CN102610775A - Lithium ion battery and diaphragm thereof - Google Patents
Lithium ion battery and diaphragm thereof Download PDFInfo
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- CN102610775A CN102610775A CN2012100561187A CN201210056118A CN102610775A CN 102610775 A CN102610775 A CN 102610775A CN 2012100561187 A CN2012100561187 A CN 2012100561187A CN 201210056118 A CN201210056118 A CN 201210056118A CN 102610775 A CN102610775 A CN 102610775A
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Abstract
The invention belongs to the technical field of lithium ion batteries, in particular to a diaphragm with a rough surface. At least one surface of the diaphragm is the rough surface subjected to roughening; and the roughness of the rough surface is 0.5 to 5 mum. Compared with the prior art, the diaphragm has a relatively large surface friction coefficient and a relatively large static friction force; during coiling, the phenomenon of relative deviation caused by relative sliding between a coiling core of a coiling machine and the diaphragm is avoided; the width consistency and the coiling alignment are improved, and the problem of deformation of an electric core is solved; and moreover, the hardness of the electric core is improved due to the variation of the surface interface property. Furthermore, the invention also provides a lithium ion battery with the diaphragm.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion battery that has the barrier film of rough surface and comprise this barrier film.
Background technology
Along with the development of progress of industry with society; Natural resources is the not exhaustive exploitation and the use in the difficult production-goods source of reusable edible particularly; Natural resources such as coal and oil will soon approach exhaustion, and under this background, people are constantly seeking the new green alternative energy.
Along with the continuous progress and development of energy substitution product, lithium ion battery becomes the focus that people pay close attention to gradually.Lithium ion battery is a kind of pollution-free green secondary energy sources that can repeatedly reuse, and meets the requirement of environmental protection and sustainable development, thereby more and more receives people in the industry's favor, and wide application prospect is arranged.
But along with the develop rapidly of lithium ion battery manufacturing technology in recent years, people are also increasingly high to the requirement of battery performance and outward appearance.In process of production, owing to receive the restriction of material and technology, concerning manufacturing enterprise, the consistency of electric core distortion and electric core size is not good, and the fail safe of the hardness of electric core deficiency and electric core not enough or the like all be problem demanding prompt solution.
Lithium ion battery generally comprises electric core and holds the pack case of said electric core, and is poured in the electrolyte in the said pack case, and said electric core comprises positive pole, negative pole, and is interval in the barrier film between positive pole and the negative pole.Wherein, positive pole, barrier film and negative pole are generally processed electric core through winding process or lamination technology.
In order to address the above problem, we have carried out lot of test work, and the result finds; The interface of barrier film and both positive and negative polarity diaphragm is the key of problem place: because common membrane surface is smooth relatively; When reeling, will cause barrier film and pole piece (comprising positive plate and negative plate) the small dislocation on width and length direction, and then cause the off-dimension of the back battery of reeling; And between being equivalent to barrier film and pole piece behind the perfusion electrolyte, added lubricant; The slide relative of barrier film and diaphragm will make electric core distortion or deliquescing, even electric in-core short circuit occurs, causes potential safety hazard.
In view of this, necessaryly provide a kind of and can improve problems such as the distortion of electric core, electric core hardness deficiency and dimensional uniformity be not good, and the lithium ion battery that can improve the barrier film of battery safety and comprise this barrier film.
Summary of the invention
One of the object of the invention is: to the deficiency of prior art, and provide a kind of and can improve problems such as electric core distortion, electric core hardness deficiency and dimensional uniformity be not good, and can improve the barrier film of electric core security performance.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of lithium ion battery is used barrier film, and the one side at least of said barrier film is for through the rough surface of roughening treatment, and the roughness of said rough surface is 0.5～5 μ m, when the roughness of barrier film during less than 0.5 μ m, improves DeGrain; When the roughness of barrier film during,, can increase the difficulty that become because of frictional resistance during drawn needle because of the roughness of barrier film is too big greater than 5 μ m; Needs are transformed workpiece or on the volume pin, are slotted; Reduce barrier film and the contact area of rolling up pin, and when blanking, ventilate, avoid rolling up pin when extracting out; Atmospheric pressure has increased the trouble on the operation to barrier film and the pressure that the volume pin produces.
As a kind of improvement of lithium ion battery of the present invention with barrier film, the roughness of said rough surface is 1～3 μ m.
As a kind of improvement of lithium ion battery of the present invention with barrier film, said roughening treatment is to carry out friction treatment with the frosted mechanism that has predetermined lines at least one surface of said barrier film.The advantage of this method is that principle is simple, and is easy to operate.
As a kind of improvement of lithium ion battery of the present invention with barrier film, said predetermined lines is the fine and closely woven spherical crown shape lines through polishing, and the diameter of said spherical crown is less than 0.5mm.The spherical crown diameter is crossed conference and is caused barrier film damaged, and has destroyed the continuity of its processing.
As a kind of improvement of lithium ion battery of the present invention with barrier film, said roughening treatment is barrier film to be immersed in carry out chemical treatment in the inductor solution, and the advantage of this method is that treatment effect is more even, and the own static that can eradicate a mental barrier.
As a kind of improvement of lithium ion battery of the present invention with barrier film, said inductor solution is for being dissolved in multivalence alcohol interfacial agent inductor FS-202 the solution that ethyl acetate and acetone obtain.
As a kind of improvement of lithium ion battery of the present invention with barrier film, the mass fraction of said multivalence alcohol interfacial agent inductor is 1.0～5.0%, and the mass ratio of ethyl acetate and acetone is 0.4: 1～5: 1.
As a kind of improvement of lithium ion battery of the present invention with barrier film, the basis material of said barrier film be polypropylene (PP), polyethylene (PE), polypropylene (PP) with composite diaphragm, polyimides and the non-woven fabric of polyethylene (PE) in a kind of.
As a kind of improvement of lithium ion battery of the present invention with barrier film, the thickness of said barrier film is 10～30 μ m, and hot strength is 20～100kPa, and porosity is 30～50%,
With respect to prior art, the present invention has the advantage of following several respects at least:
The first, when said barrier film was used for the lithium rechargeable battery coiling, the frictional force between volume pin and the barrier film increased, and was difficult for producing slide relative, thereby had guaranteed the consistency and the coiling appearance of coiling size;
Second; Use said barrier film as anodal and negative pole " electronics dividing plate "---its two sides links to each other with the both positive and negative polarity pole piece respectively, because of its surperficial fluffy roughening degree raising, make itself and both positive and negative polarity pole piece applying degree better; Stiction improves; So both positive and negative polarity pole piece and barrier film can not produce relative slip dislocation, thereby have guaranteed that its battery of producing is not yielding, greatly reduce the deformation rate of electric core;
The 3rd, because both positive and negative polarity pole piece and barrier film can not produce relative slip dislocation, thereby make its contact surface more stable, not only promote the hardness of electric core, and avoided the safety problem that contact causes between the both positive and negative polarity.
The 4th, the barrier film through roughening treatment has only changed its surface and interface character, and the mechanical strength of original barrier film, permeability, pore size and arrange etc. do not change, and therefore, can't influence the electrical property of battery.On the contrary, even, increased its absorbability and hold facility, be beneficial to the cycle performance that improves lithium ion battery electrolyte because its surface is fluffy coarse.
The 5th, implementation method of the present invention is various, and technology is simple, and is with low cost.
Another object of the present invention is to provide a kind of lithium ion battery, and comprise anode pole piece, cathode pole piece, be interval in the barrier film between anode pole piece and the cathode pole piece, and electrolyte, said barrier film is the described barrier film of above-mentioned paragraph.
With respect to prior art; Lithium ion battery of the present invention is because its membrane surface has bigger roughness; Make barrier film and both positive and negative polarity pole piece can not produce relative slip dislocation, make its contact surface more stable, not only promoted the hardness of electric core; Also promote the dimensional uniformity and the security performance of battery, improved the problem on deformation of battery.In addition, because fluffy membrane surface has the liquid storage function, so lithium ion battery of the present invention has better cycle performance.
Description of drawings
Below in conjunction with accompanying drawing and embodiment, the present invention and useful technique effect thereof are elaborated, wherein:
Fig. 1 is ESEM (SEM) surface topography map of the barrier film in the Comparative Examples 1 of the present invention;
Fig. 2 is ESEM (SEM) surface topography map of the barrier film in the embodiment of the invention 1;
Fig. 3 is the hardness test curve chart of the battery of Comparative Examples 1 to 3 of the present invention and embodiment 1 to 3;
Fig. 4 is the normal-temperature circulating performance test curve figure of the battery of Comparative Examples 1 to 3 of the present invention and embodiment 1 to 3;
Fig. 5 is high temperature (45 ℃) the cycle performance test curve figure of the battery of Comparative Examples 1 to 3 of the present invention and embodiment 1 to 3.
Embodiment
Describe the present invention in detail below in conjunction with Figure of description and specific embodiment, still, embodiments of the invention are not limited thereto.
Comparative Examples
The preparation of cathode pole piece: with graphite is negative active core-shell material, and its weight content is 95%; With butadiene-styrene rubber (SBR) is binding agent, and its weight content is 2%; With the carbon black is conductive agent, and its weight content is 3%; Above-mentioned material is joined deionized water for stirring evenly process cathode size; Cathode size is uniformly coated on the Copper Foil, and the oven dry compacting is after cut-parts, welding negative lug make cathode pole piece.
The preparation of anode pole piece: with cobalt acid lithium (LiCoO
2) be positive electrode active materials, its weight content is 96%; With Kynoar (PVDF) is binding agent, and its weight content is 2%; With the carbon black is conductive agent, and its weight content is 2%; Above-mentioned material joined to stir in the N-methyl pyrrolidone (NMP) process anode sizing agent; Anode sizing agent is uniformly coated on the aluminium foil, and the oven dry compacting is after cut-parts, welding positive pole ear make anode pole piece.
The preparation of barrier film: with the microporous polypropylene membrane without roughening treatment is barrier film (thickness is 10 μ m, and hot strength is 20kPa, and porosity is 30%).The gained barrier film is carried out scanning electron microscopic observation, can find that this membrane surface is smoother, only have a spot of minute protrusions (as shown in Figure 1).Recording its surface roughness with Japan three rich (Mitutoyo) SJ-201 surface roughness tester is about 0.1 μ m.
The preparation of electrolyte: with concentration is the lithium hexafluoro phosphate (LiPF of 1M
6) be lithium salts, be solvent with the mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC), the weight ratio of ethylene carbonate and dimethyl carbonate is 3: 7, adds 2% electrolysis additive fluorinated ethylene carbonate (FEC) again.
The preparation of lithium ion battery: after will superposeing successively according to cathode pole piece, anode pole piece, the barrier film that aforementioned technology makes, make electric core, electric core is packed in the battery packages shell, through ageing, change into, make lithium ion battery behind the capacity etc. through winding process.
Comparative Examples 2
Being that with the difference of Comparative Examples 1 barrier film of selecting for use is different, is barrier film (thickness is 30 μ m, and hot strength is 100kPa, and porosity is 50%) with the PP/PE/PP microporous barrier without roughening treatment.The gained barrier film is carried out scanning electron microscopic observation, can find that this membrane surface is smoother, only have a spot of minute protrusions.Recording its surface roughness with Japan three rich (Mitutoyo) SJ-201 surface roughness tester is about 0.2 μ m.
All the other repeat no more with Comparative Examples 1 here.
Comparative Examples 3
Being that with the difference of Comparative Examples 1 barrier film of selecting for use is different, is barrier film (thickness is 15 μ m, and hot strength is 50kPa, and porosity is 40%) with the non-weaving cloth PETG microporous barrier without roughening treatment.The gained barrier film is carried out scanning electron microscopic observation, can find that this membrane surface is smoother, only have a spot of minute protrusions.Recording its surface roughness with Japan three rich (Mitutoyo) SJ-201 surface roughness tester is about 0.3 μ m.
All the other repeat no more with Comparative Examples 1 here.
The preparation of cathode pole piece: with graphite is negative active core-shell material, and its weight content is 95%; With butadiene-styrene rubber (SBR) is binding agent, and its weight content is 2%; With the carbon black is conductive agent, and its weight content is 3%; Above-mentioned material is joined deionized water for stirring evenly process cathode size; Cathode size is uniformly coated on the Copper Foil, and the oven dry compacting is after cut-parts, welding negative lug make cathode pole piece.
The preparation of anode pole piece: with cobalt acid lithium (LiCoO
2) be positive electrode active materials, its weight content is 96%; With Kynoar (PVDF) is binding agent, and its weight content is 2%; With the carbon black is conductive agent, and its weight content is 2%; Above-mentioned material joined to stir in the N-methyl pyrrolidone (NMP) process anode sizing agent; Anode sizing agent is uniformly coated on the aluminium foil, and the oven dry compacting is after cut-parts, welding positive pole ear make anode pole piece.
Preparation with rough surface barrier film:
The first step, the preparation of sand roller: the diameter range of sand roller and is covered with the fine and closely woven spherical crown shape lines through polishing on the roller between 30～120mm, its spherical crown diameter is less than 0.5mm;
Second goes on foot, and has the preparation of the barrier film of rough surface: use ten above-mentioned sand roller to be combined into a frosted mechanism, all have the pressure roller roller devices on each roller of this mechanism, to guarantee friction effect; Then, pending PP/PE/PP barrier film (thickness is 30 μ m, and hot strength is 100kPa, and porosity is 50%) worn according to the biography band mode of S type successively walk around all rollers, on last rolling cylinder; Starting the machine then begins to handle barrier film, and its speed control is at 10～15m/min, and Tension Control is between 5～10N/m.
The gained barrier film is carried out scanning electron microscopic observation, can find that the membrane surface of handling has a large amount of fluffy coarse minute protrusions (as shown in Figure 2).Recording its surface roughness with (Mitutoyo) SJ-201 surface roughness tester is about 4 μ m.
The preparation of electrolyte: with concentration is the lithium hexafluoro phosphate (LiPF of 1M
6) be lithium salts, be solvent with the mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC), the weight ratio of ethylene carbonate (EC) and dimethyl carbonate (DMC) is 3: 7, adds 2% electrolysis additive fluorinated ethylene carbonate (FEC) again.
The preparation of lithium ion battery: after will superposeing successively according to cathode pole piece, anode pole piece, the barrier film that aforementioned technology makes, make electric core, electric core is packed in the battery packages shell, through ageing, change into, make lithium ion battery behind the capacity etc. through winding process.
Embodiment 2
Different with embodiment 1 is that the preparation of rough surface barrier film is arranged:
The first step; The preparation of Treatment Solution: with multivalence alcohol interfacial agent inductor (raising agent FS-202; Milky white liquid) be dissolved in ethyl acetate and acetone, the mass fraction of inductor is between 1.0～5%, and the quality proportioning of ethyl acetate and acetone is 0.4: 1～5: 1;
Second step; Infusion process is handled barrier film: (thickness is 15 μ m with pending non-weaving cloth PETG barrier film; Hot strength is 50kPa, and porosity is 40%) place the container that fills above-mentioned Treatment Solution, handle half an hour after; Take out barrier film, in the drying box of humidity and Controllable Temperature, obtain having the barrier film of rough surface after the drying.In order to realize industrialization, can take the multi-cylinder continuous impregnating, the controlled drying box of temperature and humidity is set above each cylinder.
The gained barrier film is carried out scanning electron microscopic observation, can find that the membrane surface of handling has a large amount of fluffy coarse minute protrusions.Recording its surface roughness with Japan three rich (Mitutoyo) SJ-201 surface roughness tester is about 3 μ m.
All the other repeat no more with embodiment 1 here.
Embodiment 3
The preparation that different with embodiment 1 is has a rough surface barrier film is through utilizing high-velocity particles bump barrier film (polyimides/polypropylene/polyimides composite construction; Its thickness is 10 μ m; Hot strength is 20kPa; Porosity is 30%), and the control that is aided with the riot field obtains, all the other are with embodiment 1.
The gained barrier film is carried out scanning electron microscopic observation, can find that the membrane surface of handling has more fluffy coarse minute protrusions.Recording its surface roughness with Japan three rich (Mitutoyo) SJ-201 surface roughness tester is about 1 μ m.
All the other repeat no more with embodiment 1 here.
Comparative Examples 1 to 3 and embodiment 1 to 3 gained battery are contrasted as follows:
One, the outward appearance of barrier film with rough surface that embodiment 1 to 3 is prepared and the membrane coil coiled of Comparative Examples 1 to 3 electricity core compares:
The barrier film with rough surface that embodiment 1 to 3 is prepared and the barrier film of Comparative Examples 1 to 3 are reeled on same up-coiler; Make electric core; Observe the electric core outward appearance of winding; The result finds that the electric core dimensional uniformity that the fluffy coarse membrane coil in surface lays out is better relatively, and the appearance that winds is better.
Two, the distortion ratio of the electric core that the barrier film with rough surface that embodiment 1 to 3 is prepared and the membrane coil of Comparative Examples 1 lay out is done statistics:
The barrier film with rough surface of preparing embodiment 1 to 3 and the membrane coil coiled of Comparative Examples 1 electricity core are finished volume test from being wound up into, the deformation rate of statistics between this operation section, and the gained result is shown in table 1.
Table 1 is the electric core deformation rate of embodiment 1 to 3 and Comparative Examples 1
Can be known by table 1: the distortion of electric core can be effectively improved on the surface through the barrier film of roughening treatment.
Three, the electric core hardness of the membrane coil coiled of the barrier film with rough surface of embodiment 1 to 3 preparation and Comparative Examples 1 to 3 is compared:
After electric core shaping, from every group of electricity core, randomly draw 1 electric core, carry out hardness test, the result is as shown in Figure 3.Can find out from the hardness test curve of Fig. 3: the battery hardness that the surface makes through the barrier film of fluffy roughened is relatively large.
Four, the cycle performance of the battery that the barrier film with rough surface that embodiment 1 to 3 is prepared and the barrier film of Comparative Examples 1 to 3 are made compares:
At first, at room temperature carried out 800 circulations after, capacity all remains on more than 85%, and the electric core cycle performance that the coarse barrier film prepared of embodiment 1 to 3 is made is superior to the electric core that Comparative Examples 1 to 3 is made a little;
Secondly, under 45 ℃ of high temperature, carried out 300 circulations after, capacity all remains on more than 95%, and the electric core that the electric core cycle performance made of the coarse barrier film prepared of embodiment 1 to 3 is made unlike the barrier film of Comparative Examples 1 to 3 is poor.
In sum,, be difficult for producing slide relative, thereby guaranteed the consistency and the coiling appearance of coiling size because its bigger coefficient of friction makes that the frictional force between volume pin and the barrier film increases through the barrier film of roughening treatment; And use said barrier film as anodal and negative pole " electronics dividing plate "---its two sides links to each other with the both positive and negative polarity pole piece respectively; Because of its surperficial fluffy roughening degree improves, make that itself and both positive and negative polarity pole piece applying degree are better, the stiction raising; So both positive and negative polarity pole piece and barrier film can not produce relative slip dislocation; Thereby guaranteed that its battery of producing is not yielding, greatly reduced the deformation rate of electric core, simultaneously because both positive and negative polarity pole piece and barrier film can not produce relative slip dislocation; Thereby promoted the hardness of electric core, avoided the safety problem that contact causes between the both positive and negative polarity.In addition,, increased its absorbability and hold facility, be beneficial to the cycle performance that improves lithium ion battery electrolyte because its surface is fluffy coarse.
Need to prove that according to the announcement and the elaboration of above-mentioned specification, those skilled in the art in the invention can also change and revise above-mentioned execution mode.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should be in the protection range of claim of the present invention to equivalent modifications more of the present invention and change.In addition, although used some specific terms in this specification, these terms are explanation for ease just, the present invention is not constituted any restriction.
Claims (10)
1. a lithium ion battery is used barrier film, it is characterized in that: the one side at least of said barrier film is the rough surface through roughening treatment, and the roughness of said rough surface is 0.5～5 μ m.
2. lithium ion battery according to claim 1 is used barrier film, it is characterized in that: the roughness of said rough surface is 1～3 μ m.
3. lithium ion battery according to claim 1 is used barrier film, it is characterized in that: said roughening treatment is to carry out friction treatment with the frosted mechanism that has predetermined lines at least one surface of said barrier film.
4. lithium ion battery according to claim 3 is used barrier film, it is characterized in that: said predetermined lines is the fine and closely woven spherical crown shape lines through polishing, and the diameter of said spherical crown is less than 0.5mm.
5. lithium ion battery according to claim 1 is used barrier film, it is characterized in that: said roughening treatment is barrier film to be immersed in carry out chemical treatment in the inductor solution.
6. lithium ion battery according to claim 5 is used barrier film, it is characterized in that: said inductor solution is for being dissolved in multivalence alcohol interfacial agent inductor the solution that ethyl acetate and acetone obtain.
7. lithium ion battery according to claim 6 is used barrier film, it is characterized in that: the mass fraction of said multivalence alcohol interfacial agent inductor is 1.0～5%, and the mass ratio of ethyl acetate and acetone is 0.4: 1～5: 1.
8. lithium ion battery according to claim 1 is used barrier film, it is characterized in that: the basis material of said barrier film be polypropylene (PP), polyethylene (PE), polypropylene (PP) with composite diaphragm, polyimides and the non-woven fabric of polyethylene (PE) in a kind of.
9. lithium ion battery according to claim 1 is used barrier film, it is characterized in that: the thickness of said barrier film is 10～30 μ m, and hot strength is 20～100kPa, and porosity is 30～50%.
10. a lithium ion battery comprises anode pole piece, cathode pole piece, is interval in the barrier film between anode pole piece and the cathode pole piece, and electrolyte, it is characterized in that: said barrier film is that each described lithium ion battery of claim 1 to 9 is used barrier film.
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| CN201210056118.7A CN102610775B (en) | 2012-03-06 | 2012-03-06 | Lithium ion battery and diaphragm thereof |
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| CN104466262A (en) * | 2014-11-20 | 2015-03-25 | 合肥国轩高科动力能源股份公司 | Coiling needle of square lithium battery |
| CN104821415A (en) * | 2014-02-05 | 2015-08-05 | 三星Sdi株式会社 | Winding device used for secondary cell |
| CN104854751A (en) * | 2012-12-28 | 2015-08-19 | 日产自动车株式会社 | Electric device, and apparatus and method for bonding separator of electric device |
| CN105273649A (en) * | 2014-06-18 | 2016-01-27 | 味之素株式会社 | Protective film-laminated adhesive sheet |
| CN106030887A (en) * | 2014-03-12 | 2016-10-12 | 松下知识产权经营株式会社 | Thin battery and battery-mounted device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104854751A (en) * | 2012-12-28 | 2015-08-19 | 日产自动车株式会社 | Electric device, and apparatus and method for bonding separator of electric device |
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| CN104466262A (en) * | 2014-11-20 | 2015-03-25 | 合肥国轩高科动力能源股份公司 | Coiling needle of square lithium battery |
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| CN102610775B (en) | 2014-06-18 |
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