited to 48 hours.
In various execution modes of the present invention, wash and prepare the first, the used water of the second soluble-salt all uses deionized water.
In various execution modes of the present invention, the washing barrier film number of times under be limited to 1 time, on be limited to 5 times.
In various execution modes of the present invention, drying is at the lower limit of about 25 ° of C and approximately carry out under the temperature between the upper limit of 100 ° of C in air.
By above technical scheme provided by the present invention as seen, compared with prior art, the invention provides a kind of diagram modification method for improving lithium ion battery security and thermal stability, the method not only can improve the ionic conductivity of lithium ion battery separator, the fail safe of thermal stability and assurance battery, can also further improve the high rate performance of lithium ion battery, have raw material and process costs is low, method is simple to operate, environmental sound, be convenient to the advantage of industrialization, be conducive to improve the market application foreground of lithium ion battery, be of great practical significance and commercial value.
The present invention can obtain a kind of ceramic diaphragm for the manufacture of secondary cell, and it forms technique and may further comprise the steps: (1) passes through the water-soluble bath of liquid of the first soluble-salt with the organic barrier film of porousness; (2) and then with barrier film pass through the water-soluble bath of liquid of the second soluble-salt; (3) then barrier film is cleaned by the deionization water-bath; (4) dry barrier film.
With respect to scheme of the prior art, advantage of the present invention is:
In sum, compared with prior art, provided by the invention a kind of for the preparation of the method for secondary cell with organic and inorganic Ceramic Composite barrier film, the method has avoided using a large amount of organic solvents, adopts cheap inorganic solubility raw material to embed the nano inorganic ceramic particle in the mode of chemical liquid deposition on the basis of the existing organic barrier film of porousness.Be immersed in through the barrier film of said method preparation and obviously improved ionic conductivity in the electrolyte, thermal stability and fail safe, can also improve the high rate performance of battery, has cost low, method is simple, and environmental sound is convenient to the advantage of extensive industrialization, be conducive to improve the market application foreground of lithium ion battery, be of great practical significance.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples:
Fig. 1 is the production procedure schematic diagram of organic and inorganic ceramic diaphragm among the present invention.
Fig. 2 is the SEM figure of commercialization barrier film before and after PROCESS FOR TREATMENT of the present invention; Wherein A is the SEM figure of commercialization barrier film before PROCESS FOR TREATMENT of the present invention, and B is the SEM figure of commercialization barrier film after PROCESS FOR TREATMENT of the present invention.
1 – the first soluble-salt solution bath wherein; 2 – the second soluble-salt solution bath; 3 – deionization water-baths; 4 – drying units; 5 – coiler devices.
Embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for explanation the present invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.Introduce and general introduction
The present invention by way of example but not the mode that provides restriction describe.It should be noted, may not refer to the same embodiment " " described in the disclosure file or " a kind of " execution mode, and refer to have at least a kind of.
Hereinafter various aspects of the present invention will be described.Yet, it is evident that for those of skill in the art, can implement the present invention in only some or all of aspects according to the present invention.For purposes of illustration, this paper provides concrete numbering, material and configuration, so that people can thoroughly understand the present invention.Yet, it is evident that for those of skill in the art, the present invention need not concrete details and can implement.In other examples, the present invention is obscure to omit or has simplified well-known feature in order not make.
Various operations are described successively as a plurality of discrete steps, and illustrate to help most understanding mode of the present invention; Yet, in-order description should be interpreted as that these operations of hint must depend on order.
Various execution modes will be described according to the reactant of type species.It is evident that for those of skill in the art, the present invention can implement with different types of reactant of any amount, and is not those reactants that provide for the purpose of illustration and here.In addition, also it is evident that, the present invention is not limited to any specific mixing example.
Be security performance and the reduction manufacturing cost of improving secondary battery membrane, industry generally adopts the method for organic barrier film inorganic compounding.Usually habitual means are to adopt the method for organic solution casting film.Yet this method technique is loaded down with trivial details, and it is high, big for environment pollution that organic solvent is processed cost recovery.Organic inorganic nano combinedization of barrier film that the present invention proposes adopted and the distinct method of industry, is that a kind of raw material and technological operation cost are low, and environmentally safe is easy to a kind of method of large-scale production composite diaphragm.
For the manufacture of the method for secondary cell with organic and inorganic Ceramic Composite barrier film
The invention provides a kind of for the manufacture of secondary cell, particularly lithium ion battery is with the method for organic and inorganic Ceramic Composite barrier film, can be used for existing porousness barrier film is carried out modification, inorganic nano combinedization, be applied to make in the technical process of lithium ion battery, improve fail safe and the chemical property of battery.
Principle of the present invention is based on the reactant aqueous solution that a class can generate precipitation.The precipitation that generates can spontaneously deposit in the mode of liquid deposition and be adsorbed on the organic barrier film of porousness.
In various execution modes of the present invention, may further comprise the steps for the preparation of the specific embodiment of organic and inorganic composite diaphragm: (1) with the organic barrier film of porousness by containing the water-soluble bath of liquid of the first soluble-salt; (2) then with this porousness barrier film by containing the water-soluble bath of liquid of the second soluble-salt; (3) barrier film is again by the deionization water-bath; (4) dry barrier film.
In various execution modes of the present invention, provide a kind of simple for the preparation of the organic and inorganic composite diaphragm, safety, the technique that cost is low.Wherein, above-mentioned used porousness barrier film can make existing commercial any polyalkene diaphragm (Celgard, Asahi, Tonen, Entek, star source etc.), also can be the organic barrier films of any homemade other porousness.
In various execution modes of the present invention, the first soluble-salt and the second soluble-salt comprise any two kinds of materials (or many kinds of substance) that can react the generation inorganic sediment, the selection that is to say the two has relevance, comprises that any two or more can carry out mutually the material that chemical reaction generates inorganic sediment.
In various execution modes of the present invention, the concentration range of the first soluble-salt or the second soluble-salt is between 0.2M ~ 3M.
In various execution modes of the present invention, the saline solution that passes through bathe operation can be normal temperature or intensification with the aqueous solution of agitating device in carry out, under Elevated Temperature Conditions, solution operates in the mode that refluxes, and can avoid like this loss of moisture.
In various execution modes of the present invention, be limited to 0.1 hour under the time of immersion, on be limited to 48 hours.
In various execution modes of the present invention, wash and prepare the first, the used water of the second soluble-salt all uses deionized water.
In various execution modes of the present invention, the washing barrier film number of times under be limited to 1 time, on be limited to 5 times.
In various execution modes of the present invention, drying is at the lower limit of about 25 ° of C and approximately carry out under the temperature between the upper limit of 100 ° of C in air.
Preparation polyethylene (PE)/calcium carbonate (CaCO
3) barrier film
In a kind of embodiment of the present invention, PE/CaCO
3Barrier film can be prepared by following mode.The material and the reagent that are used for this research comprise: the PE barrier film
1M calcium chloride (CaCl
2) solution, 1M sodium carbonate (Na
2CO
3) solution and deionized water.The PE barrier film of at first weighing obtains first heavy (W0); Then with the 1M CaCl of PE barrier film by 80 ° of C
2The aqueous solution, maintenance solution refluxes and stirred 1 hour; Then with the 1M Na of PE barrier film by 80 ° of C
2CO
3Solution, maintenance solution refluxes and stirred 1 hour; Take out PE star source barrier film, by deionization water-bath 2 times; The PE barrier film that final drying is handled well is in the baking oven of 50 ° of C and claim its final weight (W).
Result of the test increases weight 18.1% after calculating membrane treatment, and this is worth namely CaCO
3Account for the weight of whole barrier film.Correspondingly, barrier film after treatment the ionic conductivity in common lithium-ion electrolyte improved 230%.
Preparation polypropylene (PP)/calcium carbonate (CaCO
3) barrier film
In a kind of embodiment of the present invention, PP/CaCO
3Barrier film can be prepared by following mode.The material and the reagent that are used for this research comprise: the PP barrier film (
2400), 1M CaCl
2Solution, 1M Na
2CO
3Solution and deionized water.At first weigh
Obtain first heavy (W0); Then with the 1M CaCl of PP barrier film by 80 ° of C
2The aqueous solution, maintenance solution refluxes and stirred 1 hour; Then with the 1M Na of PP barrier film by 80 ° of C
2CO
3Solution, maintenance solution refluxes and stirred 1 hour; Take out the PP membrane membrane, by deionization water-bath 2 times; The PP barrier film that final drying is handled well is in the baking oven of 50 ° of C and claim its final weight (W).
Result of the test increases weight 17.5% after calculating membrane treatment, and this is worth namely CaCO
3Account for the weight of whole barrier film.Correspondingly, barrier film after treatment the ionic conductivity in common lithium-ion electrolyte improved 210%.
Preparation polypropylene (PP)/polyethylene (PE)/polypropylene (PP) // calcium carbonate (CaCO
3) barrier film
In a kind of embodiment of the present invention, PP/PE/PP//CaCO
3Barrier film can be prepared by following mode.The material and the reagent that are used for this research comprise: the PP/PE/PP barrier film (
2325), 1M CaCl
2Solution, 1M Na
2CO
3Solution and deionized water.The PP/PE/PP barrier film of at first weighing obtains first heavy (W0); Then with the 1M CaCl of PP/PE/PP barrier film by 80 ° of C
2Water-soluble bath of liquid, maintenance solution refluxes and stirred 1 hour; Again with the 1M Na of PP/PE/PP barrier film by 80 ° of C
2CO
3Solution bath, maintenance solution refluxes and stirred 1 hour; Take out the PP/PE/PP barrier film, by deionization water-bath 2 times; The PP/PE/PP barrier film that final drying is handled well is in the baking oven of 50 ° of C and claim its final weight (W).
Preparation polyethylene (PE)/phosphoric acid hydrogen zirconium (Zr(HPO
4)
2) barrier film
In a kind of embodiment of the present invention, PE/Zr (HPO
4)
2Barrier film can be prepared by following mode.The material and the reagent that are used for this research comprise: the PE barrier film
1M zirconium oxychloride (ZrOCl
2) solution, 1M phosphoric acid (H
3PO
4) solution and deionized water.The PE barrier film of at first weighing obtains first heavy (W0); Then with the 1M ZrOCl of PE barrier film by 80 ° of C
2The aqueous solution, maintenance solution refluxes and stirred 1 hour; Then with the 1M H of PE barrier film by 80 ° of C
3PO
4Solution, maintenance solution refluxes and stirred 1 hour; Take out PE star source barrier film, by deionization water-bath 2 times; The PE barrier film that final drying is handled well is in the baking oven of 50 ° of C and claim its final weight (W).
Preparation polypropylene (PP)/phosphoric acid hydrogen zirconium (Zr(HPO
4)
2) barrier film
In a kind of embodiment of the present invention, PP/Zr (HPO
4)
2Barrier film can be prepared by following mode.The material and the reagent that are used for this research comprise: the PP barrier film (
2400), 1M zirconium oxychloride (ZrOCl
2) solution, 1M phosphoric acid (H
3PO
4) solution and deionized water.The PP barrier film of at first weighing obtains first heavy (W0); Then with the 1M ZrOCl of PP barrier film by 80 ° of C
2The aqueous solution, maintenance solution refluxes and stirred 1 hour; Then with the 1M H of PP barrier film by 80 ° of C
3PO
4Solution, maintenance solution refluxes and stirred 1 hour; Take out the PP barrier film, by deionization water-bath 2 times; The PP barrier film that final drying is handled well is in the baking oven of 50 ° of C and claim its final weight (W).
Embodiment 6
Preparation polypropylene (PP)/polyethylene (PE)/polypropylene (PP) // phosphoric acid hydrogen zirconium (Zr(HPO
4)
2) barrier film
In a kind of embodiment of the present invention, PP/PE/PP//Zr (HPO
4)
2Barrier film can be prepared by following mode.The material and the reagent that are used for this research comprise: the PP/PE/PP barrier film (
2325), 1M ZrOCl
2Solution, 1M H
3PO
4Solution and deionized water.At first weigh
Obtain first heavy (W0); Then with the 1M ZrOCl of PP/PE/PP barrier film by 80 ° of C
2The aqueous solution, maintenance solution refluxes and stirred 1 hour; Then with the 1M H of PP/PE/PP barrier film by 80 ° of C
3PO
4Solution, maintenance solution refluxes and stirred 1 hour; Take out PP/PE/PP star source barrier film, by deionization water-bath 2 times; The PP/PE/PP barrier film that final drying is handled well is in the baking oven of 50 ° of C and claim its final weight (W).
In sum, compared with prior art, provided by the invention a kind of for the preparation of the method for secondary cell with organic and inorganic Ceramic Composite barrier film, the method has avoided using a large amount of organic solvents, adopts cheap inorganic solubility raw material to embed the nano inorganic ceramic particle in the mode of chemical liquid deposition on the basis of the existing organic barrier film of porousness.Be immersed in through the barrier film of said method preparation and obviously improved ionic conductivity in the electrolyte, thermal stability and fail safe, can also improve the high rate performance of battery, has cost low, method is simple, and environmental sound is convenient to the advantage of extensive industrialization, be conducive to improve the market application foreground of lithium ion battery, be of great practical significance.
The above specific embodiment only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvement or replacement, these improvement or replacement also should be considered as protection scope of the present invention.
Claims (9)
1. one kind for the preparation of the method for secondary cell with organic and inorganic composite ceramics barrier film, it is characterized in that said method comprising the steps of:
(1) the organic barrier film of porousness is passed through the water-soluble bath of liquid of the first soluble-salt;
(2) and then with barrier film pass through the water-soluble bath of liquid of the second soluble-salt;
(3) then barrier film is passed through the deionization water-bath;
(4) dry barrier film.
Wherein said the first soluble-salt and the second soluble-salt can produce chemical reaction, and the generation inorganic sediment is deposited on the organic membrane surface of porousness.
2. method according to claim 1 is characterized in that the organic barrier film of porousness is selected from polyalkene diaphragm in the described method.
3. method according to claim 1 is characterized in that the concentration of the first soluble-salt aqueous solution that described method septation is passed through or the second soluble-salt aqueous solution is between 0.2 ~ 3.0M.
4. method according to claim 1, it is characterized in that the time that described method step (1) or step (2) septation are bathed by saline solution be controlled at 0.1 hour ~ 48 hours.
5. method according to claim 1 is characterized in that cleaning in the described method step (3) reagent that uses and is deionized water, and wash number is controlled at 1 ~ 5 time.
6. method according to claim 1, it is characterized in that saline solution in described method step (1) or (2) bathe operation be normal temperature or intensification with the condition of agitating device under carry out; Under Elevated Temperature Conditions, solution is to operate under the mode that refluxes.
7. method according to claim 1 is characterized in that drying in the described method step (4) is that temperature is controlled in the scope of 25 ° of C ~ 100 ° C and carries out in air.
8. a secondary cell is characterized in that the preparation method of described barrier film may further comprise the steps with organic and inorganic Ceramic Composite barrier film:
(1) the organic barrier film of porousness is passed through the water-soluble bath of liquid of the first soluble-salt;
(2) and then with barrier film pass through the water-soluble bath of liquid of the second soluble-salt;
(3) then barrier film is passed through the deionization water-bath;
(4) dry barrier film.
Wherein said the first soluble-salt and the second soluble-salt can produce chemical reaction, and the generation inorganic sediment is deposited on the organic membrane surface of porousness.
9. secondary cell comprises:
(1) anode;
(2) electrolyte;
(3) negative electrode;
(4) barrier film, its septation are a kind of ceramic diaphragms that is formed by technique claimed in claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102726108A CN102903879A (en) | 2012-08-02 | 2012-08-02 | Method for preparing organic-inorganic composite diaphragm used for secondary cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102726108A CN102903879A (en) | 2012-08-02 | 2012-08-02 | Method for preparing organic-inorganic composite diaphragm used for secondary cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102903879A true CN102903879A (en) | 2013-01-30 |
Family
ID=47576021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102726108A Pending CN102903879A (en) | 2012-08-02 | 2012-08-02 | Method for preparing organic-inorganic composite diaphragm used for secondary cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102903879A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103579564A (en) * | 2013-11-18 | 2014-02-12 | 番禺南沙殷田化工有限公司 | Ceramic diaphragm, and preparation method and application thereof |
| WO2019090888A1 (en) * | 2017-11-10 | 2019-05-16 | 江苏华富储能新技术股份有限公司 | Organic-inorganic composite separator for lithium battery and preparation method therefor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040013812A1 (en) * | 2000-06-29 | 2004-01-22 | Wolfgang Kollmann | Method for producing cathodes and anodes for electrochemical systems, metallised material used therein, method and device for production of said metallised material |
| CN101369645A (en) * | 2008-09-23 | 2009-02-18 | 天津力神电池股份有限公司 | Method of manufacturing diaphragm used for high security lithium ion secondary battery |
| CN102122704A (en) * | 2010-12-29 | 2011-07-13 | 中科院广州化学有限公司 | Composite microporous membrane used as lithium ion battery diaphragm as well as preparation method and application thereof |
| CN102459439A (en) * | 2009-06-17 | 2012-05-16 | Sk新技术 | Microporous polyethylene film with thermally stable hybrid-composite layers |
-
2012
- 2012-08-02 CN CN2012102726108A patent/CN102903879A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040013812A1 (en) * | 2000-06-29 | 2004-01-22 | Wolfgang Kollmann | Method for producing cathodes and anodes for electrochemical systems, metallised material used therein, method and device for production of said metallised material |
| CN101369645A (en) * | 2008-09-23 | 2009-02-18 | 天津力神电池股份有限公司 | Method of manufacturing diaphragm used for high security lithium ion secondary battery |
| CN102459439A (en) * | 2009-06-17 | 2012-05-16 | Sk新技术 | Microporous polyethylene film with thermally stable hybrid-composite layers |
| CN102122704A (en) * | 2010-12-29 | 2011-07-13 | 中科院广州化学有限公司 | Composite microporous membrane used as lithium ion battery diaphragm as well as preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103579564A (en) * | 2013-11-18 | 2014-02-12 | 番禺南沙殷田化工有限公司 | Ceramic diaphragm, and preparation method and application thereof |
| CN103579564B (en) * | 2013-11-18 | 2016-02-10 | 番禺南沙殷田化工有限公司 | A kind of ceramic diaphragm and its preparation method and application |
| WO2019090888A1 (en) * | 2017-11-10 | 2019-05-16 | 江苏华富储能新技术股份有限公司 | Organic-inorganic composite separator for lithium battery and preparation method therefor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Porous cellulose diacetate-SiO2 composite coating on polyethylene separator for high-performance lithium-ion battery | |
| Wang et al. | Self-assembly of PEI/SiO2 on polyethylene separators for Li-ion batteries with enhanced rate capability | |
| CN104064707B (en) | Inorganic/organic composite membrane, preparation method of inorganic/organic composite membrane and lithium ion secondary battery containing membrane | |
| Shi et al. | Electrolyte membranes with biomimetic lithium-ion channels | |
| CN105720236B (en) | A kind of sodium-ion battery cathode nickel foam self-supporting sheet Ni3P/C composite materials and preparation method thereof | |
| Zhang et al. | Biomimetic Dendrite‐Free Multivalent Metal Batteries | |
| Gao et al. | Rapid Production of Metal–Organic Frameworks Based Separators in Industrial‐Level Efficiency | |
| Wang et al. | Effect of different contents of organic-inorganic hybrid particles poly (methyl methacrylate) ZrO2 on the properties of poly (vinylidene fluoride-hexafluoroprolene)-based composite gel polymer electrolytes | |
| CN103915594B (en) | A kind of low ionic resistance high-temperature-reslithium lithium battery coated separator | |
| CN106920989B (en) | A kind of copper selenium compound is the sodium-ion battery of negative electrode material | |
| Su et al. | Lithium poly-acrylic acid as a fast Li+ transport media and a highly stable aqueous binder for Li 3 V 2 (PO 4) 3 cathode electrodes | |
| EP3620437B1 (en) | Linear hierarchical structure lithium titanate material, preparation and application thereof | |
| CN104638217A (en) | Modified composite diaphragm and method for preparing diaphragm | |
| Li et al. | Facile and nonradiation pretreated membrane as a high conductive separator for Li-ion batteries | |
| Profili et al. | Toward more sustainable rechargeable aqueous batteries using plasma-treated cellulose-based Li-ion electrodes | |
| CN108258241A (en) | A kind of cathode of lithium battery for inhibiting lithium dendrite growth using ZIF-8 porous carbon materials | |
| CN102569700A (en) | Ceramic coating membrane and preparation method thereof | |
| CN108075088A (en) | Lithium battery diaphragm, its preparation method and the application of the lithium salts containing sulfonated graphene | |
| Joseph et al. | Plasma enabled synthesis and processing of materials for lithium‐ion batteries | |
| CN108110324A (en) | A kind of preparation method of solid lithium ion battery | |
| Shaibani et al. | Permselective membranes in lithium–sulfur batteries | |
| CN102324481A (en) | Composite diaphragm for lithium ion battery and preparation method thereof | |
| Wang et al. | Functional separator enabled by covalent organic frameworks for high‐performance Li metal batteries | |
| Yu et al. | Unveiling sodium ion pollution in spray-dried precursors and its implications for the green upcycling of spent lithium-ion batteries | |
| CN104787799A (en) | Web-type three-dimensional perforated macroporous-mesoporous-structure titanium dioxide material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130130 |