CN105406009A - Gel black core lithium ion battery and manufacturing method thereof - Google Patents
Gel black core lithium ion battery and manufacturing method thereof Download PDFInfo
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- CN105406009A CN105406009A CN201510979653.3A CN201510979653A CN105406009A CN 105406009 A CN105406009 A CN 105406009A CN 201510979653 A CN201510979653 A CN 201510979653A CN 105406009 A CN105406009 A CN 105406009A
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- lithium ion
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- ion battery
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 60
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 69
- 239000002131 composite material Substances 0.000 claims abstract description 52
- 239000003792 electrolyte Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000004804 winding Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000002041 carbon nanotube Substances 0.000 claims description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 14
- -1 polypropylene Polymers 0.000 claims description 12
- 239000011265 semifinished product Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 239000005518 polymer electrolyte Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 5
- 239000002985 plastic film Substances 0.000 claims description 5
- 229920006255 plastic film Polymers 0.000 claims description 5
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 5
- 239000011118 polyvinyl acetate Substances 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 5
- 230000037427 ion transport Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract 1
- 230000004888 barrier function Effects 0.000 description 29
- 239000000243 solution Substances 0.000 description 22
- 239000007788 liquid Substances 0.000 description 17
- 239000012528 membrane Substances 0.000 description 14
- 238000002347 injection Methods 0.000 description 13
- 239000007924 injection Substances 0.000 description 13
- 229920003023 plastic Polymers 0.000 description 12
- 239000004033 plastic Substances 0.000 description 12
- 238000007789 sealing Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 238000007731 hot pressing Methods 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 238000007711 solidification Methods 0.000 description 8
- 230000008023 solidification Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 238000004513 sizing Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000012218 nanoagent Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a manufacturing method of a gel black core lithium ion battery. The method comprises the following steps: firstly, preparing materials to manufacture a positive plate, a negative plate and a composite diaphragm; secondly, winding and packaging the positive plate, the negative plate and the composite diaphragm to obtain a semi-finished battery cell; and lastly, filling an electrolyte into the semi-finished battery cell, and performing curing to obtain the gel black core lithium ion battery. The composite diaphragm is prepared by the following specific steps: preparing a polymer solution; immersing the diaphragm in the polymer solution; taking the diaphragm immersed with the polymer solution out, and immersing the diaphragm in deionized water; and lastly, taking the diaphragm out of the deionized water, and drying the diaphragm to obtain the composite diaphragm with high-molecular polymer layers being formed on both sides. The high-molecular polymer layers with high porosities are formed on the composite diaphragm, and connected with micro-pores of the diaphragm in a zigzag way, so that the ion transport capacity of the composite diaphragm is increased, and the gel black core lithium ion battery has a relatively wide use temperature range and a longer cycle life.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to black core lithium ion battery of a kind of gel and preparation method thereof.
Background technology
Lithium ion battery is generally divided into liquid lithium ionic cell (LIB) and solid lithium ion battery (also known as polymer Li-ion battery, PLIB), due to the liquid state organics containing flowing in liquid lithium ionic cell, thus there is the such as potential safety hazard such as internal short-circuit of battery, electrolyte leakage; Solid lithium ion battery polymer instead of liquid electrolyte, can avoid electrolytical leakage, but the ionic conductivity of polymer dielectric is lower than the electrolytical conductivity of liquid phase; And gel polymer lithium ion battery can address these problems well.Adopt the operation principle of polymer Li-ion battery and the identical of liquid lithium ionic cell of gel polymer electrolyte, electrolyte unlike polymer Li-ion battery is adsorbed on polymer substrate by liquid organic electrolyte, be easy to make battery that is ultrathin and arbitrary shape, and more flexible in the design of battery appearance, the capacity density of battery can be improved, increase the useful life of battery, expand range of application.
But the requirement of gel polymer lithium ion battery to barrier film is higher, barrier film requires to have good absorbent and higher porosity, ensures the migration of ion, reduces the resistance of Ion transfer; And the barrier film mechanical strength adopting existing method to make is not high, temperature coefficient is large, and at room temperature barrier film still can play the effect of electronic isolation, is separated by the both positive and negative polarity of battery core; When temperature raises or battery is subject to certain external pressure effect, the mechanical degradation of barrier film, so that former septate shape and thickness cannot be kept, the both positive and negative polarity at some position in battery core may be caused to form short circuit, cause safety issue.In addition, the micropore of such barrier film is mutually through, inevitably brings molecule into, easily cause micro-short circuit in battery assembling process, affects capacity hold facility and the useful life of lithium ion battery, also affects porosity and the air penetrability of barrier film.
In addition, gel polymer lithium ion battery needs to use organic compound inflammable in a large number to extract plasticizer in process of production, adds difficulty and the cost of manufacture of large-scale production, and extends the production cycle.Therefore, prior art needs to be improved.
Summary of the invention
For above-mentioned the deficiencies in the prior art, an object of the present invention there are provided the preparation method of the black core lithium ion battery of a kind of gel, and this preparation method's technique is simple, production cost is low, and with short production cycle;
Two of object of the present invention is to provide this kind of black core lithium ion battery of gel.
To achieve these goals, technical scheme of the present invention is as follows:
The preparation method of the black core lithium ion battery of a kind of gel, comprise the steps: first to prepare material, prepare positive plate, negative plate, composite diaphragm, then make battery core semi-finished product by after described positive plate, described negative plate and described composite diaphragm winding, encapsulation, electrolyte is poured in described battery core semi-finished product subsequently and be cured and get final product; Prepare described composite diaphragm specifically to comprise the steps:
(1) polymer solution is prepared: be dissolved in by high molecular polymer in solvent;
(2) diaphragm paper is soaked in polymer solution;
(3) be soaked in again in deionized water after subsequently the described diaphragm paper having soaked polymer solution being taken out;
(4) finally taken out from described deionized water by described diaphragm paper and dry and obtain the described composite diaphragm that two sides is formed with high polymer layer, described composite diaphragm is black or lead.
Compared to prior art, the present invention is when the black core lithium ion battery of making gel, particularly when making composite diaphragm, owing to successively diaphragm paper being soaked in polymer solution and deionized water, its manufacture method is unique, adopt polymer solution dipping barrier film, the molecule (being generally high molecular polymerization composition granule) in micropore on diaphragm paper all can be flooded out; And then adopt deionized water to soak diaphragm paper, the solvent that can dissolve each other with water in macromolecule polymer solution and high molecular polymer can be separated, chop the connection between high molecular polymer and solvent off, the high polymer layer of the densification that diaphragm paper arranges is made to form all multiple holes, form the high polymer layer of high porosity, be connected with the micropore complications of diaphragm paper itself, increase the ion transport capability of composite diaphragm, the final colloidal black core lithium ion battery made is made to have wider serviceability temperature scope, longer cycle life.In addition, above-mentioned manufacture method technological process is simple, and running cost is low, and process is easy to control, and cost rate advantages of higher.
Preferably, be also added with conductive nano pipe in described polymer solution, wherein said conductive nano pipe can be carbon nano-tube.
Preferably, described step (2) also comprises drying and processing, is specially and is soaked in by diaphragm paper in polymer solution after process, take out at 60 ~ 90 DEG C of baking 3 ~ 10s; Particularly, described barrier film dipping soak time is in a polymer solution 30 ~ 120 seconds by described step (2).
Preferably, described solidification is to having poured into electrolyte and the battery core heating of sealing, then naturally cool, described heating-up temperature is 80 ~ 120 DEG C, and heating time is 100 ~ 300 seconds, relative to prior art, the heating-up temperature of solidifying in the application is low, heating time is short, can avoid the side effect that long-time at elevated temperature causes to battery, improves the chemical property of the black core lithium ion battery of gel.
Particularly, described high molecular polymer be that polymethyl methacrylate, polypropylene are fine, one or more in Kynoar, Kynoar-hexafluoropropylene copolymer, poly(ethylene oxide), polyvinyl acetate.
Particularly, described solvent is one or more in propene carbonate, cyclohexanone, acetone, butanone, 1-METHYLPYRROLIDONE, DMF, DMA and dibutyl phthalate.
Particularly, the mass fraction of high molecular polymer described in described polymer solution is 0.5% ~ 9.5%.
Preferably, the thickness of described high polymer layer is 1 ~ 8 μm, and the porosity of high polymer layer is 70% ~ 85%; Relative to prior art, this high polymer layer is thinner, and porosity is larger, shortens the distance of lithium ion motion, reduces the interface internal resistance in lithium ion battery, thus improves the chemical property of lithium ion battery.
Preferably, in described step (3), the dip time that be impregnated in by described barrier film in deionized water is 60 ~ 120 seconds.
Preferably, in described step (4), the bake out temperature of described oven dry is 60 ~ 85 DEG C, adopt low temperature drying, barrier film clot can be prevented, during high temperature drying, water loss on barrier film is too fast, the structure of high polymer layer is for remaining stable, and its agglomerating force increases, and is easy to cause barrier film curling.
Preferably, described barrier film is polyolefine isolating film, is made up of polyethylene and/or polypropylene; The described barrier film number of plies is n >=1 (n is integer).
The black core lithium ion battery of a kind of gel adopting preparation method as above to make, it comprises the naked battery core of positive plate, negative plate and composite diaphragm winding and encapsulates envelope plastic film and the electrolyte of described naked battery core, wherein said electrolyte is gel polymer electrolytes, described gel polymer electrolyte is poured in described envelope plastic film, and can be cured with described naked battery core, this gel polymer electrolytes is one or more mixtures in ethylene carbonate, diethyl carbonate and dimethyl carbonate, wherein not containing plasticizer.
Preferably, conductive agent in described positive plate and described negative plate is conductive nano agent, general employing carbon nano-tube, mainly conductive nano agent is as less in particle diameters such as carbon blacks than traditional conductive agent, the surface of positive active material or negative active core-shell material can better be coated on, greatly can improve the conductive capability between molecule and molecule, promote lithium ion battery charge-discharge performance, meet the requirement of at present lithium ion battery being filled soon.
The black core lithium ion battery of gel of the present invention, the electrolyte no longer containing free state in its battery core, thus avoids the harm of electrolyte leakage, corrosion; Simultaneously owing to there occurs curing reaction between positive plate, negative plate and composite diaphragm and gel polymer electrolytes, the positive plate of battery core, between composite diaphragm and negative plate, tight bond is together, battery core is defined entirety that one has certain mechanical strength, adds the mechanical strength of lithium ion battery; And the electrolyte in the present invention and the high polymer layer on composite diaphragm can be compatible, it can promote the transmission of lithium ion in composite diaphragm, makes lithium ion battery have the superperformances such as high-energy-density, long circulation life and low internal drop in wider temperature range; And in the present invention, decrease the use of plasticizer, reduce production difficulty, improve production security; In addition, because composite diaphragm except playing the effect of isolation both positive and negative polarity as common batteries barrier film, it also has higher porosity, thus himself also has the characteristic promoting ion transfer, and common diaphragm and electrolyte almost inconsistent, ion transmits and has substantially come by diffusion in barrier film, and the lithium ion battery that therefore the present invention makes has high-energy-density, the superperformance such as long circulation life and low internal drop in wider temperature range; In addition, adopt the black core lithium ion battery of gel that technical solution of the present invention is produced, preparation technology is simple, running cost is low, and process is easy to control, rate of finished products is high, fail safe advantages of higher.
Accompanying drawing explanation
Fig. 1 is the cycle performance comparison diagram of the embodiment of the present invention 1 and comparative example 1;
Fig. 2 is the charging and discharging curve comparison diagram of the embodiment of the present invention 1 and comparative example 1;
Fig. 3 is the cycle performance figure of the embodiment of the present invention 2;
Fig. 4 is the charging and discharging curve figure of the embodiment of the present invention 2;
Fig. 5 is the cycle performance figure of the embodiment of the present invention 3;
Fig. 6 is the charging and discharging curve figure of the embodiment of the present invention 3;
Fig. 7 is the effect schematic diagram after the black core lithium ion battery of gel of the present invention blocks.
Embodiment
For further setting forth the technological means and effect thereof that the present invention takes, be described in detail below in conjunction with the preferred embodiments of the present invention.
Embodiment 1
This embodiment makes the black core lithium ion battery of gel on the basis of manufacture craft of continuing to use conventional aluminum plastic film flexible-packed battery, the parts such as this battery positive plate, negative plate, composite diaphragm, electrolyte and plastic-aluminum packaging film, when it makes, first to prepare positive plate, negative plate, composite diaphragm; Specific as follows.
(1) making of positive plate
Prepare anode sizing agent: be dissolved in 1-METHYLPYRROLIDONE (NMP) by the Kynoar (PVDF) of 1 ~ 5 weight portion, then the carbon nano-tube of 4 ~ 12 weight portions is added, it is made fully to mix, finally add the positive active material of 80 ~ 100 weight portions, this positive active material is chosen as cobalt acid lithium, LiMn2O4, LiFePO 4, one or more in high-nickel material and trielement composite material, the present embodiment adopts cobalt acid lithium, and cobalt acid lithium, carbon nano-tube, mass ratio between Kynoar three is 93:4:3, anode sizing agent is made after mixing and stirring,
Coating positive plate: the upper and lower surface ready anode sizing agent being coated on 16 μm of aluminium foils, and toast at 130 DEG C, except desolventizing NMP, obtain described positive plate;
(2) making of negative plate
Prepare cathode size: be dissolved in by the Kynoar of 1 ~ 8 weight portion in 1-METHYLPYRROLIDONE (NMP), then the carbon nano-tube of 3 ~ 8 weight portions is added, it is made fully to mix, finally add the graphite of 85 ~ 95 weight portions, wherein the mass ratio of graphite, carbon nano-tube and Kynoar three is 92:3:5, makes cathode size after mixing and stirring;
Coating negative plate: the upper and lower surface ready cathode size being coated on 12 μm of Copper Foils, and baking, except desolventizing NMP, obtains described negative plate at 130 DEG C;
(3) making of composite diaphragm
Prepare polymer solution: be dissolved in 1-METHYLPYRROLIDONE by high molecular polymer Kynoar-hexafluoropropylene copolymer and appropriate conductive nanotube (carbon nano-tube), wherein in this polymer solution, the mass fraction of Kynoar-hexafluoropropylene copolymer is 0.5% ~ 9.5%, in the present embodiment preferably 5%, obtain polymer solution;
Coating diaphragm paper: the individual layer polyolefin PP/PE diaphragm paper of 20 μm to be directly immersed in above-mentioned polymer solution after 60 seconds, take out and toast 10 seconds at 90 DEG C, and then this diaphragm paper to be dipped in deionized water 60 seconds, take out subsequently, toast 6 minutes at 85 DEG C, dried, obtained the described composite diaphragm that two sides is formed with high polymer layer; The thickness of wherein said high polymer layer is 1 ~ 8 μm, and the porosity of high polymer layer is 70% ~ 85%;
(4) making of electrolyte
The mixture of the ethylene carbonate of lithium hexafluoro phosphate and (volume ratio is 1:1:1), diethyl carbonate, dimethyl carbonate is mixed and made into the lithium hexafluorophosphate electrolyte solution of 1mol/L;
(5) battery core makes
The wherein above making about positive plate, negative plate, composite diaphragm, electrolyte order in no particular order, the positive plate completed above-mentioned, negative plate, composite diaphragm winding makes naked battery core, specification is 3.1mm × 32mm × 48mm, after toasting a period of time under vacuo, toast 10 hours under being specially 90 DEG C of conditions, load in the aluminum-plastic composite membrane packaging of rushing casing forming; By aluminum-plastic composite membrane hot-pressing, edge-sealing, and retain liquid injection port formation battery core semi-finished product; Finally, the electrolyte of 2-5g is poured in battery core semi-finished product by liquid injection port, by liquid injection port hot-pressing, edge-sealing, after leaving standstill 5-10h, carry out curing reaction; In the present embodiment, the injection rate of concrete electrolyte is 2.3g, heating-up temperature is 87 DEG C, and heating time is 200 seconds, and the positive plate in aluminum-plastic composite membrane, negative plate, barrier film and electrolyte react, after solidification, battery core is cooled naturally, the positive plate of battery core, negative plate and barrier film are bonded together; Wherein, curing temperature is higher, larger to the side effect of battery, and the curing temperature of existing gel lithium ion battery is generally higher, and adopts 87 DEG C in the present embodiment, can improve the chemical property of the black core battery of gel in the present invention further; Finally test the battery made, its capacity is 550mAh, and as shown in Figure 1, charge-discharge performance as shown in Figure 2 for capability retention.
Embodiment 2
The manufacture method of the gel black core lithium ion battery of the present embodiment is substantially identical with embodiment 1, and difference is the setting of Material selec-tion and design parameter, and existing concise and to the point its concrete steps of description are as follows:
(1) making of positive plate
Prepare anode sizing agent: be dissolved in 1-METHYLPYRROLIDONE (NMP) by the Kynoar (PVDF) of 4 weight portions, then the carbon nano-tube of 4 weight portions is added, it is made fully to mix, finally add the LiMn2O4 of 92 weight portions, mass ratio wherein between LiMn2O4, carbon nano-tube, Kynoar three is 92:4:4, makes anode sizing agent after mixing and stirring;
Coating positive plate: the upper and lower surface ready anode sizing agent being coated on 12 μm of aluminium foils, and toast at 120 DEG C, except desolventizing NMP, obtain described positive plate;
(2) making of negative plate
Prepare cathode size: be dissolved in by the Kynoar of 5 weight portions in 1-METHYLPYRROLIDONE (NMP), then the carbon nano-tube of 3 weight portions is added, it is made fully to mix, finally add the native graphite of 92 weight portions, wherein the mass ratio of graphite, carbon nano-tube and Kynoar three is 92:3:5, makes cathode size after mixing and stirring;
Coating negative plate: the upper and lower surface ready cathode size being coated on 12 μm of Copper Foils, and baking, except desolventizing NMP, obtains described negative plate at 130 DEG C;
(3) making of composite diaphragm
Prepare polymer solution: be that the Kynoar-hexafluoropropylene copolymer of 1:1 and polyvinyl acetate and conductive nanotube are dissolved in the acetone and 1-METHYLPYRROLIDONE that mass ratio is 3:1 by mass ratio, wherein in this polymer solution, the mass fraction of Kynoar-hexafluoropropylene copolymer and polyvinyl acetate is 9.5%, obtains polymer solution;
Coating diaphragm paper: two-layer 20 μm of thick polyolefin PP/PE diaphragm papers to be directly immersed in above-mentioned polymer solution 40 seconds, toast 6 seconds at 80 DEG C after taking-up, then pore-creating in deionized water is dipped into, take out oven dry subsequently, obtain the described composite diaphragm that two sides is formed with high polymer layer; The thickness of wherein said high polymer layer is 1 ~ 8 μm, and the porosity of high polymer layer is 70% ~ 85%;
(4) making of electrolyte
The mixture of the ethylene carbonate of lithium hexafluoro phosphate and (volume ratio is 1:1:1), diethyl carbonate, dimethyl carbonate is mixed and made into the lithium hexafluorophosphate electrolyte solution of 1mol/L;
(5) battery core makes
The wherein above making about positive plate, negative plate, composite diaphragm, electrolyte order in no particular order, the positive plate completed above-mentioned, negative plate, membrane winding make naked battery core, specification is 3.1mm × 32mm × 48mm, toast 10 hours under 90 DEG C of conditions under vacuo, load in the aluminum-plastic composite membrane packaging of rushing casing forming; By aluminum-plastic composite membrane hot-pressing, edge-sealing, and retain liquid injection port formation battery core semi-finished product; Finally, the electrolyte of 2.8gd is poured in battery core semi-finished product by liquid injection port, by liquid injection port hot-pressing, edge-sealing, after leaving standstill 7h, carry out curing reaction; During solidification, concrete heating-up temperature is 80 DEG C, and heating time is 150 seconds, and the positive plate in aluminum-plastic composite membrane, negative plate, barrier film and electrolyte react, and battery core naturally cooled, make the positive plate of battery core, negative plate and barrier film be bonded together and get final product after solidification.
Carry out battery testing subsequently, its capacity is 550mAh, and as shown in Figure 3, the pure manganese material cycle performance of this gel black core lithium ion battery is good, and 1C circulates 500 weeks capability retentions more than 87% for capability retention; Charge-discharge performance as shown in Figure 4.
Embodiment 3
The manufacture method of the gel black core lithium ion battery of the present embodiment is substantially identical with embodiment 1, and difference is the setting of Material selec-tion and design parameter, and existing concise and to the point its concrete steps of description are as follows:
(1) making of positive plate, negative plate
In the present embodiment, positive active material is the mixture of trielement composite material and LiFePO 4, negative active core-shell material is the mixture of graphite and native graphite, wherein, in positive plate, the mass ratio of positive active material, carbon nano-tube and binding agent Kynoar is 90:3:7; In negative plate, the mass ratio of negative electrode active material, carbon nano-tube and binding agent Kynoar is 90:3:7;
(2) making of composite diaphragm and electrolyte
The solute of polymer solution to be mass ratio the be polyvinyl acetate of 1:2 and the mixture of poly(ethylene oxide) and appropriate conductive nanotube, solvent is N, dinethylformamide, mass fraction is 4.5%, and barrier film is three layers 10 μm thick polyolefin PP barrier films, and diaphragm paper soaks 1 minute in a polymer solution, 3s is toasted at 60 DEG C, soak 2 minutes in deionized water again, finally toast 5 minutes at 80 DEG C, obtain the described composite diaphragm that two sides is formed with high polymer layer; The thickness of wherein said high polymer layer is 1 ~ 8 μm, and the porosity of high polymer layer is 70% ~ 85%; The production method of electrolyte is identical with embodiment 1;
(5) battery core makes
The positive plate completed above-mentioned, negative plate, composite diaphragm winding makes naked battery core, and making specification is 3.1mm × 32mm × 48mm, toasts 10 hours under vacuo under 90 DEG C of conditions, loads in the aluminum-plastic composite membrane packaging of rushing casing forming; By aluminum-plastic composite membrane hot-pressing, edge-sealing, and retain liquid injection port formation battery core semi-finished product; Finally, the electrolyte of 3.0g is poured in battery core semi-finished product by liquid injection port, by liquid injection port hot-pressing, edge-sealing, after leaving standstill 7h, carry out curing reaction; During solidification, concrete heating-up temperature is 80 DEG C, and heating time is 150 seconds, and the positive plate in aluminum-plastic composite membrane, negative plate, barrier film and electrolyte react, and battery core naturally cooled, make the positive plate of battery core, negative plate and barrier film be bonded together and get final product after solidification.
Carry out battery testing subsequently, its capacity is 550mAh, and as shown in Figure 5, the pure ternary material cycle performance of this gel black core lithium ion battery is good for capability retention, and 1C circulates 500 weeks capacity maintenance matter rates more than 89%.Charge-discharge performance as shown in Figure 6.
Comparative example 1
The manufacture method of this comparative example lithium ion battery and the difference of embodiment 1 are Material selec-tion and manufacture method, and existing concise and to the point its concrete steps of description are as follows:
(1) making of positive plate, negative plate
Conductive agent in positive plate and negative plate is conductive black;
(2) making of barrier film and electrolyte
Diaphragm paper is immersed in after in macromolecule polymer solution and directly dries, and obtain required barrier film, and dry without the need to continuing to be soaked in water again, the production method of electrolyte is identical with embodiment 1;
(5) battery core makes
The positive plate completed above-mentioned, negative plate, membrane winding make naked battery core, and making specification is 3.1mm × 32mm × 48mm, toast 10 hours under vacuo under 90 DEG C of conditions, load in the aluminum-plastic composite membrane packaging of rushing casing forming; By aluminum-plastic composite membrane hot-pressing, edge-sealing, and retain liquid injection port formation battery core semi-finished product; Finally, the electrolyte of 3.0g is poured in battery core semi-finished product by liquid injection port, by liquid injection port hot-pressing, edge-sealing, after leaving standstill 7h, carry out curing reaction; During solidification, concrete heating-up temperature is 80 DEG C, and heating time is 150 seconds, and the positive plate in aluminum-plastic composite membrane, negative plate, barrier film and electrolyte react, and battery core naturally cooled, make the positive plate of battery core, negative plate and barrier film be bonded together and get final product after solidification.
Carry out battery testing subsequently, its capacity is 500mAh, and as shown in Figure 1, charge-discharge performance as shown in Figure 2 for capability retention.
Known from Fig. 1 and Fig. 2, compared to comparative example 1, gel black core lithium ion battery pure cobalt material circulation smooth performance prepared by embodiment 1,1C circulates 500 weeks capacity maintenance matter rates more than 95%, and the battery capacity conservation rate prepared in comparative example 1 is only about 90%; And the gel prepared in the present embodiment black core lithium ion battery efficiency for charge-discharge is apparently higher than the lithium ion battery in comparative example 1.
Electrolyte no longer containing free state in black its battery core of core lithium ion battery of gel prepared by the present invention, thus avoids the harm of electrolyte leakage, corrosion; Simultaneously owing to there occurs curing reaction between positive plate, negative plate and composite diaphragm and gel polymer electrolytes, the positive plate of battery core, between composite diaphragm and negative plate, tight bond is together, battery core is defined entirety that one has certain mechanical strength, add the mechanical strength of lithium ion battery, make it have the security performance of superelevation, directly cut in two under full power state, as shown in Figure 7, this gel black core lithium ion battery also there will not be bulging, leakage, the problem such as on fire.
Above-described embodiment, just preferred embodiment of the present invention, is not used for limiting the scope of the present invention, therefore all equivalences done with the structure described in the claims in the present invention, feature and principle change or modify, and all should be included within the claims in the present invention scope.
Claims (10)
1. the preparation method of the black core lithium ion battery of gel, comprise the steps: first to prepare material, prepare positive plate, negative plate, composite diaphragm, then make battery core semi-finished product by after described positive plate, described negative plate and described composite diaphragm winding, encapsulation, electrolyte is poured in described battery core semi-finished product subsequently and be cured and get final product; It is characterized in that, prepare described composite diaphragm and specifically comprise the steps:
(1) high molecular polymer and conductive nano pipe are dissolved in solvent prepare polymer solution;
(2) diaphragm paper is soaked in polymer solution;
(3) subsequently the described diaphragm paper having soaked polymer solution is soaked in deionized water again;
(4) finally described diaphragm paper is taken out from described deionized water and dry and obtain the described composite diaphragm that two sides is formed with high polymer layer.
2. the preparation method of the black core lithium ion battery of gel according to claim 1, is characterized in that: described high molecular polymer is that polymethyl methacrylate, polypropylene are fine, one or more in Kynoar, Kynoar-hexafluoropropylene copolymer, poly(ethylene oxide), polyvinyl acetate; Described solvent is one or more in propene carbonate, cyclohexanone, acetone, butanone, 1-METHYLPYRROLIDONE, DMF, DMA and dibutyl phthalate.
3. the preparation method of the black core lithium ion battery of gel according to claim 1, is characterized in that: described conductive nano pipe is carbon nano-tube.
4. the preparation method of the black core lithium ion battery of gel according to claim 1, is characterized in that: the mass fraction of high molecular polymer described in described polymer solution is 0.5% ~ 9.5%.
5. the preparation method of the black core lithium ion battery of gel according to claim 1, it is characterized in that: the thickness of described high polymer layer is 1 ~ 8 μm, the porosity of described high polymer layer is 50% ~ 85%.
6. the preparation method of the black core lithium ion battery of gel according to claim 1, is characterized in that: described step (2), is 30 ~ 120 seconds by described diaphragm paper dipping soak time in a polymer solution.
7. the preparation method of the black core lithium ion battery of gel according to claim 1, it is characterized in that: in described step (3), the dip time that be impregnated in by described diaphragm paper in deionized water is 60 ~ 120 seconds.
8. the preparation method of the black core lithium ion battery of gel according to claim 1, it is characterized in that: described step 2) also comprise drying and processing, described drying and processing, for being soaked in by diaphragm paper in polymer solution after process, takes out at 60 ~ 90 DEG C of baking 3 ~ 10s.
9. the preparation method of the black core lithium ion battery of gel according to claim 1, it is characterized in that: in described step (4), the bake out temperature of described oven dry is 60 ~ 85 DEG C.
10. the black core lithium ion battery of gel adopting the preparation method as described in any one of claim 1 ~ 9 to make, it comprises the naked battery core of positive plate, negative plate and composite diaphragm winding and encapsulates envelope plastic film and the electrolyte of described naked battery core, it is characterized in that: described electrolyte is gel polymer electrolytes, described gel polymer electrolyte is poured in described envelope plastic film, and can be cured with described naked battery core.
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| CN107994250A (en) * | 2016-10-26 | 2018-05-04 | 丰田自动车株式会社 | Rechargeable nonaqueous electrolytic battery and its manufacture method |
| US20210066692A1 (en) * | 2018-09-21 | 2021-03-04 | Lg Chem, Ltd. | Separator and electrochemical device comprising same |
| CN116272415A (en) * | 2023-03-15 | 2023-06-23 | 杭州怡莱珂科技有限公司 | A kind of in-situ microporous polymer membrane, preparation method and application thereof |
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| CN101393975A (en) * | 2008-10-10 | 2009-03-25 | 深圳市邦凯电子有限公司 | Colloidal state polymer battery and composite diaphragm manufacturing method therefor |
| CN103872282A (en) * | 2014-03-31 | 2014-06-18 | 河南理工大学 | Polymer lithium ion battery diaphragm and preparation method thereof |
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| CN101393975A (en) * | 2008-10-10 | 2009-03-25 | 深圳市邦凯电子有限公司 | Colloidal state polymer battery and composite diaphragm manufacturing method therefor |
| CN103872282A (en) * | 2014-03-31 | 2014-06-18 | 河南理工大学 | Polymer lithium ion battery diaphragm and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107994250A (en) * | 2016-10-26 | 2018-05-04 | 丰田自动车株式会社 | Rechargeable nonaqueous electrolytic battery and its manufacture method |
| US20210066692A1 (en) * | 2018-09-21 | 2021-03-04 | Lg Chem, Ltd. | Separator and electrochemical device comprising same |
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Application publication date: 20160316 |