CN108258176A - A kind of lithium battery diaphragm - Google Patents
A kind of lithium battery diaphragm Download PDFInfo
- Publication number
- CN108258176A CN108258176A CN201711475750.4A CN201711475750A CN108258176A CN 108258176 A CN108258176 A CN 108258176A CN 201711475750 A CN201711475750 A CN 201711475750A CN 108258176 A CN108258176 A CN 108258176A
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- Prior art keywords
- battery
- diaphragm
- layer
- enhancement layer
- conductive layer
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Classifications
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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 belongs to technical field of lithium batteries, and in particular to a kind of battery diaphragm.The battery diaphragm in an organic whole for providing enhancing electric conductivity, puncture resistance energy and thermal stability for the first time of the invention.Battery diaphragm provided by the invention, including film base and respectively positioned at the conductive layer and enhancement layer of film base both sides, wherein, the layer matrix of conductive layer, the layer matrix of enhancement layer and film base are integral, there is no internal interface, so as to prevent composite diaphragm of the prior art because battery life is influenced caused by conductive layer and enhancement layer come off the problem of.
Description
Technical field
The invention belongs to technical field of lithium batteries, and in particular to a kind of battery diaphragm.
Background technology
Lithium battery includes being currently in the lithium-sulfur cell of research hotspot and the lithium ion battery having been widely used, and both this is
It is made of anode, cathode, diaphragm and electrolyte.Diaphragm applied to lithium battery has microcellular structure, and lithium ion can be made suitable
Profit and electronics by that can not pass through, and exactly movement of the lithium ion between positive and negative electrode realizes the charging and discharging of battery, therefore
Diaphragm has very important influence to the chemical property and security performance of lithium battery.
Outstanding septum for lithium ion battery requires good electrolyte wellability, and existing lithium battery diaphragm is typically
It is often weaker to the wetting capacity of electrolyte by insulating polymer polymer, cause diaphragm and electrolyte and electrode it
Between there are larger contact resistances；It is not embedded into electrode in addition, lithium battery is likely due to lithium ion at work and generates lithium crystalline substance
Branch, these lithium dendrite arms can puncture the high molecular polymer of limited mechanical properties；Also, diaphragm is in height made from high molecular polymer
Easy contraction distortion under temperature, this causes battery, and there are security risks during temperature raising due to because non-normal working.
For this purpose, Chinese patent literature CN106356488A discloses the system of a kind of lithium battery or lithium-sulfur cell composite diaphragm
Preparation Method, this method are that conductive nano coating and ceramic functional coating are respectively coated in the both sides of diaphragm matrix.When in use, will
The conductive coating of composite diaphragm is set towards side of the positive electrode, is first conducive to the infiltration of electrolyte, is reduced diaphragm and electrode and electricity
Solve the contact resistance between liquid；Second the conductive coating can also act as second electrode, provide more reaction sites, so as to improve
The chemical property of battery.The ceramic functional coating of the composite diaphragm can improve the puncture resistance and thermal stability of diaphragm
Energy.However, the conductive coating and ceramic functional coating in the technology are to be applied conductive material and ceramic material using binding agent
Prepared by being overlying on diaphragm matrix surface, this results in the combination between conductive coating and ceramic functional coating and diaphragm matrix strong
Degree is weaker, with the propulsion of battery working time, it may appear that the phenomenon that coating part or even large area come off has seriously affected electricity
The service life in pond.
In conclusion how to overcome the problems, such as the combination force difference between each layer of lithium battery composite diaphragm, this is remained
The technical issues of field technology personnel are urgently to be resolved hurrily.
Invention content
The technical problem to be solved in the present invention be to overcome in the prior art the conductive coating of lithium battery battery diaphragm and
The defects of binding force of the ceramic coating respectively between diaphragm matrix is weak, and then offer one kind can enhance electric conductivity, machine simultaneously
The battery diaphragm in an organic whole of tool performance and heat resistance.
The goal of the invention of the present invention is achieved through the following technical solutions：
A kind of battery diaphragm, including film base and functional layer, the functional layer includes conductive layer and/or enhancement layer, described
Conductive layer includes conductive layer matrix and the conducting particles being dispersed therein, and the enhancement layer includes enhancement layer matrix and is scattered in it
In enhancing particle, the material of the conductive layer matrix and/or the enhancement layer matrix and the material of the film base are same
Insulating materials.
The invention provides functional layer battery diaphragm not easily to fall off for the first time, wherein, conductive layer matrix and/or
The material of enhancement layer matrix and film base are same insulating materials, and there is no internal interfaces, of the prior art so as to prevent
Composite diaphragm because caused by conductive layer and enhancement layer come off influence battery life the problem of.When simultaneously, conductive layer and enhancing are set
Can just obtain during layer while enhance electric conductivity, the battery in an organic whole of puncture resistance energy and thermal stability every
Film.
The thickness of the conductive layer and/or the enhancement layer is 10~25 μm.
The thickness of the film base is 20~50 μm.
The conducting particles accounts for 15~40wt% of the conductive layer and/or the enhancing particle accounts for the enhancement layer
25~50wt%.
Battery diaphragm provided by the invention by limiting the ratio of conducting particles and enhancing the ratio of particle, is ensureing
The stress entirety homogeneity of battery diaphragm imparts the enough functionality of battery diaphragm again simultaneously.By the thickness for limiting conductive layer
Degree so that be conducive to the transmission of lithium ion while electric conductivity gives full play to again；By limiting the thickness of film base, that is, ensure that every
The service life of film does not influence the transmission of lithium ion again；By limiting the thickness of enhancement layer, battery diaphragm mechanicalness is being improved
The thickness of battery diaphragm has been maximally reduced while energy and thermal stability again.
The insulating materials is in Kynoar-hexafluoropropylene copolymer, Kynoar or polyvinylpyrrolidone
It is one or more.
The material of the conducting particles is conductive carbon material；Preferably, the conductive carbon material is acetylene black, conductive charcoal
It is one or more in black, carbon nanotube and porous carbon.
The grain size of the acetylene black, the conductive black and the porous carbon be 20~500nm, the length of the carbon nanotube
Spend is 1~5 μm.
The material of the reinforced particulate is ceramic material；Preferably, the ceramic material is aluminium oxide, boron carbide, two
It is one or more in silica, titanium dioxide.
The grain size of the reinforced particulate is 10~50nm.
Battery diaphragm provided by the invention, by the way that Kynoar-hexafluoropropylene copolymer is selected to be used as the material of film matrix
Matter can avoid the problem that battery diaphragm is swollen under electrolyte long period of soaking；By selection with excellent conductive performance
Carbon material and the ceramic material for not influencing electrochemical reaction, advanced optimized the electric conductivity of battery diaphragm, chemical property,
Thermal stability and puncture resistance energy.
The preparation method of the battery diaphragm, includes the following steps：
With film base material liquid：Insulating materials with organic solvent is mixed, is completely dissolved the insulating materials, film base is made
Feed liquid；
Function equipment layered material liquid：It by conducting particles or enhancing particle, mixes, makes described exhausted with insulating materials and organic solvent
Edge material is completely dissolved, and functional layer feed liquid is made；
Diaphragm forming：The film base material liquid is taken, is film-made, then coats the functional layer feed liquid and secondary in its at least one side
Film forming；
Preferably, before the coating step is carried out, make the conducting particles in the functional layer feed liquid, and/or make
The enhancing particle uniformly disperses in the functional layer feed liquid.
By battery diaphragm made from the preparation method of battery diaphragm provided by the invention, in an organic whole, in diaphragm
Interface is not present in portion, can prevent coming off for functional material, and step is simple to operation.
The insulating materials is completely dissolved by the way of heating sealing stirring.
In the diaphragm forming step, be additionally included in control before the coating step conducting particles feed liquid and/
Or the operation that the enhancing feed temperature is 70~80 DEG C；
Or it is additionally included in the operation for completing that compound film temperature is 70~80 DEG C after control coating after the coating step.
The behaviour for completing to be ultrasonically treated after the coating step to composite membrane is additionally included in the diaphragm forming step
Make.
The frequency of ultrasonic wave is 18~23kHz.
The present invention further by the preparation process of battery diaphragm design heating, ultrasound and etc., can promote to apply
Rapid fusion between coating and film matrix so as to improve homogeneity inside battery diaphragm, further increases battery diaphragm and electricity
The service life in pond.
A kind of battery, including：The composite diaphragm or the composite diaphragm according to made from the preparation method, wherein,
The battery, including：Lithium-sulfur cell and lithium ion battery.
In the battery, the conductive layer of the diaphragm is towards anode side, and the enhancement layer of the diaphragm is towards battery
Negative side.
Battery performance provided by the invention is good, durable.
Description of the drawings
In order to illustrate more clearly of the technical solution in the specific embodiment of the invention, specific embodiment will be retouched below
Attached drawing is briefly described needed in stating, it should be apparent that, the accompanying drawings in the following description is some realities of the present invention
Mode is applied, it for those of ordinary skill in the art, without creative efforts, can also be attached according to these
Figure obtains other attached drawings.
The structure for the battery diaphragm that Fig. 1 is provided by the embodiment of the present invention；
The reference numerals are as follows in above-mentioned attached drawing：
1- conducting particles；2- films base；3- enhances particle.
Specific embodiment
Technical scheme of the present invention is clearly and completely described below in conjunction with attached drawing, in the description of the present invention.
Obviously, described embodiment is part of the embodiment of the present invention, instead of all the embodiments.It is in addition, disclosed below
Involved technical characteristic can be combined with each other as long as they do not conflict with each other in different embodiments of the present invention.
Embodiment 1
Battery diaphragm provided in this embodiment, using vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) as film base
The material of body has conductive layer and enhancement layer in the both sides of film matrix, conducting particles acetylene black is wherein dispersed in conductive layer respectively,
Reinforced particulate nano aluminium oxide is dispersed in enhancement layer.The conductive layer of the battery diaphragm and the thickness of enhancement layer are 15 μm,
The thickness of central portion is 25 μm.
The present embodiment provides the battery diaphragm that changes through the following steps that preparing：
5g PVDF-HFP are dissolved in 200mL acetone, heating sealing stirring to PVDF-HFP is completely dissolved, and is recycled
Automatic spray device carries out film on a glass, is placed in 110 DEG C of baking ovens and dries, obtains PVDF-HFP basement membranes；
2g PVDF-HFP is taken to be dissolved in 200mL acetone, after heating sealing stirring is completely dissolved to PVDF-HFP, are added in
0.5g grain sizes are the Al of 30nm2O3, after stirring evenly, coated on PVDF-HFP basement membranes, and dry, obtain single side coating pottery
The PVDF-HFP films of enamel coating；
2g PVDF-HFP is taken to be dissolved in 200mL acetone, after heating sealing stirring is completely dissolved to PVDF-HFP, are added in
0.8g acetylene blacks after stirring evenly, are coated, and dry in the opposite side of PVDF-HFP basement membranes, obtain the PVDF- of dual coating
HFP films；
The PVDF-HFP films after dual coating are soaked in electrolyte, activation is for 24 hours.In the present embodiment, 1M is selected
LiPF6, EC/DMC/DEC=1：1：1 electrolyte.It can certainly select other electrolyte that can be suitable for lithium particle movement.
Embodiment 2
Battery diaphragm provided in this embodiment, using material of the Kynoar as film matrix, in the both sides of film matrix
There are conductive layer and enhancement layer respectively, conductive black is wherein dispersed in conductive layer, reinforced particulate dioxy is dispersed in enhancement layer
Change titanium.The thickness of the conductive layer of the battery diaphragm is 10 μm, and the thickness of enhancement layer is 25 μm, and the thickness of central portion is 20 μm.
The present embodiment provides the battery diaphragm that changes through the following steps that preparing：
5g Kynoar (PVDF) is dissolved in 200mL N-Methyl pyrrolidones, heating sealing stirring is complete to PVDF
Fully dissolved recycles automatic spray device to carry out film on a glass, is placed in baking oven and dries, obtain PVDF basement membranes；
2g PVDF is taken to be dissolved in 200mL N-Methyl pyrrolidones, after heating sealing stirring is completely dissolved to PVDF, are added
Enter the titanium dioxide that 0.5g grain sizes are 10nm, after stirring evenly, be warming up to 75 DEG C, coated on PVDF basement membranes, and dry,
Obtain the pvdf membrane of single side coated ceramic layer；
2g PVDF is taken to be dissolved in 200mL N-Methyl pyrrolidones, after heating sealing stirring is completely dissolved to PVDF, are added
Enter 0.8g conductive blacks, after stirring evenly, be heated to 70 DEG C, then coated, and dry in the opposite side of PVDF basement membranes, obtain double
The pvdf membrane of face coating；
The pvdf membrane after dual coating is soaked in electrolyte, activation is for 24 hours.In the present embodiment, 1M is selected
LiPF6, EC/DMC/DEC=1：1：1 electrolyte.It can certainly select other electrolyte that can be suitable for lithium particle movement.
Embodiment 3
Battery diaphragm provided in this embodiment, using material of the polyvinylpyrrolidone (PVP) as film matrix, in film base
There are conductive layer and enhancement layer in the both sides of body respectively, and carbon nanotube is wherein dispersed in conductive layer, and particle increasing is dispersed in enhancement layer
Strong body silica.The thickness of the conductive layer of the battery diaphragm is 25 μm, and the thickness of enhancement layer is 25 μm, and the thickness of central portion is
50μm。
The present embodiment provides the battery diaphragm that changes through the following steps that preparing：
5g PVP are dissolved in 200mL N-Methyl pyrrolidones, heating sealing stirring to PVP is completely dissolved, and is recycled
Automatic spray device carries out film on a glass, is placed in baking oven and dries, and obtains PVP basement membranes；
2g PVP is taken to be dissolved in 200mL N-Methyl pyrrolidones, after heating sealing stirring is completely dissolved to PVP, are added in
0.5g grain sizes are the silica of 30nm, after stirring evenly, are coated on PVP basement membranes, and dry, obtain single side coated ceramic
The PVP films of layer；
2g PVP is taken to be dissolved in 200mL N-Methyl pyrrolidones, after heating sealing stirring is completely dissolved to PVP, are added in
0.8g carbon nanotubes after stirring evenly, are coated, and dry in the opposite side of PVP basement membranes, obtain the PVP films of dual coating；
The PVP films after dual coating are soaked in electrolyte, activation is for 24 hours.In the present embodiment, 1M LiPF are selected6,
EC/DMC/DEC=1：1：1 electrolyte.It can certainly select other electrolyte that can be suitable for lithium particle movement.
Embodiment 4
Battery diaphragm provided in this embodiment, using vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) as film base
The material of body has conductive layer and enhancement layer in the both sides of film matrix respectively, is wherein dispersed with porous carbon in conductive layer, in enhancement layer
It is dispersed with reinforced particulate nano aluminium oxide.The thickness of the conductive layer of the battery diaphragm is 15 μm, and the thickness of enhancement layer is 15 μm,
The thickness of central portion is 25 μm.
The present embodiment provides the battery diaphragm that changes through the following steps that preparing：
5.5g PVDF-HFP are dissolved in 200mL acetone, heating sealing stirring to PVDF-HFP is completely dissolved, then profit
Film is carried out on a glass with automatic spray device, is placed in 110 DEG C of baking ovens and is dried, obtains PVDF-HFP basement membranes；
2g PVDF-HFP is taken to be dissolved in 200mL acetone, after heating sealing stirring is completely dissolved to PVDF-HFP, are added in
1g grain sizes are the Al of 30nm2O3, it after stirring evenly, is coated on PVDF-HFP basement membranes, is placed in ultrasound 30s under 18kHz, then
Drying obtains the PVDF-HFP films of single side coated ceramic layer；
2g PVDF-HFP is taken to be dissolved in 200mL acetone, after heating sealing stirring is completely dissolved to PVDF-HFP, are added in
0.4g acetylene blacks after stirring evenly, are coated in the opposite side of PVDF-HFP basement membranes, are placed in ultrasound 50s under 20kHz, then dry
It is dry, obtain the PVDF-HFP films of dual coating；
The PVDF-HFP films after dual coating are soaked in electrolyte, activation is for 24 hours.In the present embodiment, 1M is selected
LiPF6, EC/DMC/DEC=1：1：1 electrolyte.It can certainly select other electrolyte that can be suitable for lithium particle movement.
Obviously, the above embodiments are merely examples for clarifying the description, and is not intended to limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation thus extended out or
Variation is still in the protection scope of this invention.
Claims (14)
1. a kind of battery diaphragm, including film base and functional layer, the functional layer includes conductive layer and/or enhancement layer, described to lead
Electric layer includes conductive layer matrix and the conducting particles being dispersed therein, and the enhancement layer includes enhancement layer matrix and is dispersed therein
Enhancing particle, which is characterized in that the material of the material of the conductive layer matrix and/or the enhancement layer matrix and the film base
Matter is same insulating materials.
2. battery diaphragm according to claim 1, which is characterized in that the thickness of the conductive layer and/or the enhancement layer
It is 10~25 μm.
3. battery diaphragm according to claim 1 or 2, which is characterized in that the thickness of the film base is 20~50 μm.
4. according to claim 1-3 any one of them battery diaphragms, which is characterized in that the conducting particles accounts for the conductive layer
15~40wt% and/or the enhancing particle account for 25~50wt% of the enhancement layer.
5. according to claim 1-4 any one of them battery diaphragms, which is characterized in that
The insulating materials is one in Kynoar-hexafluoropropylene copolymer, Kynoar or polyvinylpyrrolidone
Kind is a variety of.
6. according to claim 1-5 any one of them battery diaphragms, which is characterized in that the material of the conducting particles is conduction
Carbon material；Preferably, the conductive carbon material is one or more in acetylene black, conductive black, carbon nanotube and porous carbon.
7. battery diaphragm according to claim 6, which is characterized in that the acetylene black, the conductive black and described more
The grain size of hole carbon is 20~500nm, and the length of the carbon nanotube is 1~5 μm.
8. according to claim 1-7 any one of them battery diaphragms, which is characterized in that the material of the reinforced particulate is pottery
Ceramic material；Preferably, the ceramic material is one or more in aluminium oxide, boron carbide, silica, titanium dioxide.
9. according to claim 1-8 any one of them battery diaphragms, which is characterized in that the grain size of the reinforced particulate is 10
~50nm.
10. a kind of preparation method of claim 1-9 any one of them battery diaphragms, which is characterized in that include the following steps：
With film base material liquid：Insulating materials with organic solvent is mixed, is completely dissolved the insulating materials, film base-material is made
Liquid；
Function equipment layered material liquid：By conducting particles or enhancing particle, mixed with insulating materials and organic solvent, make the insulation material
Material is completely dissolved, and functional layer feed liquid is made；
Diaphragm forming：Take the film base material liquid, be film-made, then its at least one side coat the functional layer feed liquid and it is secondary into
Film；
Preferably, before the coating step is carried out, make the conducting particles in the functional layer feed liquid, and/or make described
Enhance particle to uniformly disperse in the functional layer feed liquid.
11. the preparation method of battery diaphragm according to claim 10, which is characterized in that in the diaphragm forming step,
It is additionally included in that carry out controlling the conducting particles feed liquid and/or the enhancing feed temperature before the coating step be 70~80 DEG C
Operation；
Or it is additionally included in the operation for completing that compound film temperature is 70~80 DEG C after control coating after the coating step.
12. the preparation method of the battery diaphragm according to claim 10 or 11, which is characterized in that the diaphragm forming step
In be additionally included in the operation for completing to be ultrasonically treated after the coating step to composite membrane, the frequency of ultrasonic wave for 18~
23kHz。
13. a kind of battery, which is characterized in that including：Claim 1-9 any one of them composite diaphragm or according to claim
Composite diaphragm made from 10-12 any one of them preparation methods, wherein, the battery, including：Lithium-sulfur cell and lithium-ion electric
Pond.
14. battery according to claim 13, which is characterized in that the conductive layer of the diaphragm is towards anode side, institute
The enhancement layer of diaphragm is stated towards battery cathode side.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711475750.4A CN108258176A (en) | 2017-12-29 | 2017-12-29 | A kind of lithium battery diaphragm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711475750.4A CN108258176A (en) | 2017-12-29 | 2017-12-29 | A kind of lithium battery diaphragm |
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| CN108258176A true CN108258176A (en) | 2018-07-06 |
Family
ID=62724590
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| CN201711475750.4A Pending CN108258176A (en) | 2017-12-29 | 2017-12-29 | A kind of lithium battery diaphragm |
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Cited By (4)
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| CN109244328A (en) * | 2018-09-25 | 2019-01-18 | 合肥先杰新能源科技有限公司 | Lithium ion battery separator and preparation method thereof |
| CN109449494A (en) * | 2018-11-06 | 2019-03-08 | 成都市银隆新能源产业技术研究有限公司 | The preparation method and lithium ion battery of lithium ion battery solid electrolyte interface layer |
| CN110854345A (en) * | 2019-12-02 | 2020-02-28 | 安徽新衡新材料科技有限公司 | High-performance lithium-sulfur battery diaphragm and preparation method and application thereof |
| CN112117420A (en) * | 2020-09-30 | 2020-12-22 | 珠海冠宇电池股份有限公司 | Battery separator, preparation method thereof and lithium ion battery |
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